LNG, LPG and GTL Plants Industrial Gases and Cryogenic Applications

LNG, LPG and GTL plants Industrial gases and cryogenic applications

Moss Maritime LNG Carrier

H.D. Simon V12

SAMSON AG MESS- UND REGELTECHNIK Weismüllerstraße 3 60314 Frankfurt am Main Germany

2007-10-29/V 1.7

100 years – a flourishing company

In its 100-year-long history, SAMSON has played an important role as an inventor, pioneer, and mediator in the development and manufacturing of instrumentation and control technology.

Brand names, trade names and trade marks mentioned in the reference application may be brand names without special identification and are thus subject to legal rules and regulations.

All nationally and internationally known brand names are herewith acknowledged as such.

SAMSON AG can not be held liable for any misuse, misappropriation or violations of patents or third party rights resulting from such misuse and probable consequences.

Neither SAMSON AG, nor the author and translator of this document can be held liable in any shape or form for any errors or omissions that may have occurred during the diligent preparation of texts, charts, illustrations, etc.

SAMSON AG can not be held liable for the illegal distribution, copying, misuse or other actions that violate the rights of the copyright owner(s).

SAMSON AG • MESS- UND REGELTECHNIK • Weismüllerstraße 3 • 60314 Frankfurt am Main • Germany Phone: +49 69 4009-0 • Fax: +49 69 4009-1507 • E-mail: [email protected] • Internet: http://www.samson.de

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Table of contents

Page 1. SAMSON-GROUP 10

2. The gas trade grows increasingly significantly 11 2.1 Projected annual growth in demand 2000 to 2020 12 2.2 Global Gas production by region 12 2.3 Proved Gas Reserves – Middle East – Russia – Asia Pacific 13

3. LNG Export and Import 14 3.1 LNG-Liquefaction-Plant, Export-Terminal 15 3.2 LNG-Regasification-Import-Terminal 15

4. Recovering oil or gas at great depths 16 Floating storage and off-loading (FSO) or Floating production storage and offloading 4.1 16 (FPSO) 4.2 Floating LNG Production and Regasification 17 4.2.1. The Floating and Regasification Unit (FRU) Concept 17 4.3 The Floating Storage and Regasification Unit (FSRU) Concept 18

5. Liquefied Natural Gas or Liquefied Petroleum Gas - a crucial difference? 19 5.1 Liquefied petroleum gas (LPG) 19 5.2 Liquefied natural gas (LNG) 19

6. What is LNG? 19 6.1 Natural Gas Composition 19 6.2 Where does LNG come from? 20 6.3 Is LNG flammable? 20 6.4 Is LNG explosive? 20 6.5 LNG production block scheme 20 6.6 The basic single flow LNG process comprises 21 6.7 The advanced single flow LNG process comprises 21 6.8 MFC® (Mixed Fluid Cascade) process 22

7. What countries import LNG? 23 7.1 Where is LNG import terminals located in the United States? 23

8. Which countries export LNG? 23 SAMSON Offshore reference: New modules installed on the Sakhalin II Molikpaq Tie- 8.1 24 In offshore project 8.2 This list of natural gas fields includes major fields of the past and present. 25 8.3 The greatest gas fields of the world sorted on size. 26

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Page 8.4 2004 LNG Exporters 26 8.5 2004 LNG IMPORTERS 27 8.6 LNG LIQUEFACTION FACILITIES - WORLDWIDE (August 2005) 27-28

9. LNG REGASIFICATION - IMPORT TERMINALS, WORLDWIDE 29-30 (August 2005)

10. How is LNG transported? 31 LNG carriers come in two forms: Moss tankers with spherical reservoirs and 10.1 31 membrane tankers. 10.2 250,000 cubic meters of LNG per carrier 32

11. Floating Storage Production and Regasification components. 33 11.1 Process Flow-scheme of Boil-off Re-liquefaction Unit 33 11.2 A single packaged reliquefaction has the following major components: 34 11.2.1. Boil Off Compressor 34 11.2.2. Nitrogen Expander/Compressor Unit 34 11.2.3. Cryogenic Plate-fin Heat Exchanger 35 11.2.4. Piping and Ancillaries. 35 11.2.5. BOG Collector System 35 11.3 Heat exchangers, a key component of natural gas plants. 36-37 11.4 The Cold Box 38 11.4.1. The benefits of this type of cold box are evident 38

11.5 For example: Linde H2/CO separation plant with a coldbox 39

11.6 For example: H2 CO plant with condensation process in Mai Liao, Taiwan 40 11.7 SAMSON Cryogenic Valve Type 3248 41 11.8 SAMSON Cold box reference: SAMSON Valve installation near to cold box 42 11.9 SAMSON reference: Air separation unit in Isfahan, Iran 43 11.10 SAMSON reference: Air separation unit for company Schott in Mainz, Germany 44 SAMSON reference: Air separation unit of company Messer Griesheim, Hanau, 11.11 45 Germany 11.12 SAMSON reference: Air separation unit of Air Products in Ghent, Belgium 46 11.13 For example: Space 47 SAMSON reference: The following companies install the Cryogenic Valve 11.14 48 Type 3248 in your plants. 11.15 SAMSON control valves 49 11.15.1. SAMSON valve Series 240 49 SAMSON Control valve Type 3241-9 DWA for PSA plants (Pressure Swing 11.15.2. 50 Adsorption) 11.15.3. Ten good reasons to choose the Type 3241 Control Valve 51-52

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Page 11.16 SAMSON valve Series 250 53 11.17 SAMSON’s gas handling 54 11.18 SAMSON’s handling with liquids 54 Copy of the AIR LIQUIDE Certificate for the Cryogenic test with the SAMSON 11.19 55 Types 3241, 3251 and 3254 11.20 SAMSON’s Bellows seal: Sealed for life 56 11.21 SAMSON Positioners completely integrated 57 11.22 SAMSON reference: A pipeline with five Natural Gas Metering Stations 58 11.23 SAMSON reference: PT PERTAMINA EP Jambi, Sengeti, Jambi, Indonesia 59

12. SAMSON Self-operated Pressure Regulators for special applications 60 SAMSON Self-operated equipment for cryogenic media application example 12.1 61 (schematic drawing)

13. How is LNG stored? 62 13.1 How is natural gas stored? 62 13.2 Tank monitoring and remote data transmission with SAMSON Media 6 63

14. How is LNG used? 64 14.1 Why use LNG? 64 14.2 Typically Natural Gas is used as: 64

15. What is a Rapid Phase Transition? 65

16. What is a "peak-shaving" facility? 65

17. What about security? 65

18. SAMSON FSO and LPG reference: Bayu-Undan gas recycle project 66 18.1 Floating storage and off-loading (FSO) 67 18.1.1. LPG Gas Handling System for a Condensate / LPG - FSO 68 18.2 BOG Reliquefaction Unit 69 18.3 Refrigeration System 70 18.4 Instrumentation and Controls 70-71 18.5 Inertgas system 72 18.6 The project data of the Bayu-Undan gas recycle project FSO are: 73 18.7 One of the largest mooring FSO systems in the world 73 The following SAMSON control valves with accessories were installed in the FSO 18.8 74-77 Bayu-Undan gas recycling project:

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Page 19. SAMSON reference: FPSO- and LNG- Project 78 19.1 North West Shelf Project Interests 79 19.2 SAMSON FPSO reference: COSSACK PIONEER Refurbishing FPSO- Project 80-82 19.3 SAMSON LNG reference: KARRATHA- Project, Western Australia 82 Extract of the control valves which were delivered by SAMSON for the FPSO 19.4 83 and LNG plant: 19.5 SAMSON FPSO reference: „AOKA MIZU“ 84-85 19.6 SAMSON FPSO reference: ”SMART 1” 86-88 19.7 SAMSON FPSO reference: “BERGE CARMEN” 89 19.8 SAMSON FPSO reference: “CUULONG MV9” 90 19.9 SAMSON FPSO reference: “STYBARROW VENTURE MV16” 91-92 19.10 SAMSON FSRU reference: “GOLAR SPIRIT” LNG to FSRU conversion project 93-94 19.11 Worldwide Distribution of FPSO’s 94 19.12 SAMSON reference: FPO-, FPSO-, FSRU-, and LNG- Projects 95 19.13 Ship Classification 96 SAMSON reference: It follows an extract of Gas Carriers, which are fitted with 97 19.14 SAMSON products 103

20. GAS processing plants 104 20.1 Partial condensation processes Liquid methane washes 104 20.2 Liquid nitrogen washes 104 20.3 Separation of hydrogen and LPG from refinery fuel gas 104 20.4 Purge gas separation 104 20.5 Rare gas processing 104 20.6 Carbon dioxide liquefaction 104 20.7 Physical and chemical washes 104 20.8 RECTISOL® wash 105

21. Gas production industries produces gas using various technologies: 106 21.1 This is air 106 21.2 Industrial gases – components for synthesis processes 106

21.3 Oxygen (O2) 107 21.3.1. Reactions with oxygen 107 21.3.2. Oxygen improving economy and reducing the investment costs 108 21.3.3. Oxidation processes using oxygen 108

21.4 Nitrogen (N2) 109 21.4.1. Multi-Industry Uses: 109 21.5 Rare or noble gases 109 21.5.1. Argon (Ar) 110

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Page 21.5.2. Xenon (Xe) 110 21.5.3. Helium (He) 110

21.6 Ozone (O3) 110

21.7 Hydrogen (H2) 111 21.7.1. Reactions with hydrogen 111 21.7.2. For example: Space & Aeronautics, ARIANE Tanks 112

21.8 Carbon Dioxide (CO2) 113 21.8.1. Reactions with carbon dioxide 113

21.9 Acetylene (C2H2) 114 SAMSON reference: BASF PolyTHF (Tetrahydrofuran [THF]) plant in Caojing 21.9.1. 115 (Shanghai) 21.9.2. SAMSON reference: Bayer isocyanates project in Caojing (Shanghai) 116 21.10 Carbon Monoxide (CO) 117 21.10.1. Processes for Manufacturing Carbon monoxide 117 21.10.2. Reactions with carbon monoxide 117

22. On-site gas supply 118 22.1 On-site supply of hydrogen 118 118 22.1.1. Steam reforming 119 ThyssenKrupp-Uhde Steam reforming – process options for the production of 120 22.1.2. Hydrogen (H2) 121 SAMSON reference: Onsite plant for the production of hydrogen in the Steam- 22.1.3. 121 Reforming procedure.

23. Air Separation Technology Overview 122 23.1 Pressure swing adsorption (PSA) 122 23.2 SAMSON reference: Linde AG ECOVAR® - C (C = cryogenic process) 123 124 23.2.1. Nitrogen Membrane plants 125 23.3 Adsorption plants 126

23.3.1. Diagram of a Nitrogen (N2) PSA plan) 126

23.4 Cryogenic Nitrogen (N2) plants 127 127 23.4.1. Diagram of a small Nitrogen (N ) plant 2 128 ® 23.4.2. SAMSON Nitrogen (N2) plant reference: The Mahler NITROSWING System 129 23.5 On-site supply with oxygen 130 130 23.5.1. Diagram of a Oxygen adsorption VPSA plant 131 23.6 SAMSON reference: Temperature swing adsorption (TSA) 132

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Page 23.6.1. Detail view of the new Onsite plant: 133 23.7 Cryogenic oxygen plants 134 23.7.1. Diagram of a cryogenic oxygen plant 134 23.7.2. SAMSON reference: Hydrogen generating plant for Spain 135

136 24. SAMSON reference: PSA plants 144

25. Gas-to-Liquid (GTL) 145 25.1 Primary chemicals on the basis of mineral oil/natural gas and carbon 145 25.2 Synthesis gas chemistry 146

Air Products is a leading supplier of oxygen to the emerging Gas-to- 26. 147 Liquid (GTL) industry. 26.1 Air Products is developing new technology 147 26.1.1. Synthesis Gas 147 26.2 Fischer-Tropsch process 148

27. ThyssenKrupp-Uhde Partial oxidation (gasification) 149

Lurgi’s MPG gasification plus RECTISOL® GAS purification – advanced 28. 150 process combination for reliable SYNGAS production 28.1 Lurgi’s history in gasification 150 SAMSON reference: Lurgi’s HP-POX Pilot Plant a Milestone to improved Syngas 28.2 151 Production 28.3 The HP-POX demonstration plant 152 SAMSON reference: The reactor, the heart of the research HP POX (High Pressure 28.4 153 Partial Oxidation) high-pressure synthesis gas plant in Freiberg, Germany.

29. Lurgi’s Gas purification technologies 154 29.1 GAS Purification for gasification based Hydrogen plant 155

29.2 MPG based H2 Plant 156

30. Forces of Change – Gas Development Technologies 157

31. Service stations for example: 158 31.1 CANADA 158 31.2 USA 158 31.3 BRAZIL 158 31.4 SWEDEN 159 31.5 GREAT BRITAIN 159

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Page 31.6 NETHERLANDS 159 31.7 AUSTRIA 160 31.8 FRANCE 160 31.9 SPAIN 160 31.10 TURKEY 161 31.11 IRAN 161 31.12 EGYPT 161 31.13 CHINA 162 31.14 THAILAND 162 31.15 SINGAPORE 162

163 32. Literature cited 165

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SAMSON-GROUP Founded in 1907, SAMSON has become a worldwide leading manufacturer of expertly engineered control valves, positioners, and accessories for all industrial processes.

Prominent manufactures of special valves belong to the successful SAMSON-Group:

VETEC

Ventiltechnik

GmbH GmbH

SAMSON production plants

WELLAND &

Tuxhorn AG

SAMSON is represented in more than 62 countries with more than 2,900 employees worldwide and more than 45 subsidiaries worldwide with more than 100 engineering and service centers worldwide.

SAMSON is one of the largest privately held control valve suppliers in the world.

SAMSON’s valve engineering expertise includes all process involved in hydrocarbon processing.

The wide range of products proven in practice can be customized in close cooperation with the customer to provide a commercially acceptable solution to meet the requirements of even the most complex applications.

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1. The gas trade grows increasingly significantly Natural gas is becoming one of the most important primary energy sources for the 21st century. Year

This is ExxonMobil forecast of world gas inter-regional trade balance for 2010, 2020 and 2030. Net exports are blue, imports red, and the units are billions of cubic feet per day (GCFD). In addition, net imports as a percentage of total consumption are shown for the importing regions.

On a worldwide basis, export volume represents an increasingly significant share of supply as it grows from approx. 8% of total demand in 2003 to approx. 22% in 2030 when exports are expected to be close to 110 GCFD. From a base of approx. 23 GCFD in 2003, ExxonMobil expect exports will more than 48 GCFD by 2010 85 GCFD by 2020 110 GCFD by 2030 is an increase from Year 2003 to 2030 of approx. 90 GCFD or 375%. LNG is projected to represent about 14% of total demand in 2020.

Europe will require the most dramatic increase. Imports are expected to grow by approx 40 GCFD increasing Europe’s import dependency from about 40% today to approx 70% in 2030. Pipeline supplies from the Russia/Caspian region and North Africa (mainly Algeria) will continue to represent the major source of imports although LNG’s share is expected to grow.

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Imports into North America and Asia Pacific are relatively small today, but each will grow to over 20 GCFD by 2030, significantly raising their importance.

Over this horizon, ExxonMobil expect natural gas to shift from a regional to a more global market, enabled by advances in LNG.

ExxonMobil expect LNG volume to grow close to 300% by 2030, 16 GCFD in 2003 to approx 65 GCFD by 2030, more doubling its share of global supplies by 2030.

1.1. Projected annual growth in demand 2000 to 2020

Natural gas is the world’s fastest growing primary energy source.

1.2. Global Gas production by region

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1.3. Proved Gas Reserves – Middle East – Russia - Asia Pacific

The global market for natural gas is much smaller than for oil because gas transport is difficult and costly, due to relatively low energy content in relation to volume. Currently, only about 16 percent of global gas production is internationally traded, with less than 4 percent of the trade accounted for by LNG. In spite of the high cost of gas transportation and the remote location of some future supply regions, increasing international trade in natural gas is expected.

Global gas reserves are abundant, but of an uneven distribution.

The North American market is self sufficient in natural gas, although gas is traded within the region. Canada is expected to remain a net exporter of gas to the United States.

Substantial natural gas reserves are located in Europe. The gas trade within the region is extensive, with Norway and the Netherlands the main sources. Europe, however, is and will increasingly become more dependent on gas imported from other regions. Its traditional foreign suppliers, the former Soviet Union (at 20 percent of demand) and Algeria at (10 percent), are expected to increase their shares of the European gas market.

Important gas exporters in the Asia-Pacific region are Indonesia, Malaysia, Brunei, and Australia, the gas being shipped as LNG to Japan, Taiwan, and South Korea.

The Middle East is another important supply centre for natural gas. Abu Dhabi and Qatar delivers significant volumes of LNG to the Asia-Pacific region and future exports could be sent to Europe and South Asia.

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Gas demand in Africa, South Asia, and China are met by domestic or regional supplies. Some gas is being traded within South America.

With the industrialized countries the major gas importers, and the major gas supplies located in the former Soviet Union and the Middle East, the expanded use of natural gas by Europe and Japan will (like world oil utilization) become increasingly dependent on the world's most unstable regions.

While Canada provides most of the natural gas imports to the United States and Mexico could become a significant gas source, the U.S. also imports LNG from Algeria. To encourage increased domestic drilling, and, thus, future domestic gas production, some have suggested that Congress consider such possible tax reform measures as re-establishing the tax credits on unconventional gas resources and/or allowing companies to expense geological and geophysical exploration costs. Of particular interest is the lifting of the moratoria on offshore gas exploration and development, because of the large gas fields, with potentially high productive capacity, that are thought to exist in some parts of these frontier areas.

However, great controversy, reflecting differing societal values, surrounds the search for and development of gas in these areas, as opponents to drilling cite potential environmental damage and/or "corporate welfare" in the form of tax reform.

2. LNG Export and Import

UPSTREAM DOWNSTREAM

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2.1. LNG-Liquefaction-Plant, Export-Terminal

Photo: CLNG 2.2. LNG-Regasification-Import-Terminal

Photo: CLNG

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3. Recovering oil or gas at great depths There are still substantial oil and gas reserves beneath the oceans. Meanwhile the fields in the established oil or gas producing regions are getting smaller and it is becoming increasingly difficult to bring the oil or the gas to the surface. The risks to humans and the environment posed by oil recovery are considerable. New techniques and technologies are needed to recover oil and gas safely in the future.

3.1. Floating storage and off-loading (FSO) or Floating production storage and offloading (FPSO) The more easily accessible undersea oil and gas fields that lie at a depth of around three hundred metres are practically exhausted and at the end of their life cycle.

Many of the fields that do still have enough oil are at depths of around two kilometres, which is too deep to use a stationary production platform.

The solution found for the recovery of this oil and gas is floating production, storage and offloading units (FPSO). On these floating refineries, where the first phase of the refining is done, the oil or the gas from the reservoirs is pumped up, separated from the accompanying water, gas and sand, and then stored. When the storage facilities of the FPSO are full, the crude oil or the gas is transferred to the land with a shuttle tanker.

A Floating Production, Storage and Offloading vessel (FPSO; also called a "unit" and a "system") is a type of floating tank system used by the offshore oil and gas industry and designed to take all of the oil or gas produced from a nearby platform (s), process it, and store it until the oil or gas can be offloaded onto waiting tankers, or sent through a pipeline.

A FSO is a similar system, but without the possibility to do any processing of the oil or gas.

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3.2. Floating LNG Production and Regasification A new business unit has been created to bring offshore solutions to the growing Gas market (LPG, GTL, Methanol...) with a particular focus on LNG.

Main advantages are:

Cost efficient alternative to onshore LNG import terminals

Can be located in many parts of the world

Possibility of leasing and relocation

Easy permitting No land acquisition Enhanced navigational safety Field proven components

3.2.1. The Floating and Regasification Unit (FRU) Concept The FRU is also a floating LNG receiving terminal, but instead of storing the received LNG in cryogenic storage tanks in the vessel, the gas is instantly vaporized at a high rate, and is subsequently stored in subterranean reservoirs (in so-called 'salt-caverns') as a high-pressure gas at ambient temperature. This concept enables very high peak send-out rates combined with large storage capacity.

The FRU has no or limited LNG storage, as the LNG received from the carrier is instantly vaporized and transferred to the salt-cavern underneath the sea bottom at similar LNG offloading rates as used on onshore terminals and at high pressure (typically up to 150 barg/2,000 psig).

From the gas cavern storage, gas can be delivered into the gas grid at high peak rates, up to e.g. 3BCF/day. The continuous send-out would be somewhat lower, i.e. 1.5 - 2 BCF/day.

The FRU is very suitable for supplying large quantities of gas into a large pipeline distribution network, as they exist in the USA or in Europe. The large gas-cavern storage volume also enables the unit to function as a peak-shaving facility.

The FRU concept is based on the conversion of a Suezmax crude oil carrier, which is modified to provide a platform for the regasification process and to enable mooring and LNG offloading from the LNG carriers. (Suezmax is a naval architecture term for the largest ships capable of fitting through the Suez Canal.)

The FRU is equipped with an external or internal turret mooring system, but also other mooring methods are feasible depending on the environmental conditions.

The LNG tankers offloading to the floating terminal will be moored in a side-by-side configuration. Berthing, loading and de-berthing will take approximately 24 hours.

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3.3. The Floating Storage and Regasification Unit (FSRU) Concept The FSRU is the floating offshore equivalent of the onshore LNG receiving terminal. As the unit is located offshore or inshore, the LNG can be supplied directly to the unit by conventional LNG carriers.

The LNG carriers do not need to enter a port, and the location of the FSRU can be optimized with respect to the gas grid interconnection point, while staying far away from inhabited areas. Onerous site selection issues common to the onshore receiving terminal are thus avoided.

3D Illustration of FSRU concept by SBM SINGLE BUOY MOORINGS Inc. FSRU concept can be designed for a wide range of LNG storage requirements in self-supporting prismatic or membrane type tanks and has an average gas send-out capacity of 1 bscfd. This design allows for either side-by-side or tandem offloading of the LNG Carrier.

The FSRU is moored to the seabed via a turret mooring system which could be of the disconnectable type, allowing avoiding the severest hurricane conditions

3D Illustration of FSRU concept by

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4. Liquefied Natural Gas or Liquefied Petroleum Gas - a crucial difference? 4.1. Liquefied petroleum gas (LPG), Liquefied petroleum gas (LPG) made up chiefly of propane or butane, is a by-product of gasoline and diesel fuel refining. It remains a liquid under low pressure and can be stored and transferred in appropriate vessels.

5.2. Liquefied natural gas (LNG) Liquefied natural gas (LNG) is a natural product occurring in underground deposits. In terms of composition, it is more than 90 percent methane (CH4). Natural gas retains its gaseous form down to a temperature of minus 161 degrees Celsius. Below this point it becomes a liquid and occupies a far smaller volume. LNG is about 1/600th the volume of natural gas at standard temperature and pressure (STP). In this form it is referred to as LNG, liquefied natural gas.

6. What is LNG? Liquefied natural gas, or LNG, is natural gas in its liquid form. When natural gas is cooled to -161 degrees Celsius (minus 259 degrees Fahrenheit), it becomes a clear, colorless, odorless liquid. LNG is neither corrosive nor toxic. Natural gas is primarily methane, with low concentrations of other hydrocarbons, water, carbon dioxide, nitrogen, oxygen and some sulfur compounds. During the process known as liquefaction, natural gas is cooled below its boiling point, removing most of these compounds. LNG weighs less than half the weight of water so it will float if spilled on water.

6.1. Natural Gas Composition While natural gas is generally thought of as methane, about 5 - 25% of the volume is comprised of ethane, propane, butane, hydrogen sulfide, and inerts (nitrogen, CO2, and helium). The relative amounts of these components can vary greatly depending on the location of the wellhead. The following table gives the composition of the natural gas feedstock, as well as typical pipeline and wellhead compositions. Natural gas feedstock Typical pipeline Typical range of wellhead Component used in analysis (a) composition (b) components (mol %) (c) Mol % (dry) Mol % (dry) Low value High value

Methane (CH4) 94.5 94.4 7.5 99

Ethane (C2H6) 2.7 3.1 1 15

Propane (C3H8) 1.5 0.5 1 10

Nitrogen (N2) 0.8 1.1 0 15

Carbon dioxide (CO2) 0.5 0.5 0 10

Iso-Butane (C4H10) 0 0.1 0 1

N-Butane (C4H10) 0 0.1 0 2 + Pentanes + (C5 ) 0 0.2 0 1

Hydrogen sulphide (H2S) 0 0.0004 0 1 Helium (He) 0 0.0 0 5 53,680 J/g 53,463 J/g Heat of combustion, HHV - - (23,079 Btu/lb) (22,985 Btu/lb) (a) Taken from SRI, 1994. (b) Taken from Chemical Economics Handbook (Lacson, 1999) and adjusted to include H2S. (c) Taken from Ullmann’s Encyclopedia of Industrial Chemistry, 1986.

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6.2. Where does LNG come from? A majority of the world's LNG supply comes from countries with large natural gas reserves. These countries include Algeria, Australia, Brunei, Indonesia, Libya, Malaysia, Nigeria, Oman, Qatar, and Trinidad and Tobago.

6.3. Is LNG flammable? When cold LNG comes in contact with warmer air, it becomes a visible vapor cloud. As it continues to get warmer, the vapor cloud becomes lighter than air and rises. When LNG vapor mixes with air it is only flammable if it's within 5%-15% natural gas in air. If it's less than five percent natural gas in air, there is not enough natural gas in the air to burn. If it's more than 15 percent natural gas in air, there is too much gas in the air and not enough oxygen for it to burn.

6.4. Is LNG explosive? As a liquid, LNG is not explosive. LNG vapor will only explode if in an enclosed space. LNG vapor is only explosive if within the flammable range of 5%-15% when mixed with air.

6.5. LNG production block scheme

Linde Engineering: LNG plant block diagram

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6.6. The basic single flow LNG process comprises A plate-fin heat exchanger set in a cold box, where the NG gas is cooled-down to LNG temperatures by a two stage single MR (Mixed Refrigerant) cycle.

A separation vessel, where the mixed refrigerant (MR) is separated in a liquid fraction, and which provides the cold temperature after expansion in a J-T (Joule- Thompson) valve for the NG precooling and liquefaction. The gas from the separator provides the LNG subcooling temperature after J-T expansion at the bottom of the heat exchanger.

The cycle gas streams leaving the heat exchanger are recompressed in the two stage turbo compressor.

The compressed cycle gas is cooled and partly condensed against air or water.

Basic single flow LNG process for less than 0.2 mtpa LNG

6.7. The advanced single flow LNG process comprises A SWHE (Spiral-Wound Heat Exchanger) where the natural gas is precooled liquefied and subcooled against various streams of a single mixed refrigerant cycle. A medium pressure refrigerant separator, from where the liquid is used to provide the precooling temperature after J-T (Joule-Thompson) expansion to the lower section of the SWHE. A high pressure refrigerant separator, from where the gas is cooled and partially condensed in the lower section of the SWHE. A lower temperature refrigerant separator, from where the liquid is used to provide the natural gas liquefaction temperature after J-T expansion. The gaseous refrigerant stream from this separator is used to provide the subcooling temperature after J-T expansion in the upper section of the SWHE. Advanced single flow LNG process for 0.2 to 1.0 mtpa LNG

The combined refrigerant cycle stream from the bottom of the SWHE is compressed in a two stage compressor with inter and aftercooling against air or water.

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6.8. MFC® (Mixed Fluid Cascade) process

Linde AG MFC® (Mixed Fluid Cascade) LNG process for 3 to 10 mtpa LNG

The Linde MFC® LNG process excels by a high efficiency respectively low shaft power consumption of the three mixed refrigerant cycle compressors.

The process comprises: PFHEs (Plate-Fin Heat Exchangers) for the natural gas precooling SWHEs (Spiral-Wound Heat Exchangers) for the natural gas liquefaction and LNG subcooling Three separate mixed refrigerant cycles, each with different compositions, which result in minimum compressor shaft power requirement Three cold suction turbo compressors with inter and aftercooling

Up to 8 mtpa LNG can be produced in a one train unit concerning heat exchangers and compressors.

Up to 10 mtpa LNG can be produced in a one train unit concerning the heat exchangers, however, with parallel compressors.

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7. What countries import LNG? There are 40 LNG receiving terminals located worldwide. Japan, South Korea, the United State and a number of European Counties import LNG.

Legende LNG Import Terminal Major City

7.1. Where is LNG import terminals located in the United States? LNG terminals in the United States are located in Everett, Massachusetts; Cove Point, Maryland; Elba Island, Georgia; and Lake Charles, Louisiana; and Peñuelas, Puerto Rico.

8. Which countries export LNG?

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8.1. SAMSON offshore reference: New modules installed on the Sakhalin II Molikpaq Tie-In offshore project

Yuzhno-Sakhalinsk, Russian Federation, 19 July 2006: Sakhalin Energy has successfully completed the installation of the Molikpaq Tie-In (MTI) modules. This Molikpaq Tie-In Platform is equipped with SAMSON control valves. As part of the construction and installation programme of July, two intricate modules, each the size of a 10-storey apartment block, were successfully lifted into position on the space-constrained deck using the Castoro 8, a mobile crane barge. In addition a new multi-million-dollar crane assembled locally in Kholmsk was also installed successfully.

David Greer, Sakhalin II Project Director, referred to the Molikpaq Tie-In installation as “representative of engineering at its finest”. He congratulated the Molikpaq Tie-In module team involved in the installation on “getting the job done professionally and efficiently”. The Molikpaq platform, which is the heart of the Vityaz Production Complex, is located in Astokh Feature of Piltun-Astokhskoye oil field, 17 kilometres offshore north-eastern Sakhalin.

Currently, because of the challenging ice conditions in the Okhotsk Sea, the platform is producing some 6 months a year during the ice-free season. The Molikpaq platform The new modules will be part of the connection between the platform and the new onshore and offshore oil and gas pipelines, which are currently under construction. This will allow year-round production of oil and gas from the Molikpaq.

The two modules (one for oil, one for gas), just completed by GPC, will travel in style on a 160m long self propelled vessel. The journey, which is over 7000 miles, will take just 35 days. The modules are solid steel to withstand the worst of a Sakhalin Island winter at sea – and weigh nearly 3,000 tonnes between them. First year-round production from the Molikpaq is expected in 2007.

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8.2. This list of natural gas fields includes major fields of the past and present. Remark: Some of the items listed are basins or projects that are comprised of many fields (e.g. Sakhalin has three fields: Chayvo, Odoptu, and Arkutun-Dagi).

Amounts in parentheses are estimated reserves in trillion ft³ (TCF) and 109 m3.

Trillion ft3 Country Field * 109 m3 (TCF)

Azerbaijan Shah Deniz gas field 22 786

(second gas field in South America after Bolivia unknown Venezuela)

Canada Sable Offshore Energy Project unknown

Indonesia Tangguh gas field 14 500

estimated between Iran Asalouyeh, South Pars Gas Field 11364 280 and 500

Netherlands Slochteren 66 1500 New Zealand Maui gas field unknown Bass Strait: Australia 40 1100 Greater Gorgon North Sea: Ormen Lange 11.1 397 Troll Norway Norwegian Sea and Barents Sea: 3.9 140 Snøhvit

Sakhalin-I 17.1 484 Russia Shtokman field 113 114 Urengoy gas field 280 10000 Kazakhstan Karachaganak field 51 1800

2.1 prove, Barnett Shale estimated as high 74 to 825 United States as 30

Jonah Field 10.5 297

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8.3. The greatest gas fields of the world sorted on size. No. Field * 109 m3 1 Asalouyeh, South Pars Gas Field 10000 to 15000 2 Urengoy gas field 10000 3 Shtokman field 3200 4 Karachaganak field, Kazakhstan 1800 5 Slochteren 1500 6 Greater Gorgon 1100 7 Shah Deniz gas field 800 8 Tangguh gas field 500 9 Sakhalin-I 485 10 Ormen Lange 400 11 Jonah Field 300 12 Snøhvit 140 13 Barnett Shale 60 to 90 14 Maui gas field unknown 15 Troll unknown

8.4. 2004 LNG Exporters Billion Cubic Number of % Change Since Year Feet per Liquefaction from 2003 Year (Bcf) Terminals Pacific Basin Importers Indonesia 1977 1,182 -5.0 2 Malaysia 1983 977 18.9 3 Australia 1989 430 15.9 1 Brunei Darussalam 1972 335 -1.8 1 USA 1969 59 -9.2 1 Sub-Total: 2,983 4.9 8

Middle East Exporters Qatar 1996 849 26.9 2 Oman 2000 319 2.1 1 United Arab Emirates 1977 260 1.6 1 Sub-Total: 2,983 14.2 4

Atlantic East Exporters Algeria 1964 909 -6.1 4 Trinidad 1999 494 17.9 1 Nigeria 1999 444 9.6 1 Libya 1971 22 -12.0 1 Sub-Total: 1,868 2.9 7

Total LNG Exported: 6,28 6.2 19

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8.5. 2004 LNG IMPORTERS Billion Cubic Number of % Change Since Year Feet per Regasification from 2003 Year (Bcf) Terminals Pacific Basin Importers Japan 1969 2,716-3.3 24 South Korea 1986 1,055 17.7 3 Taiwan 1990 322 24.8 1 India 2001 93New 1 Sub-Total: 4,186 3.3 29

Atlantic Basin Importers Spain 1970 61819.1 4 USA 1971 65228.9 4 France 1972 269-15.7 2 Italy 1979 208-11.1 1 Turkey 1994 151 -6.2 1 Belgium 1987 101 -15.1 1 Puerto Rico 2000 24 -7.7 1 Greece 1999 19 -5.0 1 Portugal 2003 46 130.0 1 Dominican Republic 2003 6 -40.0 1 Sub-Total: 2,094 8.3 17

Total LNG Imported: 6,280 6.2 46

Dates in parentheses indicate the first year the county either imported or exported LNG. Information source: BP Statistical Review of World Energy 2005

8.6. LNG LIQUEFACTION FACILITIES - WORLDWIDE (August 2005) Number Capacity Start Country Facility Owner of Trains (mty)* Year AFRICA 1 Algeria Arzew GL-1Z (Bethouia) Sonatrach 6 7.95 1978 2 Algeria Arzew GL-2Z (Bethouia) Sonatrach 6 8.40 1981 3 Algeria Arzew GL-4Z (Camel) Sonatrach 3 0.90 1964 4 Algeria Skikda GL-1K, Phase 1 Sonatrach 3 2.80 1972 5 Algeria Skikda GL-1K, Phase 2 Sonatrach 3 3.00 1981 Bechtel/Phillips/British 6 Egypt Egyptian LNG 1 3.60 2005 Gas 7 Egypt SEGAS Damietta SEGAS 1 5.60 2005 8 Libya Marsa El Brega NOC (Sirte Oil Company) 3 2.30 1970 9 Nigeria Bonny Island, T1 & T2 Nigerian LNG Ltd 2 5.90 1999 10 Nigeria Bonny Island, T3 Nigerian LNG Ltd 1 2.95 2002

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Number Capacity Start Country Facility Owner of Trains (mty)* Year ASIA Woodside Offshore 11 Australia NWS Australian LNG 2 5.00 1989 Petroleum PTY Ltd Woodside Offshore 12 Australia NWS Australian LNG 1 2.50 1992 Petroleum PTY Ltd Woodside Offshore 13 Australia NWS Australian LNG 1 4.20 2004 Petroleum PTY Ltd 14 Brunei Lumut 1 Brunei LNG 5 7.20 1972 15 Indonesia Arun, Phase 1 PT Arun NGL 3 2.00 1978 16 Indonesia Arun, Phase 1 PT Arun NGL 2 4.00 1983 17 Indonesia Arun, Phase 1 PT Arun NGL 1 2.00 1986 1977- 18 Indonesia Bontang A-H (Kalimantan) PT Badak NGL 8 22.59 1999 Petronas, Shell, 19 Malaysia Bintulu MLNG 1 3 8.10 1983 Mitsubishi Petronas, Shell, 20 Malaysia Bintulu MLNG 2 (Dua) Mitsubishi, 3 7.80 1994 Sarawak Petronas, Shell, 21 Malaysia Bintulu MLNG 3 (Tiga) Mitsubishi, 2 6.80 2003 Sarawak, Nippon MIDDLE EAST 22 Oman OLNG (Qualhat) Oman LNG 2 6.60 2000 23 Qatar Qatargas 1 T1-T3 Qatargas 3 8.30 1997 24 Qatar Rasgas 1 (Ras Laffan) Rasgas 2 6.60 1999 25 Qatar Rasgas 2 (Ras Laffan) T1 Rasgas 1 4.70 2004 United 1977/ 26 Arab ADGAS (Das Island I & II) ADGAS 3 5.60 1 994 Emirates NORTH AMERICA

27 US Kenai ConocoPhillips 1 1.50 1969

SOUTH AMERICA Trinidad & 28 Atlantic LNG Atlantic LNG 1 3.30 1999 Tobago

Trinidad & 2002- 29 Atlantic LNG T2 & T3 Atlantic LNG 2 6.60 Tobago 2003

* mty = million tonnes per year Sources of information: "World LNG Map 2004 Edition " Petroleum Economist Limited in association with Qatargas, and LNG Centre; LNG Centre

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9. LNG REGASIFICATION - IMPORT TERMINALS, WORLDWIDE (August 2005) Number of Start- Storage Capacity No. Country Terminal Owner Storage up (cubic meters) Tanks Year EUROPE 1 Belgium Zeebrugge Fluxys 3 261,000 1987 2 France Fos-sur-Mer Gaz de France 2 150,000 1972 3 France Montoir-de-Bretagne Gaz de France 2 360,000 1980 4 Greece Revithoussa DEPA 2 130,000 1999 5 Italy Panigaglia SNAM Rete Gas 2 100,000 1971 6 Portugal Sines Transgas 2 240,000 2003 7 Spain Barcelona Engas 4 240,000 1970 8 Spain Huelva Engas 3 160,000 1988 9 Spain Cartagena Engas 2 160,000 1989 10 Spain Bilbao Repsol, BPAmoco, 2 300,000 2003 Iberdrola, EVE, 11 Turkey Marmara Ereglisi 3 255,000 1994 Botas 12 Turkey Aliaga (Izmir) Egegaz 2 280,000 2003 United 13 Isle of Grain Grain LNG Limited 4 200,000 2005 Kingdom ASIA 14 India Dahej (Gujarat) Petronet LNG Ltd 2 320,000 2004 15 Japan Shin Minato Sendai Gas 1 80,000 1997 16 Japan Higashi Niigata Tohoku Electric 8 720,000 1984 17 Japan Futtsu Tokyo Electric 8 860,000 1985 18 Japan Sodegaura Tokyo Electric, 35 2660,000 1973 Tokyo Gas 19 Japan Higashi Ohgishima 9 540,000 1984 Tokyo Electric 20 Japan Ohgishima Tokyo Gas 3 600,000 1998 21 Japan Negishi Tokyo Gas 1 1250,000 1969 Tokyo Electric 22 Japan Sodeshi 2 177,200 1996 Shimizu LNG - Shizuoka Gas 23 Japan Chita Kyodo 4 300,000 1977 Chubu Electric, Toho Gas 24 Japan Chita LNG 7 640,000 1983 Chita LNG - Chubu Yokkaichi LNG Electric, Toho Gas 25 Japan 4 320,000 1987 Centre Toho Gas 26 Japan Yokkaichi Works Chubu Electric 2 160,000 1991 27 Japan Kawagoe Chubu Electric 4 480,000 1997 28 Japan Senboku I Osaka Gas 4 180,000 1972 29 Japan Senboku II Osaka Gas 18 1.510.000 1972 30 Japan Himeji Osaka Gas 7 520,000 1977 Osaka Gas, 31 Japan Himeji Joint 7 1.440.000 1984 Kansai Electric 32 Japan Hatsukaichi Hiroshima Gas 1 170,000 1996

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Number of Start- Storage Capacity No. Country Terminal Owner Storage up (cubic meters) Tanks Year 33 Japan Yanai Chuboku Electric 6 480,000 1990 Ohita LNG - Kyushu 34 Japan Ohita 5 460,000 1990 Electric, Kyushu Oil, Ohita Gas 35 Japan Tobata Kita Kyushu LNG - 8 480,000 1977 Kyushu Electric, Nippon Steel 36 Japan Fukuoka 2 70,000 1993 Saibu Gas 37 Japan Kagoshima Kagoshima Gas 1 36,000 1996 38 Japan Chita Midorihama Toho Gas 1 200,000 2001 South 39 Pyeong Taek Kogas 10 1,000,000 1986 Korea South 40 Incheon Kogas 12 1,280,000 1996 Korea South 41 Tongyeong Kogas 7 980,000 2002 Korea South 42 Gwangyang POSCO 2 200,000 2005 Korea 43 Taiwan Yung-An CPC 6 430,000 1990 NORTH AMERICA United 44 Everett Distrigas/TGE 2 160,000 1971 States United 45 Cove Point Dominion 5 370,000 2001 States United 46 Elba Island Southern LNG 3 190,000 2002 States United 47 Lake Charles CMS Energy 3 285,000 1982 States United Gulf Gateway 48 Excelerate 0 0 2005 States Energy Bridge SOUTH AMERICA Republic 49 AES Los Mina AES Corporation 1 160,000 2003 Dominican Edison Mission Puerto 50 EcoElectricta Energy, Gas 2 160,000 2000 Rico Natural Sources of information: Data from IEA 2003 Natural Gas Information, Gas Technology Institute’s World LNG Source Book 2001, and updated based on trade press reports as assembled by the Gas Technology Institute; LNG Center, the LNG & GTL Portal http://gmaiso.free.fr/lng; California Energy Commission - List of LNG Terminals in Japan January 2005; Gas Transmission Europe - LNG Map Information by Entry Point; Dominion http://www.dom.com; TGE http://www.TGEusa.com; Panhandle Energy http://www.panhandleenergy.com; Southern LNG.

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10. How is LNG transported? World demand for natural gas is rising dramatically. But not every high-demand region can be supplied by gas pipelines. Where moving natural gas by pipelines is not possible or economical, it can be transported by LNG vessels, where the most common tank types are membrane (prismatic) or Moss Rosenberg (spheres).

LNG is transported by specially designed vessels and stored in specially designed tanks. LNG is about 1/600th the volume of natural gas at standard temperature and pressure (STP), making it much more cost-efficient to transport over long distances where pipelines don't exist.

10.1. LNG carriers come in two forms: Moss tankers with spherical reservoirs and membrane tankers.

LNG vessel: Moss type

The Moss sphere is the classical design and the one used more frequently. Huge aluminium spheres up to 40 meters in diameter rest inside the ship’s hull. The optimized spherical shape makes these containers inherently stable, and so they can be made from thin material – just four centimetres of aluminium – without additional reinforcement.

With added insulation, this layer of aluminium is enough to hold the LNG at minus 163 degrees Celsius. The newer membrane carriers take a different design approach, using double-walled tanks. The innermost layer is most commonly a metal membrane 0.7 to 1 mm thick, which seals the tank. Behind it is an insulating layer made from a material such as plywood or balsa. Insulation performance is improved by the addition of a second layer of aluminium, glass fibres and polyurethane to make a sandwich.

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Shipyards are now building more membrane carriers than Moss spheres, on the strength of a Hyundai Heavy Industries study that found a gain of as much as eight percent in LNG capacity for membrane carriers over aluminium sphere vessels of equal size.

What is more, the steels now used for the membranes are qualities that vary little in their thermal expansion coefficient between 20 above and 163 degrees below zero Celsius. These qualities include Invar steels such as those employed in tankers of the Gas-Transport design.

LNG is transported in double-hulled ships specifically designed to handle the low temperature of LNG. These carriers are insulated to limit the amount of LNG that boils off or evaporates. This boil off gas is sometimes used to supplement fuel for the carriers. LNG carriers are up to 1000 feet long, and require a minimum water depth of 40 feet when fully loaded.

There are currently 136 ships which transport more than 120 million metric tons of LNG every year. (Source: University of Houston IELE, Introduction to LNG.)

10.2. 250,000 cubic meters of LNG per carrier An average carrier now has a capacity of some 150,000 cubic meters of LNG. Growth in the business, however, has led to orders for vessels having cargo capacities as large as 250,000 cubic meters. These have some technical peculiarities. Unlike all other cargo vessels, LNG carriers usually have steam turbine propulsion.

Their boilers are fired with boil-off gas (BOG), that is, gas vaporized from the LNG being transported. As a rule, 0.15 percent of the cargo boils off every day. LNG carriers in the past have thus powered their machinery by making direct use of their cargo.

In the new super carriers, however, the amount of BOG is more than the propulsion system can use, and so these vessels will be equipped with reliquefaction plants.

High-efficiency, slow-speed diesel engines will provide motive power. Reliquefaction systems have generally been too expensive.

On the one hand, they have a high first cost; on the other, their compressors consume about five megawatts of electric power.

But it will pay to install these systems in the new generation of 200,000-plus cubic meter carriers. However that reliquefaction plants will soon become established and that their costs will drop in the deck.

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11. Floating Storage Production and Regasification components. (Item 11.1 and 11.2 are quoted from TGE Gas Engineering GmbH [19]) 11.1. Process Flow-scheme of Boil-off Re-liquefaction Unit

During the voyage a proportion of the LNG is vaporized by heat ingress in the cargo containment system. The cargo tanks are well insulated with, typically 270mm cryogenic insulation, but some heat in leak producing boil-off gas (BOG) is inevitable. Typical values are about 0.1 to 0.15% of the full contents per day, which over a 21 day voyage, becomes a significant amount. Hitherto, ships have employed gas compression and use of the boil-off gas as fuel for the propulsion systems. Until now LNG carriers have been equipped with steam turbines powered by heavy fuel oil (HFO) and/or LNG BOG. However, designers of new larger ships are seeking more economic propulsion solutions which offer further economic advantages when combined with of a BOG re-liquefaction facility on-board LNG carrier.

BOG Re-liquefaction Plant Characteristics: Two BOG gas compressors, each 100% duty. Single centrifugal, integrally geared compressor assembly, driven by electric motor and assisted by expander. One multi-stream plate-fin heat exchanger. BOG collection system. LNG returns system. Ancillaries.

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11.2. A single packaged reliquefaction has the following major components: 11.2.1. Boil Off Compressor Boil off compressor (2x105%) duty: To supply the boil-off to the cryogenic heat exchangers To send boil-off gas to thermal oxidizer (in case of failure of reliquefaction plant)

11.2.2. Nitrogen Expander/Compressor Unit Nitrogen expander/compressor system (1x105%) consists of three compressor stages driven by a single electric motor and one expander stage: Compressor type: Horizontal, three stage, centrifugal with inter & after coolers. Expander type: Horizontal, single stage, single shaft turbine coupled directly to a compressor which is used as a brake for the expander.

SAMSON Control Valve

Nitrogen Expander/Compressor Unit (Example: Atlas Copco)

Cycle Compressor: Approx. 45 tonne package, 7.1m x 4m x 3m BOG machines: Approx. 25 tonne package, 4.9m x 3.5m x 2.8m

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This is an integral multi-wheel compressor with the 3rd stage compressor wheel attached to the main compressor bull-gear, but assisted by the turbo-expander. Expansion from high pressure to low is realised in the expander stage. The expander produces about 1200 kW of energy which is absorbed by the “brake” which is the 3rd stage. It is this energy which is extracted to provide the necessary cold for the liquefaction process.

The compressed Nitrogen is cooled in three gas coolers against seawater. Approximately 700 m³/h seawaters with inlet temperature of 32°C is required and has a 6°C rise through the coolers.

The Gas Coolers are Shell- and Tube-Type with seawater on the tube side and gas on the shell side for easy cleaning. Tubes are of fin-type with materials of construction compatible with the seawater environment. These are likely to be admiralty brass or titanium.

11.2.3. Cryogenic Plate-fin Heat Exchanger

They are the preferred heat exchangers (1 x 125%) in small LNG plants.

One plate-fin type cryogenic heat exchanger is used for condensing the compressed BOG by indirect heat exchange using cold nitrogen after turbine discharge as heat exchange medium.

This is a three stream exchanger housed in a carbon steel plate and frame construction.

Before entering the expansion stage of the Compander, Nitrogen is passed through the Main Heat Exchanger counter current to the expanded cold Nitrogen. This way the cold low pressure Nitrogen at the same time cools down the warm high pressure Nitrogen and condenses the BOG.

11.2.4. Piping and Ancillaries

In addition to the above main items of equipment, a separator is shown in the above flow-scheme (see page 31). In reality it may be a piping arrangement that ensures no liquid carry-over.

The injection of the LNG product is done using a piping arrangement which ensures good distribution of liquid into the bulk LNG and also allows re-absorption of any light flash gases.

11.2.5. BOG Collector System Cryogenic Heat Exchanger (Example: Chart Industries)

BOG is collected at the vapour connection of the cargo tank dome and routed to the boil-off compressor. To control suction temperature liquid from the LNG product produced by the liquefaction unit may be injected. However, this will only be required in extreme cases and at start-up.

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11.3. Heat exchangers, a key component of natural gas plants. The high density of the heat transfer area permits a compact design, so that heat exchangers with heat transfer surface from a few square meters up to approx. 10,000 m2 can be installed in one apparatus.

Photo Linde AG: Manufacturing of spiral wound heat exchangers

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The practically unrestricted range of utilisable materials allows spiral-wound heat exchangers to be used for a wide range of applications in cold, bur also warm applications. The spiral-wound heat exchanger is the core equipment in large base load LNG plants applying mixed refrigerant cycles for natural gas cooling and liquefaction.

Heat exchangers with spiral-wound tube bundles are used in petrochemical, air and gas separation plants as well in gas liquefaction units as: Coolers Heaters Liquefiers and Regenerators

The advantages are: Broad temperature and pressure range Several fluids in one exchanger Compact unit with high specific transfer area surfaces Robust behavior for start-up and shut-down Transient behavior can be ignored

The special features of the geometry and the possibilities to use a practically unrestricted range of materials open up a wide field of applications.

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11.4. The Cold Box The cryogenic process plants are the basis for a highly developed technology to manufacture components in aluminium, such as heat exchangers, columns, vessels, plate-fin heat exchangers. As a logical consequence these parts are - as far as practical - installed in a "coldbox" and pre-assembled with all necessary piping and instrumentation. After non-destructive examination and pressure testing, the pre-assembled packaged units, which may consist of two or three separate boxes, are shipped to site and erected. After the interconnecting pipes have been welded and tested, the insulation material is filled into the boxes and the plant is ready for commissioning. This procedure has proven of being the most economical and time saving way for this type of process plants. The void space is filled with the powdered mineral, Perlite, as the insulation material. Packaged units are fabricated up to 4.2 m by 6.0 m with length up to 42 m.

The packaged units (Cold Boxes) are used for a wide range of applications for treatment of cryogenic fluids and gases.

Photo Linde AG: Cold box assembly workshop The main applications are: Air and gas separation plants Gas liquefaction units Chemical and petrochemical plants Components such as: Columns Plate-fin heat exchangers Pressure vessels Separators Interconnecting piping Instrument lines for temperature & pressure Pressure difference & level indication Wall penetrations Valves Installed executable in a self supporting steel casing. Photo Linde AG: Cold box assembly 11.4.1. The benefits of this type of cold box are evident: The cryogenic process equipment and piping is all welded together and laid out as tight as possible resulting in minimized material and thermal losses and maximal safety. The cold box is mechanically completed in workshops under optimized conditions. The cold box provides external mechanical protection during transportation and in the plant itself. Apart from the “all welded” principle of the cold box interior, which is considered as the safest installation mode, the cold box enables detection of possible leakages by control of a nitrogen purge stream in the Perlite-insulated space. Fire resistance requirements can be met efficiently with a cold box. This is relevant for the compact LNG-plant layouts as well as in general for offshore LNG plant concepts.

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11.5. For example: Linde H2/CO separation plant with a coldbox Cryogenic processes like partial condensation and liquid methane wash (See section 20.1) are used for the recovery of pure carbon monoxide and pure hydrogen from gases resulting from partial oxidation or catalytic reforming processes. Carbon monoxide (See section 21.10) is mainly used for the production of acetic acid, formic acid, polyurethane, polycarbonates and methylacrylates. The desired purity of carbon monoxide depends on the prevailing requirements and can be adjusted into the ppm range with respect to the residual contents of hydrogen and methane.

To separate carbon monoxide from synthesis gas there are basically two main cryogenic process types: Condensation process Methane scrubbing process

For both cases it is mandatory that the feed gas to the process is absolutely free from water, CO2 and other components which could freeze at the low operation temperatures. Therefore process gas is initially purified in a molecular sieve adsorber station.

Feed gas from partial oxidation is normally supplied with high pressure, high CO and low CH4 content. In this case the condensation process is used. Alternatively, gases from steam reforming have lower pressure, lower CO and elevated CH4 content. In this case preferably methane wash is used and operated with methane supplied through the process gas.

Coldbox

General Scheme: Linde AG condensation process

Condensation process and methane wash process exist in several alternative configurations depending on required product purity, recovery rate, and presence of other impurities like N2 and Ar in feed. The simplest configuration of a condensation process is depicted above. It includes an adsorber station, a coldbox containing the plate fin heat exchangers to precool feed gas against product streams, the hydrogen separator and stripping column. As carbon monoxide compressor mostly a dry piston or integrally geared centrifugal compressor is used. The cryogenic equipment is manufactured and assembled in workshops and supplied as one package unit. Adsorber station and other machinery like carbon monoxide compressor, liquid methane pump or expansion turbine are supplied separately and interconnected on site. The coldbox is insulated with Perlite on site.

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11.6. For example: H2 CO plant with condensation process in Mai Liao, Taiwan

Client: Formosa BP Chemicals Corp. Process:

Partial oxidation, CO2 washes condensation process. PSA Feedstock: Naphtha Product: 3 3 20,000 Nm /h H2 99.9% and 25,400 Nm /h CO 99.8% Linde-Scope: Engineering, procurement, erection and start-up supervision Start-up: 2005

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11.7. SAMSON Cryogenic Valve Type 3248 Application Final control element designed as control equipment for use in the field of cryogenics. The valve Type 3248 is suitable for liquids and gasses as well as for Cold boxes.

Valve size 1” to 6” Pressure rating Class 150 to 600 Temperature range –459 to 428 °F / –273 to 220 °C

The Type 3248 Cryogenic Valve is especially designed to meet the extreme requirements in cryoengineering. Standard metal bellows to meet strict emission requirements. Minimized heat leak thanks to the use of a metal bellows seal and a cryogenic extension bonnet Valve body available in globe or angle styles Installation in vacuum-insulated pipelines, air separation plants and peripheral plants made possible by a cover plate on the cryogenic extension bonnet Valve maintenance possible without removing it from the pipeline Top entry through the cryogenic extension bonnet allows easy access to the seat, plug and bellows after removal of the actuator The Kvs coefficients can be modified in wide ranges by replacing the seat and valve plug. Standard version Temperature range from –320 to +428 °F (–196 to 220 °C) Metal bellows and self-adjusting V-ring packing made of pure PTFE or PTFE/carbon

Type 3248-1 With Type 3271 Pneumatic Actuator with 240 to 700 cm2 effective diaphragm area. Type 3248-7 With Type 3277 Pneumatic Actuator with 240 to 700 cm2 effective diaphragm area and for integral positioner attachment. Further versions Temperature range from –320 down to –459 °F (–196 down to –273 °C) Free of oil and grease for oxygen service High-purity version Type 3248-7 Pipe jacketing for installation in vacuum-insulated plant Control Globe valve components Type 3248-7 Control Angle valve Welding-neck ends (On request) Valve sizes 4” and 6” in Class 300 with 1400 cm2 pneumatic actuator (On request) Pneumatic actuator with additional hand wheel Differential pressures for valves in Class 600 (On request) Cryogenic valve conforming to DIN EN in DN 25 to 150 and PN 16 to 100

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11.8. SAMSON Cold box reference: SAMSON Valve installation near to cold box

SAMSON Valves are installation near to cold box to provide Hydrogen.

After arrival from Germany all valves are tested on pressure, leakage and function, before they are allowed to go in the plant.

SAMSON coldbox valve Type 3248

Photo: Air Liquide

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11.9. SAMSON reference: Air separation unit in Isfahan, Iran

SAMSON coldbox valve Type 3248

FAJR PETROCHEMICAL CO. is affiliated to NPC, Iran Located in Bandar Imam “Special Economic Free Zone” in Mahshar, Imam Khomini Harbor

Plant designer: AIR PRODUCT, UK The plant is under process since 2002.

The SAMSON control valves Type 3248 are fit in at the air separation unit (Coldbox).

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11.10. SAMSON reference: Air separation unit for company Schott in Mainz, Germany

SAMSON control valves

SCHOTT AG Hattenbergstr. 10 55122 Mainz Germany General contact Phone:+49 (0)6131/66-0 Fax:+49 (0)6131/66-2000 [email protected] www.schott.com

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11.11. SAMSON reference: Air separation unit of company Messer Griesheim, Hanau, Germany

The SAMSON control valves Type 3248 are fit in at the air separation unit (Coldbox) of the company Messer, Hanau, Germany.

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11.12. SAMSON reference: Air separation unit of Air Products in Ghent, Belgium

This air separation unit for company Air Products in Ghent in Belgium is equipped with control valves of SAMSON AG.

Air Products produces industry gasses and equipment as:

Oxygen/Nitrogen/Argon Hydrogen/Syngas

Helium Specialty Gases Air Separation Equipment Hydrocarbon Processing Equipment Natural Gas Liquefaction Equipment

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11.13. For example: Space

Air Products GTL Offerings: Process Equipment and Technology Air Separation Units (ASU) Liquefied Natural Gas (LNG) Membrane, Adsorption and Cryogenic Separation Units Gas Heated Reformer (EHTR) ITM Oxygen/ITM Syngas Integration Technologies Engineering and Operations Support Services Engineering Studies Operations Support Services

Air Products will selectively Co-Develop and Invest in Oxygen and Syngas supply Projects; and Methanol, FT Liquids and LNG Production Projects.

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11.14. SAMSON reference: The following companies install the Cryogenic Valve Type 3248 in your plants.

Arabian Industrial Gases Company

BERGUM IMPIANTI S.P.A. Chevron Nigeria Ltd. (CNL)

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11.15. SAMSON control valves Series 240, 250 and 280 Control Valves include pneumatic and electric globe valves, three-way valves, and angle valves. Their application range covers control tasks in process engineering and industrial applications as well as in supply and power plant engineering. The modular system allows easy retrofitting and servicing.

The control valves consist of the valve and the actuator. They can be equipped with pneumatic, electric, electro hydraulic or hand-operated actuators. For controlling purposes and travel indication, accessories such as positioners, limit switches and solenoid valves can either be attached directly or according to IEC 60534-6 (NAMUR rib).

The valve bodies are available in cast iron, spheroidal graphite iron, and cast steel, cast stainless or cold- resisting steel, forged steel or forged stainless steel as well as in special materials.

All parts of the valve and the pneumatic actuator housing in the completely corrosion-resistant version are made of stainless steel.

11.15.1. SAMSON valve Series 240 Series 240 Control Valves are available in nominal sizes ranging from DN 15 to DN 300 (½” to 12”) and up to a nominal pressure PN 40 (Class 300).

Control valves in the standard version are suitable for temperature ranges between –10 and +220 °C (15 and 430 °F). An insulating section allows the temperature range to be extended to –200 and +450 °C (–325 and +840 °F). The plug stem is sealed either by a self-adjusting PTFE V-ring packing or an adjustable packing. To meet stricter emissions control requirements, a stainless steel bellows is used.

The Type 3241 Control Valve can be equipped with a heating jacket that may also include the bellows.

For example:

Actuator Type 3277 Actuator Type 3277 Actuator Type 3277 Actuator Type 3277 made of stainless steel, made sheet steel, plastic coated made Sheet steel, plastic coated made of stainless steel, Ex i positioner Type 3730 Ex i positioner Type 3730 Ex d positioner Type 3731 Ex i positioner Type 3730 Special version in stainless steel, Die-cast aluminium, cromated Die-cast aluminium, cromated Special version in stainless steel, Valve Type 3241 Valve Type 3241 Valve Type 3241 Valve Type 3241 with metal bellow and body made of Carbon steel, made of stainless steel made of forged stainless steel made of forged stainless steel

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11.15.2. SAMSON Control valve Type 3241-9 DWA for PSA plants (Pressure Swing Adsorption) Type 3241-9 DWA with double-acting pneumatic Piston actuator Type 3275, for integral positioner attachment and/or limit switch.

The actuator is characterized by: Small overall height Powerful thrust due to the supply pressure of max. 6 bar Low friction Temperature range from -30 to 80 °C

The actuator is fixed to a joke which is designed to hold a pneumatic or electro pneumatic positioner. His type of direct attachment has the following advantages: Tight and accurate linkage Adjustments are not affected during transport Travel pick-off protected against touching and external influences, meeting to requirements of the German Accident Prevention Regulations (VBG 5) Easy pneumatic connection between actuator and positioner.

Rated travel: 15 to 30 mm, higher travel ranges on request.

Versions: Type 3275 with effective actuator area 314 cm2 or 490 cm2 or 804 cm2

Size: ½” to 6”, Temperature rang: –29 ... 220 °C (–20 ... 430 °F)

Valve body manufactured of: Stainless carbon steel in acc. with ASTM specification Forged steel or stainless forged steel Stainless carbon steel Undivided valve bonnet

Valve plug: Soft sealing Lapped-in metal. The control valves are designed according to the modular assembly principle and can be equipped with various accessories: Positioners, solenoid valves and other accessories according to IEC 60534-6-1 and NAMUR recommendation.

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11.15.3. Twelve good reasons to choose the SAMSON Type 3241 Control Valve

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11.16. SAMSON valve Series 250 Control valve for process engineering applications with high industrial requirements.

Series 250 Control Valves are used when large nominal sizes and/or high pressures are involved in process engineering, power plant or supply engineering.

In addition to globe, three-way and angle valves, four-flanged valve bodies with bottom plug stem guides, and valves with axial multi-stage throttling plugs, customized valve constructions to meet customer specifications can be engineered as well.

The valves are manufactured in nominal sizes from DN 15 to DN 500 (½” to 16”) and for nominal pressures between PN 16 and PN 400 (Class 150 to 2500).

The standard versions of these control valves are suitable for temperatures ranges between –10 and +220 °C (15 and 430 °F). This temperature range can, however, be extended by using an adjustable high-temperature packing to a temperature range between –10 and +350 °C (15 and 660 °F) and by using a bellows seal or an insulating section to a temperature range between –200 and +500 °C (–325 and +930 °F).

Valve body optionally made of: Carbon steel Stainless carbon steel or High-temperature (Heat-treated) or cold-resisting carbon steel

For example:

Actuator Type 3271 Actuator Type 3271 Actuator Type 3271 Actuator Type 3271 made sheet steel, plastic coated made of stainless steel, made of stainless steel, made Sheet steel, plastic coated Ex i positioner Type 3730 Valve Type 3253 Valve Type 3254 Ex i positioner Type 3780 Die-cast aluminium, cromated made of Carbon steel made of carbon steel Die-cast aluminium, cromated Valve Type 3251 Valve Type 3256 made of Carbon steel, with hand wheel made of stainless steel

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11.17. SAMSON’s gas handling

Flow divider ST III and V-Port Plug

Control valve Type 3251 Silencer Flow divider ST I

Flow divider Effective solution A control valve can be adapted to an existing pipeline by installing a silencer downstream of the valve, which helps to restrict the differential pressure across the valve at full load. At the same time, it expands the outlet to achieve an outlet velocity at the valve which does not exceed 0.3 Mach. Combined with the SAMSON flow divider in the valve, Silencer the silencer (System of two to five attenuation plates Type 3381-3-5 in a body) attains an excellent noise performance and V-Port Plug reduces the dynamic load on the valve plug. 11.18. SAMSON’s handling with liquids Cavitation can occur in control valves handling fluids, causing loud noise as well as damaging valve components and ultimately leading to additional costs in process plants. A standardized procedure to evaluate the destructiveness of cavitation-induced still does not exist whereas noise emission can reliably be predicted with the new international EN 60534-8-4 standard.

SAMSON: Anti cavitation trims Optimized trim for low-noise and low-wear pressure reduction for liquids with differential pressures up to 180 bar or 2610 psi.

AC-1 Trim AC-2 Trim AC-3 and AC-5 Trim Includes the following special One to four attenuation plates are Special features features: Raised seat, parabolic integrated into seat of the AC-2 Trim Raised seat, Multi-stage parabolic plug, plug with integrated guide in the upstream of the parabolic plug and the additional plug guiding integrated into the seat, seat. plug guide. optionally low-wear version equipped with The differential pressure may not The differential pressure may not exceed stellited seating surfaces or hardened trim exceed 40 bar or 580 psi. 40 bar or 580 psi. The differential pressure may not exceed 100 (1450 psi) or with AC-5 180 bar (2610 psi).

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11.19. Copy of the AIR LIQUIDE Certificate for the Cryogenic Test with the SAMSON Types 3241, 3251 and 3254

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11.20. SAMSON’s Bellows seal: Sealed for life Our maintenance-free, hysteresis-free bellows seals guarantee zero leakage over the entire service life of the control valve. With SAMSON's environmentally friendly bellows seals, you are always on the safe side and plant downtime required to replace the valve packing is a thing of the past. What's more, they reduce your total cost of ownership while yet still keeping your emissions considerably below the stringent limits specified in the Clean Air Act and the TA-Luft. See for yourself by monitoring the control chamber between the bellows and the backup packing system. You can trust our bellows seals. We manufacture the entire bellows seal assemblies ourselves to ensure top quality.

The control valves are designed for oil and for heat transfer systems using organic heat transfer media.

Metal bellows Backup packing

Control connection

Metal bellows

The plug stem is additionally sealed with packing at the top flange. This packing serves as backup packing. The metal bellows can be monitored for leakage or a sealing medium can be applied by means of a test connection. The bellows seal can be used for valves of Series 240 from –200 to +400 °C, and Series 250/280 from –200 to +450 °C.

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11.21. SAMSON Positioners completely integrated

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11.22. SAMSON reference: A pipeline with five Natural Gas Metering Stations

5 SAMSON Control Valves Type 251-1 DN 8”, ANSI 600 with hand wheel and with i/p- Positioners Type 3767 before the assembly into the pipe.

Location: Bangladesh

Unusual feature Valves are mounted in very remote natural gas pipelines (1090 psig ≈ 75 bar) where no compressors are maintained. Therefore these valves and the positioners are working with Natural Gas as operating medium.

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11.23. SAMSON reference: PT PERTAMINA EP Jambi, Sengeti, Jambi, Indonesia

SAMSON control valve Type 3241

Gas filter separator plant Capacity: 7 MMSCFD gas and 450 Barrels per day (BPD) condensate at an operation pressure of 275 psig.

SAMSON Control valves of type 3241 are installed for pressure control and level control. The auxiliary energy supply is natural gas.

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12. SAMSON Self-operated Pressure Regulators for special applications Industrial gases, such as argon, nitrogen and oxygen, are stored in liquefied condition at cryogenic temperatures and at a constant pressure in thermally insulated storage tanks. Suitable pipelines transport the medium to the consumer. The extreme operating conditions (pressures up to 50 bar and temperatures down to -200°C) require the use of special control valves.

Application Pressure regulators for cryogenic gases and liquids as well as other liquids, gases and vapors with operating pressures up to 50 bar. Set point range 0.2 bar to 40 bar - Temperature range -200 °C to +200 °C Free of oil and grease TÜV type tested

The Types 2357-... Pressure Regulators are especially designed for the use in cryogenic services, but are also suitable for handling gases, liquids and vapors under different operating conditions.

Special features Low-maintenance, self-operated P regulators Wide set point range and easy set point adjustment Rugged design and small overall height Free of oil and grease Pressure Build-up Regulator Type 2357-3 Versions with fail-safe action and integrated The pressure regulators consist of a control valve, an pressure relief valve operating diaphragm and a set point adjuster.

Types 2357-1/6 Pressure Reducing Regulators Pressure regulators with globe valve, which maintain the downstream pressure at the adjusted set point. The valve closes when the downstream pressure rises.

Pressure build-up regulator with fail-safe action For reverse operating direction. The upstream pressure is transmitted to the operating diaphragm. The valve closes when the upstream pressure rises.

Fail-safe action: The plug in the pressure build-up regulator operates as a safety valve and relieves the upstream pressure. The pressure acts on the plug from below. The valve opens to relieve the pressure.

Types 2357-2/7 Excess Pressure Regulators Pressure regulators with angle valve, which maintain the upstream pressure at the adjusted set point. When the upstream pressure rises, the valve opens until the pressure across the valve has assumed the adjusted set point. Type 2357-2 can additionally be equipped with a non-return valve unit. In thermally insulated storage tanks, the excess pressure is relieved into the consumer pipeline before the safety valve responds.

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12.1. SAMSON’s Self-operated equipment for cryogenic media Application example (schematic drawing)

3 Excess Pressure Regulator Type 2357-2

9 Level Meter Type Media 5

2 Pressure Build-up Regulator Type 2357-1

1 Tank for cryogenic liquid Pressure Build-up Regulators 2 Types 2357-1/6 Excess Pressure Regulators 3 Types 2357-2/7 Pressure Reducing Regulators 4 Types 2357-1/6 Safety Temperature Monitor (STM) 5 Type 2040

6.1 Shut-off valve

6.2 Shut-off valve 7 Additional evaporator 8 Evaporator 9 Level Meter Type Media 5 5 Safety Temperature 10 Safety valve 4 Pressure Reducing Monitor (STM) Type 2040 11 Filter Regulator Type 2357-6 12 Shut-off valve

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13. How is LNG stored? When LNG is received at most terminals, it is transferred to insulated storage tanks that are built to specifically hold LNG. These tanks can be found above or below ground and keep the liquid at a low temperature to minimize the amount of evaporation. If LNG vapors are not released, the pressure and temperature within the tank will continue to rise.

LNG is characterized as a cryogen, a liquefied gas kept in its liquid state at very low temperatures. The temperature within the tank will remain constant if the pressure is kept constant by allowing the boil off gas (BOG) to escape from the tank.

This is known as auto-refrigeration. The boil-off gas is collected and used as a fuel source in the facility or on the tanker transporting it. When natural gas is needed, the LNG is warmed to a point where it converts back to its gaseous state. This is accomplished using a regasification process involving heat exchangers.

13.1. How is natural gas stored? Natural gas may be stored in a number of different ways. It is most commonly stored underground under pressure in three types of facilities. The most commonly used are depleted reservoirs in oil and/or gas fields because they are more available. Aquifers and salt cavern formations are also used under certain conditions. The characteristics and economics of each type of storage site will dictate its suitability for use.

Two of the most important characteristics of an underground storage reservoir are its capability to hold natural gas for future use and its deliverability rate. The deliverability rate is determined by the withdrawal capacity of the associated valves and compressors and the total amount of gas in the reservoir. In other states, natural gas is also stored as LNG after the natural gas has been liquefied and placed in aboveground storage tanks.

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13.2. Tank monitoring and remote data transmission with SAMSON Media 6 It requires perfect logistics if gas suppliers want to please their customers, as there is nothing more important than providing supplies in time.

The Media 6 Digital Transmitter for Differential Pressure and Flow by SAMSON with its digital measured value processing and display opens up new opportunities to gas suppliers and customers. The measured tank level can be displayed either on site on a large LCD display, in the control station or at the consumer via a network. It is suitable for application in tank monitoring or tank filling logistics. The integrated microelectronics of Media 6 saves data of four gas types and the tank geometry. The actual tank level is calculated from the differential pressure and the saved information. It is displayed with its exact numerical value and as a bar graph for instant recognition.

Remote data transmission

connection to a PC and the SAMSON TROVIS-VIEW software allows the settings for Media 6 to be transmitted directly at the place of installation and facilitates reading the data related to the tank and gas used.

The integrated modem transfers data over telephone (analog or digital network) or via radio data transmission (GSM) to the control station of the gas supplier.

Simultaneously, text messages can be sent to allocated mobile telephones or pocket computers.

Data is polled at regular intervals and in the event of a limit alarm or an intervention by the control station of the supplier, providing up-to-dale information on tank contents or consumption trends.

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14. How is LNG used? LNG is normally warmed to make natural gas to be used in heating and cooking as well as electricity generation and other industrial uses. LNG can also be kept as a liquid to be used as an alternative transportation fuel.

14.1. Why use LNG? Natural gas is the cleanest burning fossil fuel. It produces less emissions and pollutants than either coal or oil. The North American supply basins are maturing and as demand for natural gas increases in California and throughout the United States, alternative sources of natural gas are being investigated.

Natural gas is available outside of North America, but this gas is not accessible by pipelines. Natural gas can be imported to the United States from distant sources in the form of LNG.

Since LNG occupies only a fraction (1/600) of the volume of natural gas, and takes up less space, it is more economical to transport across large distances and can be stored in larger quantities. LNG is a price-competitive source of energy that could help meet future economic needs in the United States.

14.2. Typically Natural Gas is used as: Pipeline Fuel Oil & Gas Vehicle Fuel 2.8 % Industry 0.1 % Operations 4.9 % Electric Power 23.8 % Industrial

33.2 %

Commercial 13.7 %

Residential 21.5 %

Although the majority of Americans know very little about liquefied natural gas (LNG), it has been an important part of the nation’s energy mix for almost 100 years. Currently, there are more than 100 production, transport and storage facilities across the country. When LNG is returned to its gaseous state, it is used across the residential, commercial and industrial sectors for purposes as divergent as cooking, fuelling vehicles, generating electricity and manufacturing paper, metal and glass.

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15. What is a Rapid Phase Transition? When enough LNG is spilled on water at a very fast rate, a Rapid Phase Transition, or RPT, occurs. Heat is transferred from the water to the LNG, causing the LNG to instantly convert from its liquid phase to its gaseous phase. A large amount of energy is released during this rapid transition between phases and a physical explosion can occur. While there is no combustion, this physical explosion can be hazardous to any nearby person or buildings.

16. What is a "peak-shaving" facility? LNG peak-shaving facilities are used for storing surplus natural gas that is to be used to meet the requirements of peak consumption later during winter or summer. Each peak-shaving facility has a regasification unit attached but may or may not have a liquefaction unit. These facilities without a liquefaction unit depend upon tank trucks to bring LNG from other nearby sources to them. Of the approximate 113 active LNG facilities in the United States, 57 are peak-shaving facilities.

The other LNG facilities include marine terminals, storage facilities, and operations involved in niche markets such as LNG vehicular fuel. (Source: University of Houston IELE, Introduction to LNG.)

17. What about security? All LNG ships must comply with all pertinent local and international regulatory requirements, which include regulations and codes set forth by

the International Maritime Organization (IMO), the U.S. Maritime Administration (MARAD), the U.S. Coast Guard (USCG), and the U.S. Department of Transportation (DOT), as well as the hosting Port Authority.

DOT regulations must be followed at onshore LNG facilities and marine terminals. The Research and Special Programs Administration, DOT, regulations include 49 CFR Part 193 - Liquefied Natural Gas Facilities: Federal Safety Standards.

These standards specify sitting, design, construction, equipment, and fire protection requirements that apply to new LNG facilities and to existing facilities that have been replaced, relocated, or significantly altered.

Offshore marine terminals must follow regulations set by the USCG. The USCG monitors the safety of coastal waters around the U.S. and ensures the safety of ships while in U.S. waters and in port by preventing other ships from getting near LNG tankers.

The USCG works with local harbor authorities and LNG facility personnel to ensure that proper procedures are followed. The USCG and MARAD are the federal agencies responsible for sitting offshore LNG facilities and are currently developing regulations.

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18. SAMSON FSO and LPG reference: Bayu-Undan gas recycle project (Item 18.1 to 18.7 are quoted from TGE Gas Engineering GmbH [4])

The Bayu-Undan gas recycle project is a world-class offshore project to develop the gas liquids resources of its field, which is located in the Timor Sea in 80 meters of water about 500 km northwest of Darwin, Australia and about 350 km southeast of Dili / East Timor.

The field contains estimated 400 million barrels of gas condensates and LPG as well as 3.4 trillion cubic feet of natural gas. According to the current phase of the project, the natural gas shall be exported via pipeline to the Australian cost, while the gas condensates and the LPG shall be exported via a permanently turret- moored floating storage and off-loading facility (FSO).

The development project is a co-venture of six companies with Phillips Petroleum (91-12) Pty. Ltd as the unit operator.

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18.1. Floating storage and off-loading (FSO)

They have contracted the design and fabrication of the FSO to Samsung Heavy Industries and the complete LPG gas handling system for the FSO has been subcontracted to TGE Gas Engineering GmbH as an EPCS contract. Which means that TGE as a leading engineering contractor for onshore and offshore gas handling systems for LPG and LNG is responsible for the basic and detailed engineering, the procurement of all equipment for the gas plant and supervision during construction and commissioning. TGE has been involved in this project since the early beginning, i.e. our expertise has been utilized already during development of the contract specifications for this first purpose-built LPG and condensate FSO.

FSO

Photo TGE: Drilling, production and processing platform

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The FSO is located approximately 2 km from the DPP (drilling, production and processing platform), where sales quality of condensate, propane and butane is to be produced and exported to the FSO via three sub-sea pipelines. The accommodation area and general machinery rooms are located in the fore part in front of the turret, while the gas plant machinery is located on the deck. Six LPG tanks are arranged along the centre line between four condensate tanks on each side (portside and starboard). The total storage capacity is approx. 95,000 m³ (600k barrels) for LPG and 130,000 m³ (820k barrels) for condensate.

The project includes two phases. The first one started in February 2004, for the development of liquids and the second one for the development of LNG. In phase 1 three production and treatment platforms, relevant facilities and an FSO vessel for the storage of liquids have been installed. The second phase entails the construction of a 26-inch diameter 500-kilometer long sea line that will link the field to Darwin where an onshore LNG plant with a 3.5 million tonnes/year capacity is under construction.

Under a 17-year long contract, gas produced will be sold to two Japanese companies, Tokyo Electric and Tokyo Gas that bought a 10.08 % interest in the integrated project. The LNG production has started in the first quarter of 2006.

18.1.1. LPG Gas Handling System for a Condensate / LPG - FSO Block diagram of gas handling system

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The import streams are cooled down by the refrigeration system approximately to the saturation temperature at atmospheric pressure, i. e. tank pressure, and then throttled into the tank.

The boil off gas (BOG) reliquefaction system serves to keep the tank pressure by balancing the heat ingress through the tank insulation and has ample capacity to compensate also the small amounts of flash gas from the refrigerated import flow.

A purge condenser for the propane stream completes the reliquefaction system. This arrangement allows handling also qualities of c-propane BOG with higher ethane content (off-spec.), if this should be imported to the FSO for short periods. The export system consists mainly of the pumps plus one vaporizer per segregation.

The inert gas system is needed for purging operations of the cargo tanks and the cargo hold spaces. All equipment except for the inert gas plant is installed on open deck.

18.2. BOG Reliquefaction Unit BOG = Boil Off Gas The portion of LNG that is vaporized in storage or during transportation is normally used as fuel gas in the plant or for the carrier.

Photo TGE: BOG Reliquefaction Unit SAMSON Control Valve

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18.3. Refrigeration System The refrigeration system consists of four units with oil flooded screw compressors and kettle type chillers.

Due to the demanded refrigeration capacity and temperature difference two units in series operation are installed to cool the propane stream from +30°C to approx. -39°C. One unit serves to cool the butane stream from +30°C to approx. -5°C. The fourth unit serves as stand-by and is designed to substitute any of the other three units.

Propane is used as refrigerant. Condensation of the refrigerant is performed in plate type heat exchangers with titanium plates against sea water.

Main capacity data for the units are given below.

Suction volume Refrigeration capacity Shaft power

[m³/h] [kW] [kW] Unit 1 (C3) 7,500 3,100 1,300 Unit 2 (C3) 7,500 1,400 1,100 Unit 3 (C4) 5,700 2,300 900 Unit 4 (Spare) 7,500 3,100 1,300

18.4. Instrumentation and Controls The project requires standardizing all instrumentation equipment for the overall project including the platforms. Furthermore all monitoring, alarm and control functions are to be integrated into one DCS for the overall project. Local PLCs are not allowed.

For transportation reasons each unit was to be separated in two skids.

Photo TGE: Compressor Skid of Refrigeration Unit

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SAMSON Valve

SAMSON Valves Photo TGE: Chiller Skid of Refrigeration Unit The worldwide first combined FSO for LPG and gas condensates will commence commercial operation in early 2004 under Phillips Petroleum. The remote location of the Bayu-Undan gas field requires a very durable and reliable design.

TGE Gas Engineering GmbH as a leading and very experienced engineering contractor for onshore and offshore LPG storage facilities has designed and delivered the complete gas handling system to Samsung Heavy Industries, where the FSO is currently under construction.

Huge refrigeration units will be used to cool down the imported propane and butane to the storage temperature at the FSO.

A reliquefaction plant is installed to control the pressure of the LPG cargo tanks.

The export system allows unloading to a shuttle tanker within 24 hours.

The SAMSON control valve will be adjusted.

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18.5. Inertgas system With respect to full redundancy two identical combustion type inertgas generators with a capacity of each 6,000 m³/h have been designed. Both inertgas generators are equipped with blowers of 2 x 100 % capacity and can serve either the condensate tanks or the LPG tanks and hold spaces. For LPG service refrigeration dryer and an adsorption dryer complete the system. The blowers of the inertgas system will also be used for purging with air.

The dryers are designed for 12,000 m³/h of dry air at a dew point of - 50°C. The same flow rate is considered for the electric heater, which is integrated into the system for rapid warming up of the tanks for inspections after cargo operation at about -44 °C (for c-propane). All controls of the complete inertgas system including burner controls are also integrated into the DCS.

The operator of the project is an affiliate of ConocoPhillips. Tokyo Electric Power Co. (TEPCO) and Tokyo Gas Co., Ltd. (Tokyo Gas) have officially finalized their participation in the Darwin LNG Project. TEPCO and Tokyo Gas have participated in the development of Bayu-Undan Field located in the Joint Petroleum Development Area (JPDA) of Timor-Leste and Australia, the pipeline from the JPDA to Australia and sales of LNG produced near Darwin, Australia from feed gas sourced from the field. They believe the participation in the LNG business chain will secure a stable and economic supply of the fuel and city gas feed stocks

System Availability and Maintenance Requirements The complete FSO is to be designed for 25 years lifetime, being exposed to tropical marine conditions.

Considering the remote location of the Bayu-Undan field and maintenance requirements during the lifetime of the FSO there are significant consequences for design criteria like material selection, coating, arrangement of equipment for easy accessibility, etc. Redundancy is requested especially for all equipment which needs permanent availability like the import system and tank pressure control system. A 2 out of 3 voting is requested for all transmitters with safety trip function.

Photo TGE: LPG-FSO

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18.6. The project data of the Bayu-Undan gas recycle project FSO are: Shipyard: Samsung Heavy Industries, Korea Year of completion: 2003 Classification: LRS (Lloyds Register of Shipping) Vessel: 95,000 m3 LPG-FSO Length over all: 248 meter Breadth moulded: 54 meter Depth moulded: 31 meter Displacement: 200.000 tons Number of cargo tanks: 6 Cargo manifolds: 2 liquid lines, 2 x 12”, ANSI 150 lbs flanges 2 vapor lines, 2 x 10”, ANSI 150 lbs flanges

18.7. One of the largest mooring FSO systems in the world 400 million barrels of condensate & LPG FSO storage capacity of 1.4 million barrels of hydrocarbons 3.4 trillion cubic feet of natural gas 22 planned wells to exploit the 25 km x 12 km field 25 production year life span US$ 1.8 billion development costs Located 500km north west of Darwin, Australia Located 250km south of Suai, East Timor Located in the Timor Sea’s Joint Petroleum Development Area (JPDA), formerly the Zone of Co-operation a (ZOCA) Located in an area prone to extreme weather - cyclones

Photo: Thales GeoSolutions (Australasia) Ltd

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18.8. The following SAMSON control valves with accessories were installed in the FSO Bayu-Undan gas recycling project:

Insulation Accessories Valve Valve Body Diaphragm section Plug Size (ASTM Material) cases Positioner Limit Solenoid Supply (ASTM Material) Type 3780 switches Valve in Pressure with HART® Type 3776 Stainless Regulator Control Valve Piece communication Steel Type 4708 Figure Type ANSI Actuator Valve Bonnet Flow divider Seat Class (ASTM Material) cm2

Stainless 3” to 4” A351 CF8M no steel solid Stellite WN 1.4301

3 valves with 6 3241-7 A 182 F 316 6 Piece No No 6 Piece a flow divider WN 1.4571 Forged 300 STI and 350 to 700 with Stellite stainless 1valve with facing steel STIII Stainless 1” A351 CF8M no steel WN 1.4571 WN 1.4301 WN 1.4571 9 3241-7 A 182 F 316 Sealing ring No 9 Piece 9 Piece 9 Piece Forged for soft 300 no 240 stainless sealing: steel PTFE with glass fiber

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A 182 F 316 Stainless Forged 1” to 6” A351 CF8M steel solid Stellite stainless WN 1.4301 steel 20 3241-7 20 Piece No No 20 Piece A 182 F 316 2 valves with WN 1.4571 Forged 300 a flow divider 240 to 700 with Stellite stainless STI facing steel

A 182 F 316 Stainless Forged 2” A351 CF8M steel solid Stellite stainless WN 1.4301 steel 2 3241-7 2 Piece No No 2 Piece A 182 F 316 WN 1.4571 Forged 150 no 240 with Stellite stainless facing steel

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Actuator paints with 6” A351 CF8M No offshore WN 1.4571 seawater 2 3251-1 paintwork. 2 Piece No 2 Piece 2 Piece A 182 F 316 Forged with a flow 150 1400 WN 1.4571 stainless divider STI steel

Stainless 3” A351 CF8M No steel WN 1.4571 WN 1.4301

1 3244-7 1 Piece No 1 Piece 1 Piece A 182 F 316 Forged 150 No 350 WN 1.4571 stainless steel

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Balancing CrNi steel, WN 1.4571 bellow made Set point with sealing 41-23 1” A 351 CF8M of Stainless range ring for soft Valve closes steel 0.75 to 3.5 6 sealing NBR No No No No when the WN 1.4571 psi downstream 99,2 sq. in pressure rises. 150 WN 1.4571 No WN 1.4571 (640 cm2)

Balancing CrNi steel, WN 1.4571 bellow made Set point with sealing 41-23 1” A 351 CF8M of Stainless range ring for soft Valve closes steel 65 to 145 sealing 1 No No No No when the WN 1.4571 psi PTFE downstream pressure rises. 6,2 sq. in 150 WN 1.4571 No WN 1.4571 (40 cm2)

Positioners, solenoid valves, limit switches and other accessories according to IEC 60534-6 and NAMUR recommendation. All valves with inspection certificate 3.1 B according to DIN EN 10204 inclusive material traceability and additional inspection certificate of Lloyd's registers of shipping.

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19. SAMSON reference: FPSO- and LNG- Project The floating production storage and offloading vessel “Cossack Pioneer” produces crude oil, gas and condensate and is part of the North West Shelf Venture's offshore production facilities.

Oil is exported from Cossack Pioneer via shuttle tankers for international markets. Gas and condensate is transported via pipeline to the North Rankin platform and then to the onshore gas plant near Karratha.

112km north-west of Karratha, Western Australia 34km east of Location: North Rankin platform Facility: Floating production, storage and offloading facility Storage capacity: 1.15 million barrels No of wells: 10 production wells Production capacity: 150,000 barrels of oil per day Commissioned: 1995 Refurbished: 1999 Water depth: 80 metres Producing fields: Wanaea, Cossack, Lambert, Hermes Permits: WA-11-L, WA-9-L, WA-16-L Discovered: 1989 Wanaea, 1990 Cossack, 1996 Hermes, 1996 Lambert

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19.1. North West Shelf Project Interests

Domestic Natural Gas

LNG

Oil

China LNG*

*CNOOC NWS Private Limited is also a member of the North West Shelf Venture but does not have an interest in the North West Shelf Venture infrastructure.

The Woodside-operated onshore gas plant near Karratha in Western Australia is Australia's largest gas plant. It processes natural gas, liquefied natural gas, liquid petroleum gas and condensate for Australian and international markets. As part of the Woodside-operated North West Shelf Venture, Australia's largest resource project, the plant produces 11.9 million tonnes of LNG a year for export and supplies about 65% of Western Australia's natural gas.

Two offshore pipelines transport gas and condensate from the North Rankin, Goodwyn and Cossack Pioneer offshore facilities to the onshore plant where it is processed and distributed. LNG is exported via an 850 metre jetty with a loading rate of 10,000 cubic metres an hour. It takes about 22 hours to berth and load an LNG ship. LPG and condensate are exported via a 450 metre jetty. Propane and butane are loaded at about 1500 cubic metres an hour and condensate at 1000 cubic metres an hour.

Location: Karratha, 1260km, north of Perth, Western Australia Work force: ~ 430 (240 staff and 190 contractors) 1984 Domestic gas phase 1989 LNG Trains 1 and 2 Commissioned 1992 LNG Train 3 2004 LNG Train 4

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19.2. SAMSON FPSO reference: “COSSACK PIONEER REFURBISHING”

COSSACK PIONEER

Conversion to a Floating Production Storage and Offloading (FPSO) Vessel Particulars Length 278.71 m Year of conversion 1995 Breadth 51.82 m Operator Woodside Petroleum (W.A. Oil) Pty Ltd Wanaea / Cossack Field, offshore Depth 25.60 m Held Western Australia Deadweight 149,9 Depth 80 m Classification ABS91 t Production capacity 115,000 barrels per day Year built 1972 Cargo capacity 1,150,000 barrels Mooring System Disconnectable Rigid Turret Mooring

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The conversion of the Cossack Pioneer from a tanker to a Floating Production, Storage and Offloading (FPSO) facility was the 22nd in the series of FPSO and FSO conversions undertaken by Keppel Shipyard since 1981. It was one of the biggest and most complicated conversions Keppel has handled. The conversion contract for the tanker was awarded by Woodside Petroleum (W.A. Oil) Pty Ltd, a consortium consisting of Woodside Petroleum Ltd, BHP Petroleum (North West Shelf), BP Developments Australia Ltd, Chevron Asiatic Limited, Japan Australia LNG (MIMI) Pty Ltd and Shell Development (Australia) Pty Ltd.

Piping System The estimated 13,000 metres of piping installed highlights the complexity of the conversion. On the main deck and the process skids, the running of the pipes involved some 23 piping systems, including oil and gas lines. Pipe supports were also designed and installed.

A special feature of the pipe work was the extensive use of super Duplex and Duplex stainless steel pipes for some of the piping systems, such as product and fire water lines. A large proportion of these pipes range from 250mm to 500mm in diameter with wall thickness from 18mm to 32mm.

Mooring System An 1100-tonne SBM rigid turret mooring arm system was installed on the bow. Additional 250 tonnes of reinforcements were installed in the fore peak tank.

Mooring equipment and an offloading platform were installed at the stern to facilitate tandem mooring of shuttle tankers and handling of offloading hoses.

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Communication and Navigation Systems Honeywell communication systems were purchased and installed. These systems included public address system, production and marine radios, PABX system, data network and IMMARSAT A and C satellite communication system. SAMSON has for the Cossack Refurbishing Project 50 pieces control valves type 3241 and 3251 in super Duplex and Duplex stainless delivered.

19.3. SAMSON LNG reference: KARRATHA- PROJECT, Western Australia

Natural gas, condensate and oil North West Shelf Venture - Karratha onshore gas plant supplies about two thirds of Western Australia's natural gas demand (556 terajoules a day). LNG 11.7 million tonnes a year Karratha LNG Plant Expansion - 5th LNG train (additional 4.2 million tonnes a year) Condensate Condensates are hydrocarbon gases found in reservoirs that condense to form liquids at atmospheric conditions. They are rich in naphtha and are used as a primary feedstock for petrochemical plants. Condensate is used by petrochemical plants for ethylene production in the manufacture a variety of products including plastics.

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19.4. Extract of the control valves which were delivered by SAMSON for the FPSO and LNG plant: Type 3241 Globe Valve This valve is used for a wide range of applications in process engineering and industrial plants as well as in supply and power plant engineering.

Standard valves are available conforming to DIN, ANSI und JIS standards. Valve bodies are manufactured in cast iron, spheroidal graphite iron, cast steel, cast stainless or cold-resisting steel.

Special version produced for the FPSO- Project COSSACK PIONEER with super Duplex stainless steel. Nominal size DN 15 … 300 ½” … 12” Nominal pressure PN 10 … 40 ANSI Class 150 … 300 JIS 10/20 K Temperature range –200 … +450 °C, –320 … +800 °F

Valve plug with metal sealing, soft sealing, or lapped-in metal.

Further versions are available with adjustable packing, bellows seal, insulating section, heating jacket or flow divider to reduce noise emissions.

Type 3251 Globe Valve Control valve for applications in process engineering and industrial plants as well as in supply and power plant engineering.

Suitable for large nominal sizes and/or high pressures according to DIN and ANSI standards. Valve bodies available in high- temperature, cold-resisting or cast stainless steel.

Special version produced for the FPSO- Project COSSACK PIONEER with super Duplex stainless steel. Nominal size DN 15 … 200 ½” … 8” Nominal pressure PN 16 … 400 ANSI Class 150…2500 Temperature range –200 … +500 °C, -325 … 930 °F

Valve plug with metal sealing, soft sealing, or lapped-in metal.

Further versions are available with bellows seal, insulating section, heating jacket, flow divider to reduce noise emissions, or pressure-balanced plug.

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19.5. SAMSON FPSO reference: “AOKA MIZU”

Nexen Petroleum U.K. Limited have awarded Bluewater Ettrick Production (UK) Limited, a contract for the production facilities and operations for the Ettrick field, located in the United Kingdom (UK) sector of the Central North Sea. The Ettrick field is located in the Outer Moray Firth about 120 km Northeast of Aberdeen in blocks 20/2a and 20/3a. Bluewater will utilise the "Aoka Mizu”, which will undergo an extensive conversion programme for the project. Bluewater will design, supply and operate the FPSO including topsides and a disconnectable turret mooring system. Bluewater plans to install and commission the Aoka Mizu to commence production at the Ettrick field by the 1st quarter 2008. Test drive the "Aoka Mizu" in the construction phase

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The Aoka Mizu’s main features are: Providing safe and stable floating platform for production facilities Producing well effluents through operation and control of the subsea system, including the wells Minimising the environmental impact resulting from the production of well effluents Receiving well effluents from well risers Processing incoming well effluent and separation into oil, water and gas Storing dry crude at the required temperature Treating produced water for re-injection into the reservoir Treating seawater for injection into the reservoir, mixed with produced water Injecting chemicals for process enhancement and protection of subsea and process equipment Treating and compressing produced gas for export, gas lift and fuel Offloading dry crude to tandem moored shuttle tankers Exporting gas through a subsea pipeline system Providing accommodation for operations and maintenance personnel, which also serves as safe haven with life-saving and evacuation equipment Providing a safe landing area for helicopter operations

Vessel Data Length 248.12 m Gas Lift 18 MMscfd Breadth moulded 42 m Gas Export 20 MMscfd Depth moulded 21.2 m Offloading 5,200 m3/hr Draft, design + scantling 14.9 m Dead weight tonnage 105,000 dwt Process plant Deck area 7,985 m2 Fluid capacity 35,000 bfpd Topsides area 6,000 m2 Crude production 30,000 bopd Deck payload 8,000 tonnes RVP 10 psi H2S< 3ppm

Location CO2 < 0.1 mole % Ettrick Field, North Sea BS&W < 0.5%

Performance data Water Injection Storage capacities Capacity 55,000 bwpd Exportable crude (98%) 95,000 m3 (600,000 bbls) Oxygen Content < 1 ppb Slop tanks (98%) 7,150 m3 (45,000 bbls) Fuel oil (98%) 2,982 m3 (18,000 bbls) Gas compression Capacity 35 MMscfd

Processing capacities Crude 30,000 bopd Offloading Produced water 20,000 bwpd Parcel size > 500,000 bbls

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19.6. SAMSON FPSO reference: “SMART 1” Aker Kvaerner and the Norwegian ship owner Aktieselskabet Borgestad ASA establish a new company named Aker Borgestad Operations AS, combining expertise within oil field processing and marine operations. The new company will operate oil and gas production vessels on behalf of Aker Floating Production, a company, which owns several Floating Production Storage and Offloading (FPSO) units. This business model allows Aker Floating Production to remain focused on developing business, leveraging Aker Kvaerner and Borgestad, which both have operations of assets as part of their core business.

Smart FPSO

The company Aker Floating Production standardized through modularization, planned and prepared each function and for each location. Your design allows functions to add also offshore – making the FPSO’s able to grow together with the needs of your clients.

They have made some functions so flexible that they are common for most applications. Your oil separation train is one example together with flexible utility systems. This allows starting building your FPSO’s before they have secured a lease contract – giving your clients an opportunity to produce earlier.

They have utilized the strength of an experienced management and the competence that lies within Aker in the development of “Smart FPSO” design. Aker Floating Production is entering the “own-and-operate” FPSO market with a fleet of “Smart FPSOs”.

The Smart FPSO’s will converted by existing tankers with a flexible modular design. Aker Kvaerner has signed a contract for delivery of equipment and modifications 188,697 dwt tankers, with the name S.T. Polar Alaska to convert in a product of Aker Floating Production’s type SMART 1 as FPSO vessel.

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The scope of work which will be undertaken by the Aker Kvaerner subsidiary Aker Kvaerner Process Systems includes delivery of two separation modules, one utility module and two skids for the flare system. The modules will be fabricated in Dubai and installed on the FPSO by Jurong shipyard in Singapore. Engineering, procurement and fabrication follow-up is carried out by Aker Kvaerner's Process Systems office in Oslo.

The first FPSO with SAMSON control valves were completed in the third quarter 2007 and are installed on the MA D6 field on the east coast of India.

For example: Globe valve Series 3.240 Globe Valve Type: 3241-1 Size: 6” ANSI Class 150 Body material: 1.4470 Duplex Flange form: RF raised face Ra 3,2 ... 6,3 Plug/Seat material: 1.4462 Sealing surface: Metal/metal Leakage: Class IV Cv-value: 190 log Packing: PTFE carbon spring loaded Flow direction: FTO Sound pressure level: 83 db(A)

Positioner 3730-3 Pneumatic Actuator Actuator type: 3277, 700cm2 Stroke: 30 mm Spring range: 2,1…3,3 bar Actuators with special painting: Powder-painting 180µm + Acrylic PUR RAL 2011 2 x 60µm. Fail safe position: FC

Positioner Positioner type: 3730-3 with LCD and AUTOTUNE, 4...20 mA reference variable, HART communication, 2 software limit switches/ 1 fault alarm contact. II 2 G EEx ia IIC T6 ATEX, with 1 inductive limit switch SJ 2-SN, EXPERT diagnostics, Housing material stainless Photo SAMSON AG: The control valve before the delivery steel 1.4581.

Air filter regulator type: 4708

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FPSO Aker Smart 1 will be capable of processing 60,000 barrels of oil and 80,000 barrels of liquid per day and have a storage capacity of 1,300,000 barrels of oil.

Member of the SAMSON-Group

Butterfly valve Series 14b Tight-closing, double-eccentric butterfly control valve especially for the chemical industry where aggressive Media’s are used. Our newly developed high performance shut-off and controls butterfly valve, which has its own patent and has the following special features: • Valve body made of • Steel or • Stainless steel • Body style • Wafer-Type or • Lug-Type

Control valves for the FPSO vessel "Smart 1" of the SAMSON Type 3241 after the final check. For example: Rotary Plug Valves

Member of the SAMSON-Group The range ability of the Maxifluss-Control Valve (Rotary plug valve) Type 72.X of company Vetec GmbH allows universal application. ANSI B 16.10, 150/300 lbs with flanges, face-to-face dimensions Size: 1” to 12” One end of the rugged plug or segment ball is the shaft connected to by means of a close fitting keyway. The other end is trunnion mounted. The eccentric design of plug and shaft causes the plug to lift away and clear the seat immediately as it starts to rotate. Friction between plug and seat is eliminated (triple eccentricity). The valve opens not abruptly and therefore it shows a sturdy regulation, especially with little openings. The inherent characteristic curve of the Maxifluss-Control Valve can transform into a linear or logarithmic characteristic by means of positioners and cam-plates. Maxifluss-Control Valve Type 72.3 with R250 Actuator

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19.7. SAMSON FPSO reference: “BERGE CARMEN” Mexico's company Pemex is government-operated and is the ninth largest oil and gas company in the world and the third largest producer of crude oil. Cantarell is the world's second largest oil field and the core of Mexico's oil production. Pemex has begun with the most important technical project at the moment, the expansion of the four billion barrel Ku-Maloob- Zaap (KMZ) complex.

The KMZ project comprises the development of three separate heavy oil accumulations - Ku, Maloob and Zaap - located to the northwest of Cantarell in the shallow waters of the Bay of Campeche, 105km from the city of Ciudad del Carmen. While the complex averages production of 329,000 b/d of oil and 172.1 million scf/d of gas coming from 58 wells (35 on Ku, 17 on Maloob, 5 on Zaap and 1 on the Bacab field) linked to nine platforms, and even setting production record of 363,280 b/d in August 2006, the plan now underway is to push this rate to upwards of 800,000 b/d and over 300 million scf/d by the end of the decade.

As for the FPSO, Norwegian company Bergesen Worldwide Offshore has landed the deal to convert its 360,000 dwt (deadweight tonne) Berge Enterprise ULCC into a turret moored unit capable of handling 200,000 b/d of oil production, 120 million scf/d of gas as well as storing two million barrels of oil.

The 360,000 dwt tanker “Folk Moon” ex “Berge Enterprise” is at the moment being converted in Singapore and is scheduled to start production at the Ku-Maloob-Zaap field offshore Mexico in the first quarter 2007. This will be the first FPSO in the Gulf of Mexico and one of the largest globally. The vessel is classed by DNV. The vessel “Folk Moon”, renamed to “Berge Carmen”, will be converted at company Sembawang Shipyard in Singapore, and is ready for first oil in April 2007.

Upon completion, the FPSO will have the third largest oil production capacity of all existing FPSO units in the world, as well as having the largest oil throughput of any FPSO unit. This is the first FPSO to be deployed in the Gulf of Mexico and will serve as both a hub in the area and an export terminal.

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19.8. SAMSON FPSO reference: “CUULONG MV9” Alliance was selected to perform the conceptual design, detailed engineering and procurement assistance for the Su Tu Den Field FPSO offshore Vietnam by Cuulong Joint Operating Company (CLJOC) and its partners (Petro Vietnam, Conoco UK Limited, Korean National Oil Company, SK Corporation and Geopetrol).

Location: Offshore Vietnam

Su Tu Den Field (Black Lion) field is located in Block 15-1 in the Cuu Long Basin offshore Vietnam, approximately 30 miles southeast from shore. The field is located adjacent to the Ruby field. Water depth on the field is approximately 150 feet.

FPSO: Cuulong MV9

The Cuulong MV9 FPSO, the Ruby Princess (149,500 dwt), is a new-built FPSO with storage capacity of 1,000,000 bbls. The Alliance-designed topside facility provides 65,000 BOPD of oil handling capacity, 35 mmscfd of lift gas system and 82,500 bpd of water injection. The FPSO is uniquely designed so that it can be expanded in-situ to handle 110,000 BOPD for Phase 2 of the project.

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19.9. SAMSON FPSO reference: “STYBARROW VENTURE MV16” Company MODEC is a pioneer and world leader in FPSO, FSO, and TLP technologies. In business for more than 30 years, MODEC has seen the industry expand and contract, has weathered the storms and continues to lead the way. The subsea production wells are tied back into a Floating Production Storage and Offloading (FPSO). Called the FPSO STYBARROW VENTURE MV16, the disconnectable, double-hulled unit is owned and operated by MODEC. The hull was built in Korea and then sailed to the Jurong shipyard in Singapore, where the topsides were integrated in a six-month programme.

Photo: MODEC STYBARROW VENTURE MV16

The FPSO has a storage capacity of 900,000 barrels, a total liquid process capacity of 100,000 bpd, a crude production capacity of 80,000 bpd, and gas production capacity of 45 million standard cubic feet per day. It has an internal disconnectable turret which was provided by company SOFEC. This enables the FPSO to evacuate if a cyclone were to develop in the area. As a marketable crude oil, Stybarrow will be sought after because of its blending characteristics, its low sulphur, low contaminants and moderate acid, making it a crude oil of choice for North Asian customers.

Stybarrow Oil Field, Australia Discovered in February 2003, the Stybarrow oil field is located in licence block number WA-255-P (2) in the Exmouth sub-basin, approximately 65km from Exmouth, off the north-west Australian coast. The Stybarrow oil field is located in licence block number WA-255-P (2) in the Exmouth sub-basin, off the north-west Australian coast. Stybarrow and the adjacent small oil rim of the Eskdale field, have recoverable reserves estimated to be in the range of 60 to 90 million barrels of oil. First production is expected during the first quarter of 2008. The estimated economic field life is ten years.

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Water depth is approximately 825m, making it Australia's deepest oil field development. BHP BILLITON operates the field with a 50% interest; the other 50% held by Woodside Energy Limited, Australia. Company BHP Billiton is the world's largest diversified resources company and her global headquarters are in Melbourne, Australia, with a major office in London. Supporting offices are located around the world. First Oil is planned in 1 Quarter 2008.

Positioner Type 3731-3

Photo: MODEC Silencer Type 3381

The SAMSON's customer service technician at the putting into operation of the control valves on FPSO ship STYBARROW VENTURE MV16.

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19.10. SAMSON FSRU reference: “GOLAR SPIRIT” LNG to FSRU conversion project

Foto Golar LNG: Golar Spirit

Golar LNG has been awarded two time charters by Petrobras to employ “Golar Winter” and “Golar Spirit” as a floating LNG storage and regasification vessels (`FSRU`).

Employment of Golar Spirit under this contract will commence during 2nd quarter 2008, Golar Winter will commence during 2nd quarter 2009.

Both vessels will be modified to permit regasification of LNG prior to delivery to Petrobras.

During the last five years Golar has spent significant resources on developing Floating Storage and Regasification Terminal technology. The knowledge built in this period and particularly the decision to start the conversion work for Golar Spirit without having secured firm employment put Golar in a strong position to be selected for this exciting new business.

The ship-owner, Golar LNG, will work in partnership with Keppel Shipyard, a subsidiary of Keppel Offshore & Marine Ltd, in the engineering, procurement, and construction for the project. The scope of work includes the installation of a new forward turret, side-by-side mooring system, LNG loading arms, aft thrusters with compartment and a re-gasification plant, and the replacement of cargo pumps. Work to modify Golar Spirit will be carried out at Keppel shipyard commencing in the 4th quarter 2007.

In February 2007, the Company entered into an agreement to sell new building hull 2244 to an unrelated third party. The Company has three vessels: the Golar Frost, the Golar Winter and the Golar Spirit (following the end of its long-term charter with PERTAMINA in November 2006) operating in the spot/ short-term charter market for LNG vessels, prior to them entering their intended long-term commitments. The Company has long-term customer relationships with three participants in the LNG industry, and most of the Company's revenues have been derived from these three customers, namely BG Group and its subsidiaries, Royal Dutch Shell and its subsidiaries and PERTAMINA, the state-owned oil and Gas Company of Indonesia.

The “Golar Spirit” FSRU 126.000m3 is to be positioned near Pacem of the Brazil’s northeastern coast.

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The installation of a new forward turret, side-by-side mooring system, LNG loading arms, aft thrusters with compartment and a regasification plant, and the replacement of cargo pumps.

19.11. Worldwide Distribution of FPSO’s

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19.12. SAMSON reference: FSO-, FPSO-, FSRU-, and LNG- Projects SAMSON has proved itself to the leading control valve manufacturer for gas handling systems and it was equipped with SAMSON products more than 20 gas carriers (please see item 19.14). Special expertise has developed for a variety of different gas carrier types like: • Floating storage and offloading units (FSO) • Floating production storage and offloading (FPSO) • LPG carriers • LNG carriers and LNG-FSRU (floating storage and regasification units) Reference list for FSO-, FPSO-, FSRU-, and LNG- Projects Extract Serial SAMSON Customer SAMSON Plant Customer Year Project-No. Reference Products No. 674 635 COSSACK PIONEER 3241, 3251 Woodside Energy Ltd. 1. 674 687 Refurbishing 3331, 41-23, 1999 PERTH Western Australia 703 486 FPSO-Vessel 72.4, 3780 KARRATHA, Woodside Petroleum Ltd 2. 406115 Western Australia 3251, 3780 2001 PERTH Western Australia LNG Terminal 3241, 3244, 383 354 TGE Gas Engineering GmbH BAYU-UNDAN 3. 3251, 41-23, 2001 P1152 Bonn, Germany FSO- Vessel 3780 1-0534- Bluewater Energy Services B.V. 3241, 3251, 3/0048 AOKA MIZU 4. The Netherlands 72.3, LTR 43, 2006 SAMSON, FPSO- Vessel Nexen Petroleum U.K. Limited 3730 Netherlands 3241,3251, 1 252 979 Akar Floating Production SMART 1 72.3, 2006 5. 1 308 844 Norway FPSO- Vessel BR 14b/14c, 2007 3730 Scandinavian Boiler Service Subsidiary (Asia) Pte Ltd, Singapore, BERGE CARMEN LTR 43 6. 2006 Leusch Order BW Offshore FPSO-Vessel Ball valves Oslo, Norway CUULONG MV9 7. 1 272 541 Vietnam 3730 2006 FPSO-Vessel STYBARROW 3241, 3251 2006 8. 1 231 115 Australia VENTURE MV16 3381, 72.4, 2007 FPSO- Vessel 3731-3 GOLAR SPIRIT 3241, 3251, 9. 1 348 269 Moos Maritime 2007 FRSU-Vessel 3254, 3730,

10. 1998 11. LPG carriers (please see item 19.14) to 2004

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19.13. Ship Classification Ship Classification is a system for safeguarding life, property and the environment at sea. It entails verification against a set of requirements during design, construction and operation of ships and offshore units. At that time, an attempt was made to “classify” the condition of each ship on an annual basis. The condition of the hull was classified A, E, I, O or U, according to the excellence of its construction and its adjudged continuing soundness (or otherwise). Equipment was G, M, or B: simply, good, middling or bad. In time, G, M and B were replaced by 1, 2 and 3, which is the origin of the well-known expression 'A1', meaning 'first or highest class'. The concept of classification caught on around the world. Bureau Veritas (BV) was founded in Antwerp in 1828, moving to Paris in 1832.

“Lloyd's Register of British and Foreign Shipping” was reconstituted as a self-standing 'classification society' in 1834; rules for construction and survey were published the same year.

Registro Italiano Navale (RINA) dates from 1861;

American Bureau of Shipping (ABS) traces its origins back to 1862.

Det Norske Veritas (DNV) Adoption of common rules for ship construction by Norwegian Insurance societies in the late 1850s led to the establishment of Det Norske Veritas (DNV) in 1864. Det Norske Veritas (DNV) is a global provider of services for managing risk. DNV is an independent foundation with the objective of safeguarding life, property and the environment. DNV comprises 300 offices in more than 100 countries, with 6100 employees. Registers in DNV Maritime DNV Maritime's registers, including up-to-date vessel class and survey status, register of Vessels, Class Suspensions and Withdrawals, Approved Service Suppliers, and Approved Manufacturers and Products.

Germanischer Lloyd (GL), Germany was formed in 1867 and

Nippon Kaiji Kyokai (ClassNK), Japan in 1899.

The Russian Maritime Register of Shipping (RS) was an early offshoot of the River Register of 1913.

More foundations that are recent have been Yugoslav Register of Shipping (now the Croatian Register of Shipping (CRS)) in 1949,

China Classification Society (CCS), 1956;

Korean Register (KR), 1960; and

Indian Register of Shipping (IRS), India 1975.

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19.14. SAMSON reference: It follows an extract of Gas Carriers, which are fitted with SAMSON products:

Gas Carrier Year of Reliquefaction SAMSON Shipyard Cargoes: Name completion: system: Valves: No. Photo of the Gas Carrier Capacity m3 Max. Cargo Density: Inert gas plant SAMSON Owner EPC Classification: Design temperature/ capacity: Positioner: pressure: LPG, Metaltanque Ethylene, Cascade cycle, 15 Type 3241-7 ETALEIRO ITAJAI III 1998 Ammonia, refrigerant 5 Type 41-23 Brazil VCM, Propylene 4 Type 9 Chemicals 1 3 TGE scope: 6000 m 1840 kg/m3 PSA type nitrogen METALNAVE EPCS-contract, -104 °C generation, Certificate of 3766 S.A., Brazil gas handling 5 bar g 500 Nm3/h at BUREAU system VERITAS (BV) acc. to IMO 99,5 vol. % N2

Hudong-Zhonghua LPG 17 Type 3241-7 Norgas Shipbuilding Ethylene Cascade cycle, 1 Type 3244-7 2002 Orinda (Group) Co., Ltd. Ammonia refrigerant R 404a 2 Type M 44-2 Shanghai, China VCM 4 Type 9

2 TGE scope: Norwegian 3 972 kg/m3 PSA type nitrogen EPCS-contract, 8556 m Gas Carrier generation, gas handling -104 °C 3767 (NGC), DET NORSKE 750 Nm3/h at system & cargo 7 bar g Norway VERITAS (DNV) 99,5 vol. % N2 tanks acc. to IMO

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Gas Carrier Year of Reliquefaction SAMSON Shipyard Cargoes: Name completion: system: Valves:

3 TGE scope: 3 Norwegian 8556 m 972 kg/m3 PSA type nitrogen EPCS-contract, Gas Carrier generation, gas handling DET NORSKE -104 °C 3767 (NGC), 750 Nm3/h at system & cargo VERITAS 5 bar g Norway 99,5 vol. % N2 tanks (DNV) acc. to IMO

Hudong- LPG, 17 Type 3241-7 Zhonghua Norgas Ethylene, Cascade cycle, 1 Type 3244-7 Shipbuilding 2002 Alameda Ammonia, refrigerant R 404a 2 Type M 44-2 (Group) Co., Ltd. VCM 4 Type 9 Shanghai, China 4 TGE scope: 3 Norwegian 8556 m 972 kg/m3 PSA type nitrogen EPCS-contract, Gas Carrier generation, gas handling DET NORSKE -104 °C 3767 (NGC), 750 Nm3/h at system & cargo VERITAS 5 bar g Norway 99,5 vol. % N2 tanks (DNV) acc. to IMO

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Gas Carrier Year of Reliquefaction SAMSON Shipyard Cargoes: Name completion: system: Valves:

No. Capacity m3 Max. Cargo Density: Photo of the Gas Carrier Inert gas plant SAMSON Owner EPC Classification: Design temperature/ capacity: Positioner: pressure: Hudong- LPG, 17 Type 3241-7 Zhonghua Norgas Ethylene, Cascade cycle, 1 Type 3244-7 Shipbuilding 2002 Sonoma Ammonia, refrigerant R 404a 2 Type M 44-2 (Group) Co., Ltd. VCM 4 Type 9 Shanghai, China 5 TGE scope: 3 8556 m 972 kg/m3 PSA type nitrogen Somargas EPCS-contract, -104 °C generation, Limited, gas handling DET NORSKE 3767 5 bar g 750 Nm3/h at Hong Kong system & cargo VERITAS acc. to IMO 99,5 vol. % N2 tanks (DNV)

Hudong- LPG, 17 Type 3241-7 Zhonghua Cascade / Norgas Ethylene, 1 Type 3244-7 Shipbuilding 2003 direct cycle, Napa Ammonia, 2 Type M 44-2 (Group) Co., Ltd. refrigerant R 404a VCM 4 Type 9 Shanghai, China 6 TGE scope: 3 10208 m 972 kg/m3 PSA type nitrogen Somargas EPCS-contract, generation, Limited, gas handling DET NORSKE -104 °C 3767 750 Nm3/h at Hong Kong system & cargo VERITAS 7 bar g 99,5 vol. % N2 tanks (DNV) acc. to IMO

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Gas Carrier Year of Reliquefaction SAMSON Shipyard Cargoes: Name completion: system: Valves: No. Capacity m3: Max. Cargo Density: Photo of the Gas Carrier Inert gas plant SAMSON Owner EPC Classification: Design temperature/ capacity: Positioner: pressure: LPG, Hudong-Zhonghua 17 Type 3241-7 Ethylene, Cascade / Norgas Shipbuilding 1 Type 3244-7 2003 Ammonia, direct cycle, Shasta (Group) Co., Ltd. 2 Type M 44-2 VCM, refrigerant R 404a Shanghai, China 4 Type 9 Chemicals 7 TGE scope: Norwegian 972 kg/m3 PSA type nitrogen EPCS-contract, Gas Carrier -104 °C generation, gas handling 10208 m3 3760 (NGC), 7 bar g 750 Nm3/h at system & cargo Norway acc. to IMO 99,5 vol. % N2 tanks

3 cargo Hijos de J. LPG, 13 Type 3241 compressors CELAVOVA Barreras shipyard 2003 Ammonia, 1 Type 9 BURCKARDT Vigo, Spain VCM 3 Type 44-2 2K140-2h

8 TGE scope: 970 kg/m3 PSA type nitrogen Company EPCS-contract, 3 -48 °C generation, 3767 Naviera gas handling 7000 m 6.5 bar g 600 Nm3/h at EEx ia II CT6 Globalgás system & cargo acc. to IMO 99,5 vol. % N2 tanks

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Year of Reliquefaction SAMSON Ship-Name Shipyard Cargoes completion system: Valves Max. Cargo No.: Density: Photo of the Gas Carrier Capacity Inert gas plant: SAMSON Owner EPC 3 Design m Capacity: Positioners temperature / pressure: 16 Type 3241-7 STX Shipbuilding LPG, 1 direct cycle, 3 x 4 Type 42-23 Almajedah Co., Ltd., 2003/2004 Ammonia, Sulzer compressor 1 Type 42-73 South-Korea VCM, 4 Type 9 9 Qatar TGE scope: 972 kg/m3 Membran type Shipping EPCS-contract, -48 °C nitrogen generation, Co., Doha, gas handling 23000 m3 3766 0.45 bar g 2000 Nm3/h at Qatar system & cargo acc. to IMO 99,5 vol. % N2 tanks 16 Type 3241-7 STX Shipbuilding LPG, 1 direct cycle, 3 x 4 Type 42-23 Almarona Co., Ltd., 2003/2004 Ammonia, Sulzer compressor 1 Type 42-73 South-Korea VCM, 4 Type 9

10 TGE scope: Qatar 972 kg/m3 Membran type EPCS-contract, Shipping -48 °C nitrogen generation, gas handling 23000 m3 3766 Co., Doha, 0.45 bar g 2000 Nm3/h at system & cargo Qatar acc. to IMO 99,5 vol. % N2 tanks

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Year of Reliquefaction SAMSON Ship-Name Shipyard Cargoes completion system: Valves Max. Cargo No.: Density: Photo of the Gas Carrier Capacity Inert gas plant: SAMSON Owner EPC 3 Design m Capacity: Positioners temperature / pressure: Jiangnan LPG, 15 Type 3241-7 Clamor Shipyard, Ethylene, Direct cycle, and 1 Type 3244-7 2002 Schulte Shanghai, China Ammonia, refrigerant R 404a 3 Type M 44-2 VCM 2 Type 9

11 TGE scope: 972 kg/m3 PSA type nitrogen Schulte EPCS-contract, -104 °C generation, Group, gas handling 8200 m3 3766 3.3 bar g 750 Nm3/h at Germany system & cargo acc. to USCG 99,5 vol. % N2 tanks

LPG, 15 Type 3241-7 Jiangnan Moritz Ethylene, Direct cycle, and 1 Type 3244-7 Shipyard, 2002 Schulte Ammonia, refrigerant R 404a 3 Type M 44-2 Shanghai, China VCM 2 Type 9 12 TGE scope: 972 kg/m3 PSA type nitrogen Schulte EPCS-contract, -104 °C generation, Group, gas handling 8200 m3 3766 3.3 bar g 750 Nm3/h at Germany system & cargo acc. to USCG 99,5 vol. % N2 tanks

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13 TGE scope: 972 kg/m3 PSA type nitrogen Navigator EPCS-contract, -104 °C generation, Holdings, gas handling 22000 m3 3766 3.3 bar g 1500 Nm3/h at USA system & cargo acc. to USCG 99,5 vol. % N2 tanks

LPG, 16 Type 3241-7 Another Jiangnan Ethylene, Cascade cycle, and 4 Type 42-23 4 ships of the Shipyard, 1999/2000 same Ammonia, refrigerant Propane 1 Type 42-73 Shanghai, China construction VCM 4 Type 9 14 to TGE scope: 17 972 kg/m3 PSA type nitrogen Navigator EPCS-contract, -104 °C generation, Holdings, gas handling 22000 m3 3766 3.3 bar g 1500 Nm3/h at USA system & cargo acc. to USCG 99,5 vol. % N2 tanks

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20. GAS processing plants Gas processing plants are a group of single process units. They serve for the purification and cryogenic separation of gas mixtures. Cryogenic separation technology and physical or chemical scrubbing processes come into application for these units that frequently are enquired by engineering companies implementing them as single units within a larger contract plant. Independently endusers may install them as supplement to existing gas generation facilities. The units are tailored to the individual application and requirement of the client. Frequently the complete process equipments will be assembled in the workshop and supplied as a coldbox.

The following processes are mainly used in modern plant design:

20.1. Partial condensation processes Liquid methane washes Cryogenic processes for recovering pure carbon monoxide and pure hydrogen from gases from steam reformers and partial oxidation plants. Carbon monoxide is mainly used for the production of acetic acid and formic acid, for polyurethane technology and the production of polycarbonates and methyl acrylates. The purity of carbon monoxide depend prevailing requirements and can be adjusted into the ppm range with respect to residual contents of hydrogen and methane.

20.2. Liquid nitrogen washes Cryogenic processes for purifying hydrogen and, at the same time, adjusting the stoichiometric nitrogen/hydrogen ratio for production of ammonia synthesis gas. The residual content of carbon monoxide in the ammonia synthesis gas remains less than 5 ppm and an additional purge gas separation step, in Order to recover the hydrogen, is no more required.

20.3. Separation of hydrogen and LPG from refinery fuel gas Cryogenic processes for recovering high-quality and saleable components, such as hydrogen, C3+ and LPG from refinery fuel gas.

20.4. Purge gas separation Cryogenic processes for recovering hydrogen and argon from the purge gas of ammonia synthesis gas plants, in case that the synthesis gas has been produced without a nitrogen wash.

20.5. Rare gas processing Argon may be recovered from the purge gas of ammonia plants. It can be separated and recovered as liquid argon in a cryogenic process. If suitable feedstock is available, also other rare gases like HE, Ne, Kr and Xe can be recovered.

20.6. Carbon dioxide liquefaction These are processes for the production of carbon dioxide with food quality. The main feed stocks are off gases, e.g. from ammonia production or also gases from natural sources.

20.7. Physical and chemical washes These are processes for removing acid gas (H2S+COS, C02) from various process gases. Scrubbing processes developed by company Linde AG are used, e.g. the RECTISOL® wash, which has shown excellent results in gas purification processes of almost all pertinent oil and coal gasification processes. Conventional amine washes according to outside licenses, e.g. MDEA, Sepasolv, Sulfinol or Benfield, are also used depend the technical requirements.

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20.8. RECTISOL® wash The process RECTISOL® was independently developed by Linde AG and by Lurgi AG in Germany and the patents and trade mark are used in common.

Rectisol® is a physical acid gas removal process using an organic solvent (typically methanol) at subzero temperatures. Rectisol can purify synthesis gas down to 0,1 vppm (volumetric parts per million) total sulphur (including COS) and CO2 in ppm (parts per million denotes one particle of a given substance for every 999,999 other particles) range. The main advantages of the process are the rather low utility consumption figures, the use of a cheap and easily available solvent and the flexibility in process configuration.

® A simplified flow scheme of the Rectisol process is shown above. CO2 and sulphur compounds are removed in separate fractions, resulting in a pure CO2 product (for example for urea production) and an ® H2S/COS enriched Claus gas fraction. Due to the application of Rectisol in connection with various upstream and downstream processes, a large design and operational experience is available also regarding handling of trace components.

Special features of the process are the spiral wound heat exchangers supporting energy efficiency and plant economics.

Basic Flow Diagram: Process Scheme Rectisol® Wash Commercial scale Rectisol® wash units are operated world wide for the purification of hydrogen, ammonia-, methanol syngas and the production of pure carbon monoxide and oxogases. Due to the physical nature of the process high pressure and high sour gas concentrations are particularly favorable. Rectisol® is therefore frequently used to purify shifted, partially shifted or unshifted gas downstream residue oil-, coal- or lignite gasification. Due to the low operation temperature Rectisol® is also favorable for cryogenic downstream processes, like liquid nitrogen wash, cryogenic recovery of carbon monoxide and oxogas.

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21. Gas production industries produces gas using various technologies: Cryogenic distillation for air gas: separation and isolation of Nitrogen, Oxygen and Rare gases present in small quantities in the air (Argon, Neon, Krypton, Xenon) Adsorption (Oxygen) Permeation (Nitrogen) Chemical reaction (Syngases and Hydrogen) Extraction (Helium)

21.1. This is air 78.10800 % Nitrogen 20.93200 % Oxygen 0.917000 % Argon 0.040000 % Carbon dioxide 0.001820 % Neon 0.000525 % Helium 0.000114 % Krypton 0.000050 % Hydrogen 0.000009 % Xenon

(Main ingredients: figures indicate volume percentage)

The gas production industry uses gas naturally present in the atmosphere, and then separates and purifies them for all kinds of applications.

In addition to these, they use other natural resources of gas and also produce certain gases by chemical reaction. These gases are then sent to customers by pipeline, compressed, put into cylinders, and are delivered in liquid form or, in some cases, are produced directly on the customer’s site.

21.2. Industrial gases – components for synthesis processes Industrial gases find vast and versatile application in the chemical industry. They serve as feed materials for synthesis processes, they ensure and improve the economy of processes and plants, they enhance product quality and plant safety, and they help to protect the environment.

Supply of gases must be matched specifically to the diversity of products, processes and production capacities. Essential factors in this are dependability, economy and wide-ranging applications solutions.

In the chemical industry industrial gases are used principally as chemical reactants for assuring plant safety for protection of the environment in analytical chemistry for industrial service. Oxygen, hydrogen, carbon monoxide, carbon dioxide and synthesis gas are reactants in a large number of important synthesis processes. The accompanying charts summarize common reactions working with oxygen, hydrogen, carbon monoxide and carbon dioxide.

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Among the best known are:

21.3. Oxygen (O2)

Oxygen (O2) is colorless, odorless and tasteless. Oxygen has a low boiling/ condensing point: -297.3°F (-183°C). The gas is approximately 1.1 times heavier than air and is slightly soluble in water and alcohol. Below its boiling point, oxygen is a pale blue liquid slightly heavier than water. At atmospheric pressure, liquid oxygen only takes up 1/854 of its gaseous volume. This allows large quantities of oxygen to be transported and stored in cryogenic, liquid form.

Oxygen is the second-largest volume industrial gas. It is produced as a gas or liquid by cryogenic distillation and as a relatively pure gas by adsorption technologies (PSA, VPSA, and VSA). (See section 23.)

Oxygen is highly oxidizing (a general chemical term applying to any substance, like oxygen, that accepts electrons from another substance during reaction). Oxygen reacts vigorously with combustible materials, especially in its pure state, releasing heat in the reaction process. Many reactions require the presence of water or are accelerated by a catalyst.

This is essential in the medical field (to revive patients, for respiratory illnesses …). It also has very many uses in industry: bleaching of paper pulp without endangering the environment, purification of water, manufacturing of plastics. It is applied in many combustion processes (blast furnaces, glass ovens). It is used for welding and cutting metal in combination with acetylene. It is necessary for the cryogenic engines of rockets e.g. ARIANE. Pure oxygen is used in the manufacturing of semiconductors.

21.3.1. Reactions with oxygen

Paraffins, olefins Aldehydes

Paraffins, olefins Alcohols

Oxygen Olefins Epoxides

Olefins, Aldehydes Carboxylic acids

Petroleum refining residues Synthesis gas

Hydrogen sulphide Sulphur

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21.3.2. Oxygen improving economy and reducing the investment costs Increasing use is being made of industrial oxygen in oxidation processes for the manufacture of oxides, aldehydes, and also acids and alcohols. It can greatly improve the economy of existing plants and reduce capital expenditure for new plants. The methods used are oxygen enrichment of the oxidizing air, adding oxygen to the feed stream and substituting pure oxygen for air.

The benefits of oxygen are: Larger throughput in the same size of plant by lowering the concentration of inert nitrogen Higher temperatures in the reacting stream Accelerated reactions due to higher oxygen concentration Higher selectivity of the oxidation process in parts Smaller off-gas flows Lower energy consumption.

21.3.3. Oxidation processes using oxygen

Product Feed Air Oxygen Enriched air

Acetaldehyde Ethylene

Benzoic acid Toluene Cyclohexanone Cyclohexane

Acetic acid Acetaldehyde Ethylene oxide Ethylene

Propylene oxide Propylene Nitrogen monoxide Ammonia

Terephthalic acid p-Xylene Vinyl acetate Ethylene, acetic acid

Vinyl chloride Ethylene, hydrogen chloride Hydrogen peroxide Hydrogen

Industries: aerospace, chemical, electronic, glass and enamel industry, pulp and paper, healthcare, food, oil and gas, steel, welding & cutting, biotechnology industry, public and private waste water treatment and waste disposal industries.

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21.4. Nitrogen (N2)

Nitrogen (N2) is a colorless, odorless and tasteless gas that makes up 78.09% (by volume) of the air we breathe. It is nonflammable and it will not support combustion. It is colorless, odorless and tasteless. Nitrogen gas is slightly lighter than air and slightly soluble in water. It is commonly thought of and used as an inert gas; but it is not truly inert. It forms nitric oxide and nitrogen dioxide with oxygen, ammonia with hydrogen, and nitrogen sulfide with sulfur.

Nitrogen compounds are formed naturally through biological activity. Compounds are also formed at high temperature or at moderate temperature with the aid of catalysts. At high temperatures, nitrogen will combine with active metals, such as lithium, magnesium and titanium to form nitrides. Nitrogen is necessary for various biological processes, and is often uses as a fertilizer, usually in the form of ammonia or ammonia-based compounds. Compounds formed with halogens and certain organic compounds can be explosive. Nitrogen condenses at its boiling point, -195.8o C (-320.4o F), to a colorless liquid that is lighter than water. Nitrogen has numerous applications in the industrial and research sectors. In most of these applications, it is used either physically (as a refrigerant) or chemically (as an inert gas), i.e. it is returned unchanged to the atmosphere after usage.

21.4.1. Multi-Industry Uses: The inert properties of nitrogen make it a good blanketing gas in many applications. Nitrogen blanketing is used to protect flammable or explosive solids and liquids from contact with air. Certain chemicals, surfaces of solids, and stored food products have properties that must be protected from degradation by the effects of atmospheric oxygen and moisture. Protection is achieved by keeping these items in (under) a nitrogen atmosphere. "Inerting" or "padding" is other terms used to describe displacement of air and nitrogen blanketing. "Sparging" with nitrogen is the bubbling of nitrogen through a liquid to remove unwanted volatile components, including volatile organic compounds (VOC) which may be necessary to meet pollution reduction regulations. Certain substances are difficult to pulverize or shred because they are tough or the materials will be degraded by the heat generated by mechanical processes such as grinding.

Liquid nitrogen can be used to freeze soft or tough substances prior to their entering a size reduction process. Cold vaporized nitrogen can be used to keep materials cool (and in an inert atmosphere) during grinding. Cryogenic grinding is used in diverse applications, including production of finely ground pharmaceuticals, plastics and pigments; and for shredding tires in recycling plants. Industries: chemical, food, glass, healthcare, metal, pulp & paper, oil & gas, steel, welding & cutting

21.5. Rare or noble gases The so-called "rare" or noble gases Neon (Ne), Krypton (Kr) and Xenon (Xe), are present in air in very low concentrations. Like the other "noble" or "inert" gases, helium (He), argon (Ar) and radon (Rn), Neon, Krypton and Xenon remain in the air because they do not combine with other materials to form solid or liquid compounds. All of these gases are monatomic. Neon, Krypton and Xenon can be economically recovered by adding additional purification steps in large air separation plants or ammonia production plants (which use large amounts of air as a raw material). Neon can be recovered from large nitrogen plants as well as multi-product air separation units. Krypton and Xenon have higher boiling points than oxygen, from which they can be separated by distillation in air separation plants. When these products are recovered from ammonia plant purge gas, the neon must be separated from hydrogen and nitrogen, and the krypton and xenon from methane.

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21.5.1. Argon (Ar) Argon (Ar) is a monatomic, colorless, odorless, tasteless and nontoxic gas, present in the atmosphere at a concentration of just under 1% (0.917%) by volume. Argon, along with helium, neon, krypton, xenon and radon, is a member of a special group of gases known as the “rare,” “noble,” or “inert” gases.

These gases are all monatomic and have their outermost shell of electrons filled. The terms "Noble" and "inert" indicate that members of this family of gases have extremely weak tendency to chemically interact with other materials. They all emit light when electrically excited. Argon produces a pale blue-violet light.

Argon's normal boiling point is a very cold –302.6°F (–185.9°C). The gas is approximately 1.4 times as heavy as air and is slightly soluble in water. Argon's freezing point is only a few degrees lower, –308.8°F (–199.3°C). Often used as a screen gas, argon improves the quality of welding, the manufacture of semi conductors, and allows the thermal processing of metals to give them certain physiochemical properties

Argon is the most abundant of the rare gases. It is produced, most commonly, in conjunction with the manufacture of high purity oxygen using cryogenic distillation of air.

Industries: electronics, food, metal, steel, welding & cutting Rare Gases: Neon (Ne), Krypton (Kr) and

21.5.2. Xenon (Xe) These gases which are present in very small quantities in the air, have applications in lighting, the manufacturing of tinted glass or insulation in double glazing, and in the installation of telecommunications systems in space.

Industries: laboratory & analyses, aerospace, glass Among others of the well known gases, are those which are not air gases but gases resulting from reactions like:

21.5.3. Helium (He) Apart from its main usage for inflating balloons, helium is used in the aerospace industry to pressurize the cryogenic tanks, and in other applications to detect leakages and to create an atmosphere super- conductive.

Industries: electronics, food, glass, metal, steel, welding& cutting, healthcare

21.6. Ozone (O3) Ozone is used to neutralize odours, sterilize water, disinfect and sanitize food and vegetables, to bleach textiles and paper pulp, and also in certain chemical manufacturing processes. Ozone also maintains the quality of air in coolers, storage rooms and materials for packaging.

Industries: food, pulp and paper, water purification

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21.7. Hydrogen (H2)

Hydrogen (H2) is a colorless, odorless, tasteless, flammable and nontoxic gas at atmospheric temperatures and pressures. Produced from hydrocarbons or by electrolysis of water, Hydrogen is very largely used in the chemical industry for the manufacture of polymers, the desulphurization of fuels. It is the clean fuel of the engines functioning from fuel cells. Hydrogen burns in air with a pale blue, almost invisible flame. Hydrogen is the lightest of all gases, approximately one-fifteenth as heavy as air. Hydrogen ignites easily and forms, together with oxygen or air, an explosive gas (oxy-hydrogen). Hydrogen has the highest combustion energy release per unit of weight of any commonly occurring material. This property makes it the fuel of choice for upper stages of multi-stage rockets.

21.7.1. Reactions with hydrogen

Nitrogen Ammonia

Carbon monoxide Methanol Carbon dioxide

Short-chain and desulphurized Petroleum products petroleum products

Hydrocarbons Hydrogenated hydrocarbons

Hydrogen

CO + olefins Aldehydes

NO+sulphuric acid Hydroxylammonium sulphate

Metal oxides Metals

Air (anthraquinone process) Hydrogen peroxide

Much has been said about hydrogen being the "fuel of the future" due to its abundance and its non- polluting combustion products. Less has been said about the fact that other forms of energy must be used to produce the hydrogen which will be used as fuel. Most hydrogen is bound up in compounds such as water or methane, and energy is required to break the hydrogen free from these compounds, then separate, purify, compress and/ or liquefy the hydrogen for storage and transportation to usage points. Currently, there is a great deal of interest in hydrogen fuel cell technology development and investigations into unconventional or specialized hydrogen storage systems. New technologies and equipment developed to support these applications will undoubtedly find uses in industry as well. Industries: chemical, electronic, food, glass, metal, oil & gas, steel, welding & cutting

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21.7.2. For example: Space & Aeronautics, ARIANE Tanks Since 1962, AIR LIQUIDE has partnered with the European space industry through its Cryospace subsidiary (55% Air Liquide/45% EADS). Today, Air Liquide is the main supplier of cryogenic propellants for the Ariane space program, for which it develops special reservoirs.

Hydrogen is the energy gas. Without it, there would be no rockets… space programs use a great deal of hydrogen because of its heavy energy density.

Ariane IV Tanks

With its 8.2 metric tons of liquid hydrogen and liquid oxygen, the propellants tanks of the third stage of Ariane 1 - carried a satellite weighing 1,850 kg.

The tanks on the Ariane IV, loaded with an extra 3.6 metric tons of propellants, carried a 4,700 kg payload and underwent twice the lift-off thrust. Yet it weighs only 110 kg more and it cost only half as much as the previous model. AIR LIQUIDE experienced teams managed to achieve this progress while ensuring a constantly high level of quality.

Ariane V Tanks

The oxygen tank of new-generation Ariane V launch vehicle is pressurized by a liquid helium subsystem designed and manufactured by AIR LIQUIDE and containing 1,100 liters of fluid.

Compared with pressurization by oxygen, the mass saving achieved by this vacuum-insulated tank allowed the launch vehicle's payload to increase by more than 200 kg.

AIR LIQUIDE are also joining forces with EADS-LV in Cryospace GIE, taking part in the development and production of the main stage cry technical tank for Ariane V.

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21.8. Carbon Dioxide (CO2) Extract of natural layers or starting from combustion hydrocarbons, carbon dioxide enters the composition of the atmosphere for the conservation of food, the carbonation of fizzy drinks, and the freezing of fish, meats and other foodstuffs. It is also used as a barrier blocking certain chemical reactions such as combustion. For this reason carbon dioxide is used in certain fire extinguishers.

21.8.1. Reactions with carbon dioxide

Ammonia Urea

Sodium phenolate Salicylic acid

Carbon dioxide Metal hydroxides Carbonates, hydrocarbonates

Hydrocarbons Esters

Alkylene carbonates, Alkylene oxides polyalkylene carbonates

Carbon dioxide (CO2) is a slightly toxic, odorless, colorless gas with a slightly pungent, acid taste. Carbon dioxide is a small but important constituent of air. Its typical concentration is about 0.04% or 380 ppm. Exhaled air contains as much as 4% carbon dioxide. CO2 gas is 1.5 times as heavy as air, thus if released to the air it will concentrate at low elevations. Carbon dioxide will form "dry ice" at -78.5ºC (-109.3º F).

Carbon dioxide is formed by combustion and biological processes including decomposition of organic material, fermentation and digestion. It combines with water in air to form carbonic acid which corrodes metals, limestone and marble. Large quantities are produced by lime kiln operation, ammonia production and magnesium production from dolomite.

Carbon dioxide is a versatile material, being valued by various users for its reactivity, inertness and coldness. Common uses include fire extinguishing systems; carbonation of soft drinks; freezing of food products such as poultry, meats, vegetables and fruit; chilling of meats prior to grinding; refrigeration and maintenance of ideal atmospheric conditions during transportation of food products to market; enhancement of oil recovery from oil wells; raw material for production of various chemicals and treatment of alkaline water.

Industries: food, healthcare, pulp & paper, steel, welding & cutting

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21.9. Acetylene (C2H2) Acetylene is a synthetic gas and is an important constituent of Polymer chemistry. This gaseous hydrocarbon is used (in the presence of oxygen) in metal cutting and welding constructions, and to lubricate moulds in the manufacturing of glass bottles. + H 2 Ethene Different products like Ethylenoxid, Ethanol etc..

+ HCL Vinyl chloride Polyvinylchloride (PVC)

+ CO / H O 2 Acrylic acid Polymere Acrylates

+ HCN Acrylic nitrile Polyacrylnitril (PAN)

Polyester + 2 CH2O + 2 H2 Butinediol 1,4 -Butanediol Polyurethane THF

+ 2 Cl - HCl 2 Tetrachloroethane Trichlorethene Solvent

+ H2O + ½ O2 Acetylene Acetaldehyde Acetic acid

+ Ethene +HCl Vinyl acetylene Chloroprene Rubber

+ HOAc Polyvinylacetate (PVAC) Vinyl acetate Polyvinyl alcohol (PVAL)

+ RCOOH Vinyl ester

+ R-OH Vinyl ether

+ Acetone Isoprene Rubber

Thermo- Soot cracking

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21.9.1. SAMSON reference: BASF PolyTHF (Tetrahydrofuran [THF]) plant in Caojing (Shanghai) The world’s largest PolyTHF plant now in operation in China and it is the first use of innovative BASF technology for THF.

SAMSON control valves were installed in this THF plant.

Photo: BASF AG

After less than two years of construction, BASF has started up its new PolyTHF® (polytetrahydrofuran) plant at the integrated production site at the Shanghai Chemical Industrial Park (SCIP) in Caojing, Shanghai.

By the middle of 2005, BASF will also gradually start up its neighboring THF (tetrahydrofuran) plant. With an annual capacity of 60,000 metric tons of Poly THF and 80,000 metric tons of THF, this is the largest PolyTHF production facility in the world. This is also the first investment project in China that has been wholly owned by BASF right from its inception.

A new proprietary technology for THF production is being used for the first time by BASF in Caojing. In this process, butane - obtained from widely available natural gas – is used as a raw material for manufacturing THF, which is then used to produce PolyTHF. The innovative process eliminates the intermediate step of 1,4-butanediol (BDO), which was previously necessary.

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21.9.2. SAMSON reference: Bayer isocyanates project in Caojing (Shanghai)

SAMSON control valves were installed in this isocyanates project in Caojing (Shanghai).

Photo: Bayer MaterialSience

Bayer MaterialScience began work on the first phase of its isocyanates project in Caojing, Shanghai, in October 2004. The first phase will include a hexamethylene diisocyanate (HDI) unit and a polymeric and monomeric methyl di-pphenylene isocyanate (MDI) facility. Bayer plans to bring on-stream 30,000 tpa of HDI by 2006 and another 20,000 tpa thereafter.

The MDI unit, slated for start-up by mid-2006, will source crude MDI from BASF and its partners until Bayer’s own 230,000 tpa crude MDI units is ready in 2008.

The BASF JV is to start up a 240,000 tpa MDI unit, also in Caojing, by end-2006. Bayer will also build a 160,000 tpa toluene diisocyanate (TDI) unit and a 200,000 tpa polycarbonate (PC) plant. The planned TDI unit is due on-stream in 2009; construction has already begun on the PC project. Bayer will bring on- stream the first 100,000 tpa of PC in Q2 2006. The plant’s capacity will be doubled, possibly by 2010. A 40,000 tpa compounding facility is also scheduled to start up at end-2005.

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21.10. Carbon Monoxide (CO) Carbon monoxide, with the chemical formula CO, is a colorless, odorless and tasteless gas and is used in different degrees of purity in a large number of processes. In standard quality, it is used to manufacture phosgene and acetic acid. In extremely pure form, it is used as a component of test and calibration gases, and for manufacturing synthetic diamonds. Industries: chemical, pharmaceutical

21.10.1. Processes for Manufacturing Carbon monoxide CO is generated by reforming hydrocarbon-content feed stocks as natural gas, mineral oil fractions or coal and always comes about in conjunction with hydrogen in mixture ratios characterized by the C/H ratio of the individual feed stocks.

Block Diagram: Basic process steps for CO manufacture

Feedstock CO Syngas Syngas CO Extraction Production Purification

Steam Reforming Chemical Wash Membrane Separation Processes CO Reforming Low Temperature 2 (MDEA, MEA, DEA) Shift Conversation Authothermic Reforming Physical Wash (Methane Wash, Tandem Reforming Processes (Rectisol®) Condensation Processes) Partial Oxidation Selective Adsorption

21.10.2. Reactions with carbon monoxide Carbon monoxide (CO) is a colourless, odourless poisonous gas and has a special significance as a raw material for the chemical industry. Pure CO is primarily required for the production of:

Methanol

Hydrogen Hydrocarbons

Aldehydes, alcohols

Carbon monoxide Olefins Carboxylic acids

Chlorine Phosgene

Metal carbonyls Metals

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22. On-site gas supply Environmental protection and legal requirements require reduction of pollutants in Diesel fuel and gasoline. One efficient way to accomplish that is to use industrial gases for various purification processes in oil refineries. Large quantities of gases are produced in so-called on-site plants in the immediate vicinity of the users. That is an extremely economical possibility of refinery operation.

22.1. On-site supply of hydrogen Hydrogen consumption by refineries increases rapidly with more stringent desulphurization, because the amounts of substances other than sulfur compounds which are hydrogenated also increase. That is particularly the case for nitrogen compounds. Large volumes of hydrogen are used, which can be produced economically by onsite supply. For such large users, it is economically feasible to generate the hydrogen on-site with the steam reforming process. In principal, one might also consider generation by a partial oxidation plant. That can be done practically in only a few cases, though, in which it is either necessary to process residues, or to produce a synthesis gas, as if the supply is for methanol production.

22.1.1. Steam reforming is the most widespread process for the generation of hydrogen-rich synthesis gas from light carbohydrates and water steam. The following figure shows a block flow diagram of the process. The starting materials could be natural gas, naphtha, LPG (liquefied petroleum gas) or refinery gases (feed and fuel).

The feed gas, hydrocarbon from natural gas (methane) to naphtha, and perhaps refinery gas that would otherwise be used only as a fuel within the plant, is passed through a desulphurization plant with a small quantity of recycling hydrogen. This unit includes a hydrogenator and a zinc oxide bed for the actual sulfur removal. The hydrogenator converts unsaturated hydrocarbons, which tend to crack, to alkanes. In parallel, sulfur compounds are converted to hydrogen sulfide. The sulfur compounds are trapped in the zinc oxide bed.

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Steam reforming, hydrogen reforming or catalytic oxidation, is a method of producing hydrogen from hydrocarbons. On an industrial scale, it is the dominant method for producing hydrogen. Small-scale steam reforming units are currently subject to scientific research, as way to provide hydrogen to fuel cells.

SAMSON control valves

Photo Linde AG: A part of the steam reformer

The main production processes providing CO, H2 or syngas are:

■ Steam reforming (SR), a catalyzed reaction of gaseous or liquid hydrocarbons and steam to yield a mixture of H2, CO and CO2, ■ Partial oxidation (POX), a non- catalytic reaction of hydrocarbons, petroleum coke, coal, chemical waste or biomass with steam and oxygen, ■ Autothermal reforming (AR)which combines steam reforming and partial oxidation in a single reactor, ■ Combined reforming (CR), a Photo Linde AG: Hydrogen plant combination of steam reforming and oxygen-based secondary reforming.

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22.1.2. ThyssenKrupp-Uhde Steam reforming – process options for the production of Hydrogen (H2) Flow sheet hydrogen plant

Linde hydrogen plant

1 Steam generator 2 Feed / Steam preheater II 3 Feed / Steam preheater I 4 Steam supheater 5 Feed preheater 6 Condensate preheater 7 Combustion air preheater 2. CO shift options

Reaction equations

Of Methane Ni CH4 + H2O CO + 3 H2 800 to 900 °C

Of Hydrocarbons (general) Ni -CH2- + H2O CO + 2 H2 3. CO shift options 800 to 900 °C

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The various process options in the above sections represent the addition of a process step to the conventional process with the objective of reducing the feed and/or fuel consumption. Uhde provides processes involving the steam reforming, Combined Autothermal Reforming (CAR®) and Autothermal Reforming (ATR) for the production of hydrogen. In all process routes, the reforming step is followed by shift conversion and final product purification.

SMR = Steam Methane Reforming

The best option for producing hydrogen from light hydrocarbons is steam reforming. This is where hydrocarbons are reacted with steam to produce mixtures of hydrogen and carbon oxides. The steam reforming reaction takes place in reformer tubes which are filled with catalyst. Since the reaction is endothermic, external heat is required. This is supplied by burners positioned on top of the furnace which ensure optimum uniformity of the skin temperature profile of the reformer tubes.

22.1.3. SAMSON reference: Onsite plant for the production of hydrogen in the Steam-Reforming procedure.

This hydrogen plant produces 21 million standard cubic metres H2 with a purity of 99.999 volume per cent every year.

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23. Air Separation Technology Overview Air separation plants produce nitrogen, oxygen and argon using air and electrical power as raw materials. While there are variations in process details, reflecting desired product mix and other factors, all air separation plants belong to one of two general process categories:

Cryogenic plants - Produce gas (and liquid) products using very low temperature distillation to separate air components and achieve desired product purities. Non-cryogenic plants - Produce gaseous products with near-ambient temperature separation processes that utilize differences in properties such as molecular structure, size and mass to generate oxygen or nitrogen.

Non-cryogenic air separation processes operate at near-ambient temperature and use physical property differences other than boiling point, such as molecular size and mass, to produce commercially valuable gaseous products such as nitrogen and oxygen.

The most common technologies are PSA (Pressure Swing Adsorption), used in nitrogen generators and oxygen generators; VPSA (Vacuum-Pressure Swing Adsorption), used in oxygen generators; and Membrane Separation, used to produce nitrogen gas.

These non-cryogenic gas separation technologies are also used in other industrial applications requiring separation and purification of gases. Examples are purification of hydrogen and removal of water vapor and carbon dioxide from compressed air or other gases.

23.1. Pressure swing adsorption (PSA) PSA is a unit operation for splitting gas mixtures. It is a separation method for gas mixtures in which, as the name implies the pressure is changed periodically.

A PSA process separates gases from a mixture by selectively adsorbing certain gases more strongly than other gases onto an adsorbent. As the gas mixture flows through the bed of solid adsorbent, the bed retains the more strongly adsorbed gases, while the less strongly adsorbed gases pass through the bed and can be recovered at pressure. Once an adsorbent bed is completely saturated with the adsorbed gases, dropping its pressure causes spontaneous desorption of the adsorbed components and regenerates the bed.

The well-proven PSA systems provide an economic and reliable separation and purification of a wide range of process gases. The capacities range from small plants of 100 Nm3/h to large scale plants of 300,000 Nm3/h feed gas flow.

These PSA systems are suitable for the most different applications and wide range of feed gases in the refining, petrochemical, chemical and iron/steel-making industry etc.

The main application of this process is the recovery of purification of hydrogen from raw gases, such as steam reformer, partial oxidation, refinery, ethylene, coke oven, and methanol and ammonia off-gases. The hydrogen product obtained meets every purity requirement (up to 99.9999 %) and is achieved as highest recovery rates.

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23.2. SAMSON reference: Linde AG ECOVAR® - C (C = cryogenic process) With its innovative gas supply concepts, Linde Gas is playing a pioneering role in the global market. As a technology leader, is your task to constantly raise the bar. Traditionally driven by the entrepreneurship, are working them steadily on new high-quality products and innovative processes.

Economical ECOVAR® supply systems are built around standardized components to ensure maximum cost efficiencies. SAMSON control valve Standardized design and dimensions play an important Type 3241 role in cutting the costs involved in engineering, building, installing, operating and maintaining on-site gas supply systems.

Through optimal combination of production plant and backup unit the ECOVAR® concept offers solutions with minimal capital expenditure, operational costs and consumption of utilities, such as energy and water.

Variable The ECOVAR® portfolio is extremely flexible. Systems and system modules can be combined as required to create tailored solutions that suit local requirements.

ECOVAR® systems can be designed for indoor or outdoor installation to fit available space and for availability of utilities (energy, water and compressed air).

ECOVAR® plants are generally mounted in cabinets, on skids or in containers for fast, trouble-free installation/ commissioning and relocation.

To suit individual flow, purity and pressure requirements, Linde Gas has developed a series of standard plant product lines for nitrogen, oxygen and hydrogen.

® Reliable Photo Lind Gas: ECOVAR -C plant ECOVAR® systems comprise a standard plant and a back-up unit to ensure uninterrupted supply all year round (8760 hours). Automatic control systems track fluctuations in demand, automatically activating the back-up unit to support production peaks. The back-up unit can also be activated in the event of a plant stop.

Both the production plant and back-up unit are normally monitored by the nearest Linde Gas center to ensure a reliable gas supply.

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Environmentally sound ECOVAR® systems are more environmentally friendly than conventional supply methods. Product transport and energy consumption are reduced to a minimum by producing the required gas on-site. The Linde AG ECOVAR® supply concept combines an on-site production unit and liquid storage tank for supply of nitrogen or oxygen. Basic demand is covered by the capacity of the production unit with a reserve supply available in the storage tank to meet peak consumption and emergency situations. Customers can choose among three alternatives according to the required product, purity and production capacity: ECOVAR®-M (M = membrane process) ECOVAR®-C (C = cryogenic process), or ECOVAR®-A (A = adsorption process).

All three types are marked by high reliability of supply, economical production cost and a high level of flexibility.

23.2.1. Nitrogen Membrane plants Nitrogen can be purified economically down to about 1% residual oxygen in membrane plants. The actions of the ultra thin polymer membranes and their separating ability depend on the pressure, temperature, composition of the gas stream, and the flow geometry.

Membrane plant diagram

Membrane nitrogen generators use tube bundles made of special polymers configured in a manner similar to a shell and tube heat exchanger. The air separation principle is that different gases have different permeation rates through the polymer film. Oxygen (plus water vapor and carbon dioxide) are considered "fast gases" that diffuse more rapidly through the tube walls than the "slow gases" argon and nitrogen. This allows dry air to be converted to a product that is an inert mix of mostly nitrogen gas and argon, and a low-pressure "permeate" or waste gas that is enriched in oxygen (plus water vapor and carbon dioxide) and vented from the shell.

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Nitrogen product emerges from membrane units at close to the compressed air feed pressure. In many applications this means that no supplemental product compression is required. Because there are no moving parts in the separation process, membrane units can be rapidly activated when needed and shut down when they are not. In membrane plants, compressed pre-purified air flows through long hollow fibers with semi permeable walls. Molecules of oxygen, carbon dioxide and water pass through these membranes faster than nitrogen. That results in separation of the air. The oxygen, carbon dioxide and water diffuse into the outer volume around the hollow fibers and are released as residual gas (permeate). Much of the nitrogen remains inside the hollow fiber, where it becomes concentrated and finally leaves the ends of the fibers as retentate.

The hollow-fiber membranes are assembled into modules. The modular design of a membrane plant allows flexible operation. The capacity of a membrane plant depends, among other things, on the number of modules connected in parallel. It can be expanded or reduced at any time if the requirement changes.

Membrane plants are used primarily for smaller consumptions up to 1000 Nm3/hour. They do not need much space or investment, and are robust and simple to operate.

SAMSON reference: Linde AG Membrane plant (ECOVAR®-M) for 120 m3/h nitrogen

SAMSON Self-operated-regulator (Pressure Reducing) Type 44-1 SAMSON control valve Type 3241

Photo: Linde AG

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23.3. Adsorption plants In adsorptive nitrogen recovery, one uses the different dynamics of gas molecules on adsorption on special activated charcoals. These carbon molecular sieves (CMS) have many pores and cavities with dimensions similar to those of oxygen and nitrogen molecules. As the oxygen molecules are somewhat smaller than the nitrogen molecules, they can penetrate into the cavities of the CMS faster than the nitrogen molecules.

23.3.1. Diagram of a Nitrogen (N2) PSA plant

SAMSON control valve Type 3241 with actuator Type 3275

Adsorptive pressure-swing (PSA) plants for nitrogen have basically four units: air compression, with air preparation if necessary adsorptive N2 / O2 separation product storage, with product recompression if necessary evacuation (only for vacuum plants) There are several processes for industrial nitrogen recovery by adsorption, but the most widely used one is the “1 bar/8 bar” process, which was developed in the 1970s.

Outside air is drawn in through a filter by a compressor and compressed to about 8 bar. This process air flows through adsorber A. Water, in particular, is adsorbed in the lower part of the adsorber, while oxygen is adsorbed preferentially in the rest of the adsorber. Nitrogen, or a nitrogen-rich product, is removed at the head and goes to the product buffer.

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In parallel with this adsorption step, container B, which previously operated in the adsorption phase, is regenerated by decompression to atmospheric pressure through a sound damper. When adsorber A has become loaded, after 40 to 60 seconds, the pressure is equilibrated between the containers at both ends. That makes optimal use of the remaining pressure and purity potential of the loaded adsorber. The pressure balancing lasts for 1 to 3 seconds, after which the system is adjusted to an intermediate pressure of about 4.5 bar. After the pressure balancing, adsorber A is regenerated by depressurizing to atmospheric pressure and adsorber B is switch to the adsorption phase. That is, it is loaded with process air.

Some basic rules must be followed for reliable long-term operation of the plant in this process. The CMS must be fixed absolutely firmly in place, because any “agitation” of the CMS leads to excessive dusts formation due to abrasion. The process air must be free of oil, which can actually be assured only by using oil-free compressors. Appropriate measures must be employed to prevent the moisture in the air making the CMS unusable in the long term.

23.4. Cryogenic Nitrogen (N2) plants The process of cryogenic air separation for nitrogen recovery is made up of the following steps: air compression air purification air chilling separation in the rectification column and recovery of the cooling potential.

23.4.1. Diagram of a small Nitrogen (N2) plant

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In cryogenic nitrogen recovery, the materials are usually separated in a single column. In special cases, though, it may be appropriate to use two columns for nitrogen recovery, to save energy, for instance.

As cryogenic nitrogen plants are economical even as relatively small units, these plants often do not require their own refrigeration using a turbine, and instead inject small amounts of liquid nitrogen.

Small cryogenic plants are assembled, ready to use, in the shop and then subjected to a test run. That assures that customers will later be able to put them into operation with a brief and reliable start-up. For larger plants, the individual units are prebuilt and tested at the plant. That also speeds up on-site assembly and start-up.

Linde is the technological and market leader for air separation plants. An air separation plant in Terni, Italy, is pictured.

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® 23.4.2. SAMSON Nitrogen (N2) plant reference: The Mahler NITROSWING System

SAMSON valves

The Mahler NITROSWING® systems produce nitrogen to capacities of more than 200 tpd at purities with a residual oxygen content of 500 ppm. For higher purities, a subsequent treatment is required.

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23.5. On-site supply with oxygen Hydrogen has always been used in refineries. Use of oxygen is not as common, though. That may change soon under the new rules. There are two reasons for that: Excess capacities for petroleum production are being reduced for better economy. However, the new environmental laws require added capacities in some plants. As noted above, for instance, that occurs for some plants such as fluid catalytic crackers to utilize heavier feed oils, or in Claus plants, where more sulfur and considerably more ammonia appear from the hydrotreaters. Then the lack of capacity can be provided by oxygen enrichment, which requires only minor changes in existing plants. Similarly, wastewater treatment plants capacities can be increased by use of oxygen. Oxygen gasification of residues makes it possible to establish a broader economic basis for a refinery and to make it more flexible and economical. The gasification gas can be used for many purposes, particularly for hydrogen recovery, as synthesis gas, especially in C1 chemistry, and as fuel gas in an IGCC (Integrated Gasification Combined Cycle) power plant.

Pressure-swing adsorption (PSA) and cryogenic processes are generally used for oxygen recovery.

Oxygen recovery using adsorption technology is based on the property of porous adsorbents, “molecular sieves”, to bind gases at their surfaces. The two major components of air, oxygen and nitrogen, are adsorbed to different extents, depending on the pressure and temperature. The pressure dependence is utilized to separate the oxygen from the nitrogen. The process operates at elevated pressure in the adsorption phase and under vacuum in regeneration. Therefore such plants are called vacuum-pressure swing adsorption plants, or, briefly, VPSA plants

23.5.1. Diagram of a Oxygen adsorption VPSA plant

SAMSON control valve Type 3241 with actuator Type 3275

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There are systems with one, two, or three adsorbers. In each adsorber, the cycle is generally made up of three steps: adsorption phase (collection of the product) desorption phase (regeneration of the adsorber) pressure buildup (preparation for the adsorption phase). A cycle lasts for about 60 to 180 seconds at full load. As argon, another component of the air, has adsorption behavior similar to that of oxygen, the maximum purity of oxygen from adsorption plants is 95 to 95.5%. That corresponds to the proportions of oxygen and argon in the air. For economic reasons, most plants produce purities of 90% to 93%.

Adsorptive oxygen recovery is done industrially by passing air into a container of a molecular sieve so that the pressure in the container rises to 1.5 bar. Almost 100% of the nitrogen in the air is adsorbed by the molecular sieve, but only about half of the oxygen and argon. The unabsorbed oxygen and argon are drawn off as the product, temporarily stored in a buffer tank, compressed, and sent to the consumer.

When the adsorber is saturated with nitrogen, the system switches to a second adsorber after a partial pressure equilibration between the two containers. The adsorber which has just completed its adsorption phase is regenerated by evacuation to 200 – 400 mbar. Near the end of this desorption phase, product oxygen gas is added to the adsorber from above, increasing desorption of the gas molecules. This flush completes the regeneration of this adsorber and the adsorption cycle starts again. The system must be adjusted so that the adsorption phase is just as long as desorption phase required.

Linde Air Separation Unit

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23.6. SAMSON reference: Temperature swing adsorption (TSA)

SAMSON Control Valve Type 3310

Werner Wolf, leader maintenance mechanics at the company Rohrwerk Maxhütte GmbH, in front of the two TSA (Temperature swing adsorption)-containers of the new Onsite plant.

The new Onsite plant of Rohrwerk Maxhütte GmbH, Germany in the summary: from the left: Compressor station, supervision container, the two vaporizers, Coldbox (the slim container in the background) and a tank for liquid nitrogen (container in the foreground).

The former propane container can be used for Onsite nitrogen (lying, on the right) as a further buffer.

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23.6.1. Detail view of the new Onsite plant: Evaporator and the two TSA (Temperature swing adsorption-container).

Pfeiffer Butterfly Valves (Member of the SAMSON Group)

SAMSON Control Valve Type 3310

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23.7. Cryogenic oxygen plants On-site supply from cryogenic plants is an economical alternative to VPSA plants wherever higher purities and larger volumes of product are required. Depending on the customers’ requirements, this process can recover gaseous and/or liquid oxygen, oxygen and nitrogen, and, with a large air throughput, even nitrogen. The costs of cryogenic plant products are comparable with or lower than those of VPSA plants when the plants are large, if nitrogen is recovered along with oxygen.

A cryogenic air separation plant consists essentially of the following process steps: air compression process air purification chilling in the main heat exchanger separation in the rectification column recovery of the cooling power. The products are obtained by distillative separation of the air in a dual column in which the air components are separated by their different boiling temperatures. The separation takes place in the temperature range of about –117 °C to –196 °C, according to the boiling points of the air components, and depending on the pressures in the rectification column.

23.7.1. Diagram of a cryogenic oxygen plant

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After dust particles have been removed in filters, the process air is compressed in an air compressor to the process pressure, typically 6 bar. Then it is led to the molecular sieve station. At this station, containers of special adsorbers operate in cycles to remove water, carbon dioxide and many hydrocarbons from the process air.

The process air, purified in that manner, is chilled in the main heat exchanger in countercurrent to the products from the rectification column. Part of the air is expanded in an expansion turbine to provide the cooling requirement of the plant and fed into the upper column. Most of the compressed air is cooled nearly to the liquefaction temperature in the last part of the main heat exchanger and then taken to the lower part of the pressure column. The more volatile nitrogen accumulates in the gas phase, due to the rectification, and can be drawn off as compressed nitrogen at the upper part of the column. Most of the gaseous nitrogen is liquefied in the condenser and is returned as reflux to the pressure column or the low-pressure rectification column.

The oxygen-rich liquid which collects at the base of the pressure column acts as the reflux for the low- pressure columns, which the final separation into pure oxygen and nitrogen takes place. Oxygen can be removed at the lower art of the low-pressure column in both liquid and gaseous forms, while there is pure and nearly unpressurized nitrogen at the head of that column. Impure nitrogen (residual gas) is removed through another outlet in the upper portion of the column. It is suitable for regenerating the molecular sieve because it is noncombustible and extremely dry.

23.7.2. SAMSON reference: Hydrogen generating plant for Spain The company CALORIC Anlagenbau GmbH, Lohenstrasse 12, D-82166 Graefelfing, near Munich / Germany is building another hydrogen generation plant by steam reforming for a gas supplier’s on-site business. The installation is in Northern Spain. The plant will supply 1200 Nm³/h hydrogen with 99.94% purity. The client is one of the leading international gas supplying companies and will provide hydrogen to a manufacturer of elastomers. The plant will be completely pre-assembled in Caloric's factory and is ready for shipment end of 2006.

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24. SAMSON reference: PSA plants

Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. CALORIC Anlagenbau GmbH 3241, 72.4 1. 345 899 Unknown 2000 Graefelfing, Germany 41-23, 3331 CALORIC Anlagenbau GmbH 3241, 3510, 2. Khalista, China 2000 Graefelfing, Germany 3331 CALORIC Anlagenbau GmbH 3. 380 011 SAPIO, Sweden 3241 2000 Graefelfing, Germany CALORIC Anlagenbau GmbH 4. 423 635 HC 4588 3241, 3767 2001 Graefelfing, Germany CALORIC Anlagenbau GmbH HC4607 ZHUHAI, 5. 416 404 3241 2001 Graefelfing, Germany China CALORIC Anlagenbau GmbH 3241, 3510 6. 454 226 HM 4643 2001 Graefelfing, Germany 3331 CALORIC Anlagenbau GmbH HC 4634 - 7. 468 107 3241, 3787 2002 Graefelfing, Germany VISCOLUBE CALORIC Anlagenbau GmbH 3241, 3331, 8. 477 118 HM 4663 P.T. SORINI 2002 Graefelfing, Germany 72.4 CALORIC Anlagenbau GmbH HC 4609, Höganäs, 9. 437 906 3241, 3730 2002 Graefelfing, Germany Sweden CALORIC Anlagenbau GmbH HC 4418 Golnaz, 10. 512 356 3241, 3331 2003 Graefelfing, Germany Iran CALORIC Anlagenbau GmbH HC 4676 SMS 11. 512 220 3241, 3730 2003 Graefelfing, Germany Demag CALORIC Anlagenbau GmbH 12. 512 221 HC 4768 3241, 3730 2003 Graefelfing, Germany CALORIC Anlagenbau GmbH 13. 524 598 HC 4711 3241, 3730 2003 Graefelfing, Germany CALORIC Anlagenbau GmbH 14. 556 677 HC 4599 3241 2003 Graefelfing, Germany CALORIC Anlagenbau GmbH HC 4575, Duslo, 15. 569 616 3241, 3244 2003 Graefelfing, Germany CZ CALORIC Anlagenbau GmbH 3241, 3244, 16. 532 626 HC 4706, Carbafas 2003 Graefelfing, Germany 3241 Gas, CALORIC Anlagenbau GmbH 3241, 3244, 17. 602 889 HM 4736, China / FCI 2004 Graefelfing, Germany 3241 Gas, CALORIC Anlagenbau GmbH HC 4747, Jing Jing, 3241, 3244, 18. 602 810 2004 Graefelfing, Germany China 3241 Gas, 3241, 3244, 19. 625 000 CALORIC Anlagenbau GmbH HC 4751, Atefina 2004 Graefelfing, Germany 3241G, 3331

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. 3241, 3241G, CALORIC Anlagenbau GmbH 20. 1 187 784 HC4802 3251, 3253, 2006 Graefelfing, Germany 3730-2 3241, 3244, CALORIC Anlagenbau GmbH HC4815 21. 1 215 828 3241G, 3331, 2006 Graefelfing, Germany TKES B 3730-2 CALORIC Anlagenbau GmbH 3241, 3241- 22. 1 283 023 AVS 4823 2006 Graefelfing, Germany DVGW, 3241,fff 3335, 123 CALORIC Anlagenbau GmbH 23. 1 305 957 AVS 4825 26a, 76a, 2006 Graefelfing, Germany 3730-2, 41-23, CALORIC Anlagenbau GmbH 3241G, 3241, 24. 1 325 550 HC 4836 2007 Graefelfing, Germany 3730-2 3241, 3244, CALORIC Anlagenbau GmbH 25. 1 326 784 CO 4833 3331, 3335, 2007 Graefelfing, Germany 3730-2

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. Mahler AGS GmbH, 203100617/00 AP 3241, 3251, 26. 358 313 2000 Stuttgart, Germany South Africa 3510 Mahler AGS GmbH, Shanghai, 27. 369 700 3241 2000 Stuttgart, Germany China Mahler AGS GmbH, 2131 8 9881 H2- 3241, 3251 28. 2001 Stuttgart, Germany, Anlage 4763 Mahler AGS GmbH, Merk Gernsheim, 3241, 3510 29. 423 876 2001 Stuttgart, Germany Germany 41-23 Mahler AGS GmbH, 3241, 3251 30. 454 627 Khalista 2002 Stuttgart, Germany 41-23 Mahler AGS GmbH, 31. 498 661 223200633/00 3241, 4763 2002 Stuttgart, Germany Mahler AGS GmbH, 32. 506 167 223100636/00 3241, 4763 2002 Stuttgart, Germany Mahler AGS GmbH, 3241, 3244 33. 519 924 223400634/00 SB 2002 Stuttgart, Germany 2417 Mahler AGS GmbH, 34. 529 041 0641 223100641/00 3241, 3510 2003 Stuttgart, Germany Mahler AGS GmbH, 35. 9931 8 9601 3241 2003 Stuttgart, Germany Mahler AGS GmbH, 36. 536 266 233100643/00 3241 2003 Stuttgart, Germany Mahler AGS GmbH, 37. 9407 3241, 3510 2003 Stuttgart, Germany Mahler AGS GmbH, 38. 576 268 233100648/00 3241, 3510 2003 Stuttgart, Germany Mahler AGS GmbH, 3241, 3244 39. 583 239 233200649/00 2004 Stuttgart, Germany 41-23 Mahler AGS GmbH, Posco 1, 3241 40. 634 931 2004 Stuttgart, Germany South Korea 41-23 Mahler AGS GmbH, 3241 41. 649 134 Italy 2004 Stuttgart, Germany 41-23 Mahler AGS GmbH, 3241 42. 649 145 Messer China 2005 Stuttgart, Germany, 41-23 Mahler AGS GmbH, Posco 2 3241 43. 1 145 046 2005 Stuttgart, Germany South Korea 41-23 Mahler AGS GmbH, 255000661 Chematur 3241, 3241- 44. 1 169 260 2005 Stuttgart, Germany Sweden PSA Mahler AGS GmbH, 3241, 3241- 45. 1 190 861 255500665/00 2005 Stuttgart, Germany PSA

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. Mahler AGS GmbH, 253100666/00 3241, 3251 46. 1 190 866 2006 Stuttgart, Germany Medan / Indonesia 3510 Mahler AGS GmbH, 3241, 41-23 47. 1 195 219 Stuttgart, Germany 253200667, Lurgi II 3244, 3253 2006 Mahler AGS GmbH, 662-221205 3241, 3510S 48. 1 197 637 2006 Stuttgart, Germany Russia 41-73, 3251 Mahler AGS GmbH, 3241, 41-73 49. 1 204 177 253200664/00 2006 Stuttgart, Germany 3244 Mahler AGS GmbH, 253100669 3241, 3251 50. 1 212 997 2006 Stuttgart, Germany Yukos Syzran, Russia 3510 Mahler AGS GmbH, Samsung 672, 3241-PSA, 51. 1 231 286 2006 Stuttgart, Germany South Korea 3251 Mahler AGS GmbH, 263100674/00/HABAS 3241, 3251, 52. 1 24 1167 2006 Stuttgart, Germany Turkey 3510, 3241- Mahler AGS GmbH, Degussa 3241,S 3510 53. 1 251 262 2006 Stuttgart, Germany Brazil 3251, Mahler AGS GmbH, 261100679 & 54. 1 265 566 3241-PSA 2006 Stuttgart, Germany Sofia MED, Bulgaria Mahler AGS GmbH, Auftrag 682 3241, 3251, 55. 1 294 871 2007 Stuttgart, Germany Insa Oil, Bulgaria 4763, 41-73 Mahler AGS GmbH, 263100683 3241, 3251, 56. 1 297 582 2007 Stuttgart, Germany Stalprodukt, Poland 41-73, 4763

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. 57. 774 003 Linde Gas, Höllriegelskreuth Kuantan, 3241 2000 Germany Malaysia Linde Gas, Höllriegelskreuth Tarragona, 58. 774 129 3241 2000 Germany Spain Linde Gas, Höllriegelskreuth Bulwer-Island 2, 59. 779 124 3241 2000 Germany Australia Linde Gas, Höllriegelskreuth 2611/0993 JILIN-L, 3248, 3251 60. 311 729 2000 Germany China 3256 Linde Gas, Höllriegelskreuth A-2GB254 61. 380 031 3241 2000 Germany 2411/0977 Porto Linde Gas, Höllriegelskreuth 1410/2251 Mesaieed, 62. 309 601 3241 2000 Germany Qatar Linde Gas, Höllriegelskreuth A-2GB924 Milazzo-3, 63. 330 590 3241 2000 Germany Italy Linde Gas, Höllriegelskreuth 64. 345 755 Tjiedbergodden 3241 2000 Germany Linde Gas, Höllriegelskreuth 001 2GB881 65. 353 093 3241 2000 Germany Misc Diverse, Holborn Linde Gas, Höllriegelskreuth 1110/2258 Laichingen, 66. 353 012 3241, 3251 2000 Germany Germany Linde Gas, Höllriegelskreuth 001 2GB894 67. 369 556 3241 2000 Germany 29111051 SINES - P Linde Gas, Höllriegelskreuth 2GB898 2210/1058 3251 68. 380 030 2000 Germany KALUNDBORG, SPC-Piston Linde Gas, Höllriegelskreuth A-2GB9254 PORTA S 69. 380 031 3241 2000 Germany MARGEHERIA Linde Gas, Höllriegelskreuth 70. 369 556 SINES, Portugal 3241 2000 Germany Linde Gas, Höllriegelskreuth Antwerp- P2, 71. 345 834 3241 2000 Germany Belgium Linde Gas, Höllriegelskreuth 22101057 Wesseling, 72. 347 999 3241 2001 Germany Germany Linde Gas, Höllriegelskreuth 73. 387 123 Wesseling, Germany 3241 2001 Germany Linde Gas, Höllriegelskreuth 2GB967 LIN YUAN, 74. 387 137 3241 2001 Germany China Linde Gas, Höllriegelskreuth Seosan, 75. 390 363 3241 2001 Germany South Korea Linde Gas, Höllriegelskreuth 2GB987/22101063 76. 398 100 3241 2001 Germany Onsan-R, South Korea

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. Linde Gas, Höllriegelskreuth 001/2AL044/29101051/ 77. 426 448 3241 2001 Germany Sines, Portugal Linde Gas, Höllriegelskreuth 001/2GC241/29111066 3241, 3251 78. 410 301 2001 Germany Leuna, Germany 3767, 72.3 Linde Gas, Höllriegelskreuth 001 2AL058 3241, 3251 79. 410 337 2001 Germany 29101066 LEUNA SR Sipart Linde Gas, Höllriegelskreuth 2GC314 80. 3241 2001 Germany Münchmünster, Linde Gas, Höllriegelskreuth GTA PA, 81. 426 448 3241 2001 Germany Thailand Linde Gas, Höllriegelskreuth MAP-TA-PUT, 82. 437 852 3241 2001 Germany Thailand Linde Gas, Höllriegelskreuth Ingolstadt, Germany 3241-7 83. 434 701 2001 Germany ESSO Refinery 3241-9 Linde Gas, Höllriegelskreuth 24111070 84. 3241 2001 Germany Oldenburg, Germany Linde Gas, Höllriegelskreuth MAP-TA-PUT, 3241-7 85. 454 868 2002 Germany Thailand 3241-9 Linde Gas, Höllriegelskreuth 2GC395/22101084 86. 454 767 3241 2002 Germany Point LISAS, Trinidad Linde Gas, Höllriegelskreuth 2GC406 / ASALUYE 9, 3241-7 87. 478 308 2002 Germany Iran 3241-9 Linde Gas, Höllriegelskreuth 001 2GC44/22101093 88. 477 957 3241 2002 Germany GORLICE, Poland Linde Gas, Höllriegelskreuth 1110/2277- 89. 482 842 3241 2002 Germany MAANSHAN, China Linde Gas, Höllriegelskreuth 3241, 90. 477 830 1410/2281-ELEUSIS 2002 Germany Sipart Linde Gas, Höllriegelskreuth 14101181 Baufeld 3241 91. 491 238 2002 Germany (ELEUSIS) Sipart Linde Gas, Höllriegelskreuth 0012GC49722101092, 92. 498 564 3241 2002 Germany Scheldelaan, Belgium Linde Gas, Höllriegelskreuth 2GC547/22101103 93. 512 221 3241 2002 Germany BANDAR ASSUYEH M Linde Gas, Höllriegelskreuth 0012AL224/31101107 94. 529 650 3241, 3251 2003 Germany Burghausen, Germany 546 022 Linde Gas, Höllriegelskreuth 11102293 XIAMEN III, 3241 95. 2003 to 024 Germany China 3730-2 Linde Gas, Höllriegelskreuth SASOLBURG-R, 3241 96. 549 254 2003 Germany South Africa 3730-2

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. Linde Gas, Höllriegelskreuth 001 2AL258/22101113/ 97. 549 398 3241 2003 Germany Trecate, Italy Linde Gas, Höllriegelskreuth 11102296 – Tornio, 98. 569 730 3241, 3251 2003 Germany Sweden Linde Gas, Höllriegelskreuth 22101125, Kwinana, 99. 556 655 3241 2003 Germany Australia Linde Gas, Höllriegelskreuth 2GC769/21111115 100. 556 654 3241 2003 Germany Skikda-P, Algeria Linde Gas, Höllriegelskreuth 2210 1128 Boashan 101. 576 800 3241, 41-23 2003 Germany 2A, China Linde Gas, Höllriegelskreuth 2960 1051 Sines, 3241, 3251 102. 569 600 2003 Germany Portugal 3510 Linde Gas, Höllriegelskreuth 22101122 Daqing-2, 103. 573842 3241 2003 Germany China Linde Gas, Höllriegelskreuth 22101138 Talcahuano, 104. 573 951 3241 2003 Germany Chile Linde Gas, Höllriegelskreuth Sepon, 105. 583 450 3241 2003 Germany India Linde Gas, Höllriegelskreuth 22101130 Pohang, 106. 576 972 3241 2003 Germany South Korea Linde Gas, Höllriegelskreuth 107. 598 980 Lillo II 3241 2003 Germany Linde Gas, Höllriegelskreuth 108. 618 571 UFA-P 3241 2003 Germany Linde Gas, Höllriegelskreuth BERRE, 109. 631 449 3241 2003 Germany France Linde Gas, Höllriegelskreuth TOLEDO, 110. 634 751 3241 2003 Germany Spain Linde Gas, Höllriegelskreuth Bandar Assaluyeh M2; 111. 649 465 3241 2004 Germany Iran Linde Gas, Höllriegelskreuth Dormagen P 112. 649 468 3241 2004 Germany Germany Linde Gas, Höllriegelskreuth Togliatti 2, Italy 113. 649 576 3241 2004 Germany 2TA 019, 2210 1174 Linde Gas, Höllriegelskreuth 2TA 014, 2911 1172 114. 649 529 3241 2005 Germany Voikkaa, Finland 649 582 Linde Gas, Höllriegelskreuth DALIAN-P 115. 3241 2005 1121885 Germany 2XS 361, 2254 4948 Linde Gas, Höllriegelskreuth Con Con 116. 649 583 3241 2005 Germany 2TA 021, 2911 1166

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. Linde Gas, Höllriegelskreuth Salt Lake City 117. 649 584 3241 2005 Germany 2TA 20; 2210 0114 Linde Gas, Höllriegelskreuth Lima Ohio P 118. 649 585 3241 2005 Germany 2TA 034, 2210 0115 Linde Gas, Höllriegelskreuth 119. 649 586 Kazan, Russia 3241 2005 Germany Linde Gas, Höllriegelskreuth 120. 649 589 Caojing-P, China 3241 2005 Germany Linde Gas, Höllriegelskreuth TA FA 2 ML 121. 649 599 3241 2005 Germany 2TA 016, 2210 1180 Linde Gas, Höllriegelskreuth 122. 1 153 639 Holborn 2; Germany 3241 2005 Germany Linde Gas, Höllriegelskreuth 3241, 3241- 123. 1 165 796 22101181 Renlic 2005 Germany PSA Linde Gas, Höllriegelskreuth 1110/2339 Maanshan 124. 3241, 3251 2005 Germany II, China Linde Gas, Höllriegelskreuth 22101200 Rayong; 125. 1 189 718 3241-PSA 2005 Germany Thailand Linde Gas, Höllriegelskreuth 29101208 Delfzijl, 3241, 3251, 126. 1 189 717 2005 Germany Netherlands 3253, Linde Gas, Höllriegelskreuth Jamnagar, 127. P1968 3241-PSA 2005 Germany India Linde Gas, Höllriegelskreuth Dalian 2, 128. 1 102 032 3241-PSA 2005 Germany China Linde Gas, Höllriegelskreuth 2901205 Karlsruhe, 3241, 3251 129. 1 216 198 2006 Germany Germany 41-23, Vetec, Linde Gas, Höllriegelskreuth 11102354 Jubail VI 130. 1 215 905 3241 2006 Germany RTA 082/083 Linde Gas, Höllriegelskreuth KarlsruheS – Miro, 131. 1 210 843 3241-PSA 2006 Germany Germany Linde Gas, Höllriegelskreuth 23101194 132. 1 215 163 3241, 3251 2006 Germany Yanbu-L, Linde Gas, Höllriegelskreuth IN060306AD,S 133. 1 228 657 3241-PSA 2006 Germany Ingolstadt, Germany Linde Gas, Höllriegelskreuth 22101157 3241-PSA 134. 1 228 659 2006 Germany Toledo, Spain Actuator, STR, 1110S 2354 GSG Linde Gas, Höllriegelskreuth 135. 1 238 098 Jubail VI , 41-23 2006 Germany Saudi Arabia

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Reference list Pressure Swing Absorption (PSA) –Plant Extract as of Year 2000 Serial SAMSON Customer SAMSON Plant Project- Customer Year Reference PSA-Products No. No. Linde Gas, Höllriegelskreuth 22101211 3241-PSA, 136. 1 219 499 2006 Germany Ras Laffan P, Qatar 3275 22101157 Linde Gas, Höllriegelskreuth 3241-PSA 137. 1 228 659 TOLEDO-P ROG, 2006 Germany 3275, 3730-2 Spain 11102354, Linde Gas, Höllriegelskreuth 41-23, Type 138. 1 238 098 Yubail VI 2006 Germany Saudi Arabia 2412/2413 Linde AG, Linde Engineering, Schwarzheide, 3241-PSA 139. 1 269 580 2006 Pullach, Germany Germany 3275 Linde AG, Linde Engineering, 2210A057 3241-PSA 140. 1 283 122 2006 Pullach, Germany Neustadt 2, Germany 3275 Yubail VII 1 292 925 Linde AG, Linde Engineering, 3241, 3381. 141. Saudi Arabia 2007 1 304 501 Pullach, Germany 41-23, 41-73

1 292 929 Linde AG, Linde Engineering, 11102370, Yanbu III, 3241, 41-23, 142. 2007 1 304 508 Pullach, Germany Kingdom of Saudi 41-73, Linde AG, Linde Engineering, 2210ADAG 3241-PSA 143. 1 308 561 2007 Pullach, Germany BAOSHAN 3, China 41-23, 3730-2

Linde AG, Linde Engineering, 11102380 IJMUIDEN 144. 1 315 288 3241, 3381 2007 Pullach, Germany LF51, Netherlands

Linde AG, Linde Engineering, 1110AD2N, 3241-1; 3251, 145. 1 325 248 2007 Pullach, Germany Taichung 1-2 L, Taiwan 3381, 3730-2 Linde AG, Linde Engineering, 2910AOEK, 3241, 3251, 146. 1 327 855 2007 Pullach, Germany Kaohsiung, Taiwan 3510, 72.3, 3302 147.

148.

Result:

More than 3700 SAMSON control valves are installed in the PSA- plants of the three companies listed above.

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25. Gas-to-Liquid (GTL) LNG is also not synonymous with Gas-to-Liquids (GTL). GTL refers to the conversion of natural gas to products like methanol, dimethyl ether (DME), middle distillates (diesel and jet fuel), specialty chemicals and waxes. While the technology for producing each of these distinct products was developed years ago, only methanol is currently in widespread commercial production.

DME and specialty lubricants and waxes from natural gas are in limited commercial production. Middle distillate can be directly substituted for diesel fuel in existing compression ignition engines.

The advantage of GTL diesel is that it contains almost no sulfur or aromatics and is well suited to meet current and proposed cleaner fuel requirements of developed economies.

25.1. Primary chemicals on the basis of mineral oil/natural gas and carbon Synthesis gas chemistry also therefore is of special interest because it can be based on the raw material carbon and on mineral oil or natural gas. The summarizing the processes for the processing of mineral oil, of natural gas and of carbon shows that the fuels and the base chemicals Paraffin, Olefine, Aromatic, Acetylene and Syngas, in principle, similarly are made from the same raw materials.

Steam Cracking Olefins

Fischer- Tropsch- Synthesis Steam Reforming

Synthesis gas Partial oxidation Coal Methanol- gasification Synthesis

Methanol Mineral oil Coal Natural gas

Reforming process Carbonization Aromatics

High temperature- Carbide- Acetylene Coke Pyrolysis Synthesis

Cat-cracking

Hydrogenation of coal Benzine Hydro-cracking

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25.2. Synthesis gas chemistry Conversion Ammonia- + CO2 H NH Urea Resins 2 synthesis 3

Oxidation Paraffins CH2O Polyols

Coal Fischer- + CO Olefins CH3COOH Acetate Tropsch + CH3OH

Alcohols + CO CH3COOCH3 Acetic acid anhydride CO + H 2 Methanol- Synthesis gas CH3OH synthesis + O2 (Syngas) + CO / H2 CH3CHO

Union + H2 HO-CH2-CH2-OH Carbide CH CH OH Ethene 3 2 Polymethylene MTA-process Mineral oil Aromatic Natural gas

Methanation Substitute Mobil - process MTO-process Natural Gas (SNG) Olefins MTA=Methanol to aromatics MTO=Methanol to olefins MTG=Methanol to gasoline MTG-process Fuels Oxo-Aldehyde Oxo- synthesis + Isobutene Methyl-tert-butyl- Oxo-Alcohols ether (MTBE)

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26. Air Products is a leading supplier of oxygen to the emerging Gas-to-Liquid (GTL) industry. As the energy industry began to commercialize gas-based Fischer-Tropsch technology, Air Products was there. Air Products is one of the few companies in the world with the technical and operating experience to provide the high degree of reliability, safety and performance required for the supply of oxygen to world scale GTL plants. In 2005, Air Products supplied two 3,500 metric ton-per-day air separation plants to the world's largest and most advanced GTL facility located in Qatar and owned by ORYX GTL Limited. The same supply of oxygen is contracted to Chevron Nigeria Ltd. for its Escravos GTL facility in Nigeria. The ASU's will supply 7,000 tonnes of oxygen per day to make synthesis gas in the GTL production process.

26.1. Air Products is developing new technology Air Products is developing oxygen and synthesis gas Ion Transport Membrane (ITM) technology that has the potential to revolutionize the supply of oxygen and synthesis gas to the GTL industry.

26.1.1. Synthesis Gas The production of synthesis gas, a mixture of carbon monoxide and hydrogen (syngas) has become something of a hot topic in the industries over the past years. New technologies are changing the baseline economics of syngas production; make it an attractive feedstock for chemical synthesis and for the production of super-clean liquid fuels.

There are two main distinct uses of syngas; as a chemical feedstock and in so-called gas-to-liquid processes, which use Fisher-Tropsch (F-T) chemistry to make liquid fuels.

As feed stock for chemical synthesis, as well as being used in the production of fuel additives, including diethyl ether and methyl t-butyl ether (MTBE), acetic acid and its anhydride, syngas could also make an important contribution to chemical synthesis through conversion to methanol. And in synthesis gas production, stranded natural gas is converted into valuable and profitable liquid fuels.

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26.2. Fischer-Tropsch process The Fischer-Tropsch process is a catalyzed chemical reaction in which carbon monoxide and hydrogen are converted into liquid hydrocarbons of various forms.

Typical catalysts used are based on iron and cobalt. The principal purpose of this process is to produce a synthetic petroleum substitute for use as synthetic lubrication oil or as synthetic fuel.

Original process

The original Fischer-Tropsch process is described by the Professor Franz Fischer and following chemical equation: Dr. Hans Tropsch, (from left to right)

The inventors of a process to create liquid hydrocarbons from carbon monoxide gas and hydrogen using metal catalysts.

The initial reactants in the above reaction (i.e., CO and H2) Images: can be produced by other reactions such as the partial Max Planck Institute of Coal Research combustion of methane (in the case of gas to liquids applications):

OR by the gasification of coal or biomass:

The mixture of carbon monoxide and hydrogen is called synthesis gas or syngas. The resulting hydrocarbon products are refined to produce the desired synthetic fuel.

The carbon dioxide and carbon monoxide is generated by partial oxidation of coal and wood-based fuels. The utility of the process is primarily in its role in producing fluid hydrocarbons or hydrogen from a solid feedstock, such as coal or solid carbon-containing wastes of various types.

Non-oxidative Pyrolysis of the solid material produces syngas which can be used directly as a fuel without being taken through Fischer-Tropsch transformations. If liquid petroleum-like fuel, lubricant, or wax is required, the Fischer-Tropsch process can be applied.

Finally, if hydrogen production is to be maximized, the water gas shift reaction can be performed, generating only carbon dioxide and hydrogen and leaving no hydrocarbons in the product stream. Fortunately shifts from liquid to gaseous fuels are relatively easy to make.

Since the invention of the original process by the German researchers Franz Fischer and Hans Tropsch, working at the Kaiser Wilhelm Institute in the 1920s, many refinements and adjustments have been made, and the term "Fischer-Tropsch" now applies to a wide variety of similar processes (Fischer-Tropsch synthesis or Fischer-Tropsch chemistry)

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27. ThyssenKrupp-Uhde Partial oxidation (gasification) Today, gasification plants are considered an effective technology for upgrading "bottom of the barrel" oil residues into valuable products. Uhde is an authorized engineering partner of Shell for the Shell Gasification Process (SGP).

In a refinery environment one of the most attractive gasification products is hydrogen, which is used in hydro cracking or hydrodesulphurization units. Typically, a gasification based hydrogen plant consists of the gasification reactor, the acid gas removal unit, and a two-stage CO shift (low temp. / high temp.). Surplus syngas produced in the gasification process is typically converted into other chemical products or electric power.

As a technology-oriented company, Uhde can rely on extensive experience in the development, design and erection of oil and coal conversion plants. This experience dates back to the 1930s, since when the plants have undergone constant improvement, especially during the first oil crisis in the 70s.

To date, Uhde has designed and built 92 gasifiers worldwide based on 5 different gasification technologies (2 proprietary, 1 semi-exclusive, and 2 in licenses) for all feedstocks, whether solid, liquid or gaseous. These technologies comprise upstream and downstream processes which involve heat recovery, gas treatment, wastewater treatment and the subsequent processes for the production of hydrogen and synthesis gas products.

Shell gasification reactor and waste heat boiler

Photo Uhde: Hydrogen plant for SINCOR C.A. refinery near the Venezuelan city Puerto La Cruz

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28. Lurgi’s MPG gasification plus RECTISOL® GAS purification – advanced process combination for reliable SYNGAS production Lurgi’s Multi Purpose Gasification Process (MPG) is the reliable partial oxidation process to convert hydrocarbon liquids, slurries and natural gas into valuable syngas. The MPG burner has once again proven its capabilities in an ammonia plant based on asphalt gasification. The advantages of a quick restart without inspection and the inherent safety increase the availability and flexibility of the plant. Lurgi is operating the HP-POX demonstration plant together with the University of Freiberg, Germany. Gasification tests have been conducted successfully at pressures of up to 100 bar. The results show that syngas for high pressure synthesis such as methanol and ammonia can be produced more economically. The Rectisol® gas purification process yields ultra clean synthesis gas which is required to avoid problems in the downstream synthesis. Rectisol® removes all trace components such as cyanide, ammonia, mercury, all sulfur types and metal carbonyls, and no additional process steps for gas purification are required. Pure carbon dioxide is produced as a separate stream and is readily available for sequestration, enhanced oil recovery or other uses. The reliability of the Rectisol® process and the confidence of plant operators in this process are acknowledged by the fact that more than 75 % of the syngas produced world wide by coal, oil and waste gasification is purified in Rectisol® units (reference GTC Gasification Data Base 2004). Virtually all coal gasification plants currently under construction rely on Rectisol®.

The new, large GTL plants and hydrogen production facilities require effective CO2 removal. New developments make Rectisol® attractive for this task.

28.1. Lurgi’s history in gasification Lurgi’s process know-how in gasification started with the development of the fixed bed grate gasifier more than 70 years ago. This technology has been widely exploited and more than 120 gasifiers are in operation worldwide. The technology is especially advantageous for low-ranking coals and can handle very large ash and moisture contents. Today, more than 75 % of the syngas from coal produced worldwide is generated with this type of gasifier (reference GTC Gasification Data Base 2004).

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The joint development by Lurgi and British Gas led to the slugging type BGL gasifier. The temperature at the bottom is raised above the ash melting point and the slag that forms is routed via the proprietary slag valve at the gasifier bottom to the slag hopper. This type of gasifier has been operated for more than five years now in the SVZ plant in Eastern Germany with a feedstock mixture of municipal waste, pet coke and coal.

The Multi Purpose Gasification (MPG) is Lurgi’s entrained flow gasification process for converting hydrocarbon liquid feedstock such as refinery residues, chemical waste streams and slurries to syngas. The MPG burner has been in commercial operation for more than 30 years with a wide variety of feedstock.

28.2. SAMSON reference: Lurgi’s HP-POX Pilot Plant a Milestone to improved Syngas Production HP POX (High Pressure Partial Oxidation) high-pressure synthesis gas plant Lurgi Oel · Gas · Chemie GmbH, a subsidiary of Lurgi AG, both located in Frankfurt am Main, Germany is pursuing a research project jointly with “Institut für Energieverfahrenstechnik und Chemieingenieurwesen (IEC)”, the energy process technology and chemical engineering institute of the Technical University and Mining Academy of Freiberg in Saxony, Germany.

In order to further consolidate this position, Lurgi Oel x Gas x Chemie launched the "gas-to-chemicals" research project together with University of Freiberg, Germany. In line with this project, existing Lurgi processes for converting liquid and gaseous feedstock to synthesis gas are to be decisively enhanced in a pilot plant. In particular, operating conditions at higher working pressures are to be analyzed and established in order to achieve still larger capacities at significantly lower capital and operating costs. This will have another benefit in that it allows saving resources and sustaining ably curb energy-conditioned pollution of the environment. An optimization of the processes will prompt a development leap in the entire technology chain.

Multi Process Test Facility ATR, Gas-Pox, MPG (liquid feedstock)

Feedstock: Liquid Feedstock 500 kg/h Natural Gas 500 m3/h (0.5 MMSCFD)

Reactor: Operating Pressure 100 bar

Photo Lurgi:

HP POX (High Pressure

Partial Oxidation) high-

pressure synthesis gas

plant in Freiberg, Germany

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Among other applications, the synthesis gas produced is used for making methanol, which is a feedstock on the route to petrochemical intermediates and end products, such as polypropylene or hydrogen, as well as new energy sources like dimethylether (DME) or motor fuels. Lurgi will thus be able to offer from one single source a further complete process chain from the raw material through to the end product – which adds to its leading role in synthesis gas production worldwide.

28.3. The HP-POX demonstration plant The plant is designed as a multiprocess test facility for catalytic Autothermal reforming, so called ATR, and the non-catalytic partial oxidation (POX) of natural gas, Gas-POX, as well as the gasification of liquid hydrocarbon streams, heavy oil and residues, designated as MPG operation. The maximum throughput is 500 m3/h for natural gas feedstock and 500 kg/h for liquid feedstock, respectively. Tests have already been successfully performed with pressures of up to 100 bar.

The plant is designed as a stand-alone unit including all utility systems. Natural gas is taken from the grid and compressed; liquid feedstock and oxygen are stored on site.

High-pressure process steam is produced in a boiler. The reactor is a quench type reactor. The Syngas produced is desulphurized and flared.

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28.4. SAMSON reference: The reactor, the heart of the research HP POX (High Pressure Partial Oxidation) high-pressure synthesis gas plant in Freiberg, Germany.

SAMSON Control Valves

Processes Varied Parameters Catalytic Autothermal Reforming Pressure Partial Oxidation of Natural Gas Oxygen/Carbon Ratio (Temperature) Partial Oxidation of Liquid Feedstock Steam/Carbon Ratio Residence Time

New Results Demonstration of HP-Syngas Production Trace Components / Soot Formation Catalyst behaviour

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29. Lurgi’s Gas purification technologies The gas purification unit is the second most important process in a gasification plant, which defines plant reliability and operating costs such as maintenance and synthesis catalyst lifetime. Lurgi commands the full range of gas purification technologies, partly as proprietary technology, and specialist know how for the open art technologies, such as amine treating.

The most suitable gas purification process is selected with respect to the specification of the final ® product syngas, fuel gas, pipeline gas and by-products required such as pure CO2. Rectisol the process of choice for chemical synthesis and is also often beneficial for other applications.

Purisol® a selective physical absorption process and competes directly with UOP’s Selexol process. These processes achieve on-spec pipeline gas and fuel gas with regard to the total sulfur content remaining in the purified gas.

Lurgi also commands vast experience in amine gas treating processes such as DEA (Diethanolamine is primarily used in refineries and natural gas applications for CO2 and H2S removal), MDEA (Methyl Diethanolamine) and aMDEA. aMDEA: The first choice in gas purification technology is the aMDEA process - short for "activated Methyl Diethanolamine" - for removal of acid gases such as hydrogen sulfide (H2S) and carbon dioxide (CO2). One major criterion for an appropriate process selection is the required gas purity. Rectisol® removes all sulfur components so, typically, total sulfur content below 0.1 ppm is achieved. In addition, a pure CO2 stream with very low sulfur content can be generated, which is suited for urea production, beverage industry sequestration or just venting.

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29.1. GAS Purification for gasification based Hydrogen plant Hydrogen can be economically produced from heavy residue feedstock. The selection of the appropriate gas purification technology depends on the required hydrogen purity, the value of by- products fuel gas and CO2, and the plant emission regulations.

The feedstock is gasified in a quench type MPG unit. Carbon monoxide is converted to hydrogen in a raw gas shift, also referred to as sulfur tolerant shift. After gas cooling the acid gases have to be removed. This can be achieved with various processes.

® In the first case, the Rectisol process produces an H2S-rich sour gas suitable for the Claus unit. In addition, CO2 bulk removal is economical and a pure CO2 stream is generated which can be used for sequestration, industry usage, and which can also be vented without further treatment.

A PSA unit is used to free the raw hydrogen from trace components such as methane, nitrogen, CO and argon. The PSA off-gas is a high BTU, low-sulfur gas.

In the second case Rectisol® replaced by a selective acid gas removal process such as Purisol®. The selective acid gas removal also produces an H2S-rich sour gas suitable for the Claus Unit.

Typically, 20 – 30 % of the CO2 content of the raw gas is removed in selective gas purification process. This CO2 is produced as a separate, impure CO2 stream with a significant sulfur concentration. This sulfur impurity is normally no problem for sequestration purposes but simple venting is usually not permitted.

Since the AGR is selective, a considerable amount of CO2 passes to the PSA unit and is separated there. The PSA unit also separates the remaining sulfur impurities. The PSA off-gas exhibits a low heating value due to the high CO2 content and also contains a significant amount of sulfur.

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29.2. MPG based H2 Plant

In the third case, if the hydrogen is not required to have a high purity and the fuel gas is of low value, the PSA unit can be replaced by a methanation reactor, which converts CO and CO2 to methane. The gas purification unit has to remove all sulfur types to the ppb range and bulk CO2 removal to the low ppm range is required, since all impurities end up in the product hydrogen. Rectisol® the process of choice for this set up. A hydrogen purity of 97% can be achieved and no fuel gas is produced.

The hot gas and the slag are shock-cooled by water injection in the quench pipe. The slag is vitrified to a non-leach able solid and is routed with the water to the solids separation system, designated as the MARS unit (Metals Ash Recovery System).

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30. Forces of Change – Gas Development Technologies

Proprietary Process High Strength Steel Larger scale Bigger Ships Application and Products

Pressurized Natural Floating LNG Gas Ships

Pressurized Offshore Terminals Liquefaction

Technology is also stretching the economic and physical feasibility of connecting gas resources with distant markets. High-strength steel for pipelines is one example.

In addition, the industries and for example Qatar Petroleum are rapidly expanding the size of LNG trains in order to drive down the cost of gas liquefaction. Increases in train size from the 4.7 MTA for RasGas trains 3 and 4 to train sizes of 7 MTA and larger are possible, facilitating the capture of significant economies of scale. Only a few resources in the world, such as the North Field, are large enough to take full advantage of scale increases of this magnitude.

Continued technological advances that increase LNG ship size are also lowering transportation costs. LNG carriers significantly larger than the current 138,000 cubic meters can be built and safely operated, and offer the potential for significant reductions in the cost of long distance supply.

In addition, new technology makes higher temperature and pressure than the conventional LNG possible and includes the LNG put under pressure and makes the transport of the gas possible through this, what leads to significant energy and cost savings.

Next-generation LNG terminals can also reduce unit costs and development cycle time. The combination of these technologies can allow LNG to economically enter mature gas markets from substantially greater distances.

Technology is also giving rise to new uses for natural gas. Gas-to-Liquids technology promises to large gas reserves that are remote from markets and to deliver high-quality lube blend stocks and clean fuels at competitive costs.

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31. Service stations for example: 31.1. CANADA SAMSON CONTROLS INC. 1-105 Riviera Drive Markham, Ontario L3R 5J7

Phone: +1 905 4740354 Fax: +1 905 4740998 E-mail: [email protected] Home page: www.samsoncontrols.com

31.2. USA SAMSON CONTROLS INC. 4111 Cedar Boulevard Baytown, Texas 77520-8588

Phone: +1 281 383-3677 Fax: +1 281 383-3690 E-mail: [email protected] Home page: www.samson-usa.com

31.3. BRAZIL SAMSON CONTROL LTDA. Av. Santos Dumont, 8011, Portão 42700-000 Lauro de Freitas / BA

Phone: +55 71 33799020 Fax: +55 71 33693660 E-mail: [email protected] Home page: www.samsoncontrol.com.br

31.4. SWEDEN SAMSON MÄT- OCH REGLERTEKNIK AB Kungsporten 1A 427 50 Billdal Box 67 427 22 Billdal

Phone: +46 31 914015 Fax: +46 31 914019 E-mail: [email protected] Home page: www.samson.se

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31.5. GREAT BRITAIN SAMSON CONTROLS (LONDON) LTD. Perrywood Business Park, Honeycrock Lane Redhill, Surrey RH1 5JQ

Phone: +44 1737 766391 Fax: +44 1737 765472 E-mail: [email protected] Home page: www.samsoncontrols.co.uk

31.6. NETHERLANDS SAMSON REGELTECHNIEK B.V. Signaalrood 10 2718 SH Zoetermeer Postbus 2 90 2700 AG Zoetermeer

Phone: 0 79 - 3 61 05 01 Fax: 0 79 - 3 61 59 30 E-mail: [email protected] Home page: www.samson-regeltechniek.nl

31.7. AUSTRIA SAMSON MESS- UND REGELGERÄTE GESELLSCHAFT M.B.H. Amalienstraße 57, Postfach 33 1131 Wien 13

Phone: +43 1 8772674-0 Fax: +43 1 8772674-96 E-mail: [email protected]

31.8. FRANCE SAMSON REGULATION S.A. 1, rue Jean Corona - BP 140 69512 Vaulx en Velin Cédex

Phone: +33 4 72047500 Fax: +33 4 72047575 E-mail: [email protected] Home page: www.samson.fr

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31.9. SPAIN SAMSON S.A. Pol. Ind. Cova Solera Avda.Can Sucarrats, nº 104. Apartado 311 08191-RUBI (Barcelona)

Phone: +34 93 5 86 10 70 Fax: +34 93 6 99 43 00 E-mail: [email protected] Home page: http://www.samson.es

31.10. TURKEY SAMSON ÖLÇÜ VE OTOMATİK KONTROL SİSTEMLERİ SAN. VE TİC. A.Ş. Evren Mahallesi, Gülbahar Caddesi No: 94 34212 Günesli-İstanbul P.K. 3 89 80003 Karaköy-İstanbul

Phone: +90 212 6518746 Fax: +90 212 6518750 E-mail: [email protected] Home page: www.samson.com.tr

31.11. IRAN TECH. CONTROL INDUSTRIAL CONSULTANTS CO. Unit 607, 6th floor, Sarve Saee Tower, Mostofi Street Youssefabad 1433894593 (Tehran) PO. Box 14155/5516 Youssefabad (Tehran)

Phone: +98 21 8701112 Fax: +98 21 8724924 e-mail: [email protected]

31.12. EGYPT SAMSON CONTROLS S.A.E. - Middle East Area No. 128, First Industrial Zone Badr City, Cairo 11829

Phone: +20 2 864 3050 Fax: +20 2 864 3051 E-mail: [email protected] Home page: www.samsoncontrols.com.eg

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31.13. CHINA SAMSON CONTROLS (CHINA) CO., LTD. No. 11 Yong Chang Nan Lu, BDA Beijing 100176, P. R. of China

Phone: 0086-10- 67803011 Fax: 0086-10- 67803193 (Sale) Fax: 0086-10- 67802756 (Production) Fax: 0086-10- 67803196 (Office) e-mail: [email protected] Home page: www.samsonchina.com

31.14. THAILAND SAMSON CONTROLS LTD. 267/233-4 Sukhumvit Road, Map Ta Phut, Muang Rayong 21150

Phone: +66 38 608939 Fax: +66 38 608943 E-mail: [email protected] Home page: www.samson.co.th

31.15. SIGNAPORE SAMSON AG, R.O. SINGAPORE Technical Office - Asia/Pacific 27 Kaki Bukit View, 3rd Floor Kaki Bukit Techpark II Singapore 415962

Phone: +65 68468092 Fax: +65 67485897 E-mail: [email protected] Home page: www.samson-sea.com

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32. Literature cited 1. Gas Trade Grows Increasingly Significant Gas Trade Grows Increasingly Significant www.exxonmobil.com/files/pa/uk/energy_outlook2004_21.pdf

2. Forces of Change in the Global Gas Industry http://www.exxonmobil.com/Corporate/Newsroom/SpchsIntvws/Corp_NR_SpchIntrvw_HJL_131002.asp

3. LNG “Technical Ship Management Issues” Kishore Rajvanshy, Managing Director, Fleet Management Limited www.thedigitalship.com/powerpoints/norship05/lng/Kishore%20Rajvanshy-%20Fleet.pdf

4. LPG Gas Handling System for a Condensate/LPG FSO Dr. K. D. Gerdsmeyer, Project Manager, TGE Gas Engineering GmbH

5. References for gas carriers TGE Gas Engineering GmbH, Bonn, Germany, http://www.tge.net/

6. Linde_Technology_1_2003_EN.pdf, www.linde.com/Linde.Technology

7. Linde_Technology_1_2004_EN.pdf, www.linde.com/Linde.Technology

8. Linde_Technology_2_2004_EN.pdf, www.linde.com/Linde.Technology

9. Linde_Technology_1_2005_EN.pdf, www.linde.com/Linde.Technology

10. Linde_Technology_1_2006_EN.pdf, www.linde.com/Linde.Technology

11. Linde_Technology_2_2006_EN.pdf, www.linde.com/Linde.Technology

12. Linde AG Industrial gases in the chemical industry Werksgruppe Technische Gase, http://www.linde.com/linde-gas

13. Hydrogen Uhde a company of ThyssenKrupp Technologies FL 120 1000e 03/2005 DÖ/Hi

14. Westfalen AG, Münster, Germany Wertschöpfung aus nächster Nähe: Gasversorgung onsite. http://www.westfalen-ag.de

15. Mahler AGS GmbH, Inselstr. 140, D-70327 Stuttgart Gas Generation and Purification http://www.mahler-igs.com/index.html

16. CALORIC Anlagenbau GmbH, Lohenstrasse 12, D-82166 Graefelfing (near Munich / Germany) http://www.caloric.com/cms/front_content.php?idcat=25

17. U.S. Department of Energy, Energy Information Administration

18. The Distribution of the World's Natural Gas Reserves and Resources Joseph P. Riva, Jr., December 14, 1995

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19. ON-BOARD RELIQUEFACTION FOR LNG SHIPS by Dr. K-D.Gerdsmeyer & W.H. Isalski, TGE Gas Engineering GmbH BOG Re-Liquefaction TGE Symposium June 2005

20. Revised February 2001. NREL/TP-570-27637 Life Cycle Assessment of Hydrogen Production via Natural Gas Steam Reforming Pamela L. Spath, Margaret K. Mann, National Renewable Energy Laboratory 1617 Cole Boulevard, Golden, Colorado 80401-3393 NREL is a U.S. Department of Energy Laboratory Operated by Midwest Research Institute Battelle Bechtel

21. Linde Gas Consider onsite gas supply to meet processing needs in oil refineries. D. Schweer, G. Scholz, M. Heisel www.linde-gas.com

22. Lurgi‘s HP-POX Pilot Plant: A Milestone to Improved Syngas Production Gasification Technologies 2004 Washington, DC, October 3 –6, 2004 U. Wolf, H. Schlichting Lurgi AG http://www.lurgi.de

23. Offshore LNG Solutions SBM Single Buoy Moorings Inc. CH-1723 Marly – Switzerland http://www.singlebuoy.com/HTML/LeaseOperations/LeasedUnits.htm

24. Lehrbuch: Technische Chemie Baerns, Behr, Brehm, Gmehling, Hofmann, Onken, Renken WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006.

25. Golar LNG: Floating storage and regasification terminal Concept and engineering by moss maritime (A Company of Eni Saipem) http://www.mossww.com/mossmaritime/images/promo%20FSRU_Moss.pdf

26. King & Spalding LNG in Europe, An Overview of European Import Terminals, 2006 http://www.kslaw.com/library/publication/LNG_in_Europe.pdf

27. AIR LIQUIDE S.A. Paris, France ”Press kit” and “Gas production” http://www.airliquide.com

28. LURGI’S MPG GASIFICATION PLUS RECTISOLO GAS PURIFICATION – ADVANCED PROCESS COMBINATION FOR RELIABLE SYNGAS PRODUCTION Gasification Technologies 2005 San Francisco, October 9 – 12, 2005 Ulrich Koss, Holger Schlichting - Lurgi AG, Germany

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SAMSON AG · MESS- UND REGELTECHNIK · Weismüllerstraße 3 · 60314 Frankfurt am Main · Germany Phone: +49 69 4009-0 · Fax: +49 69 4009-1507 · E-mail: [email protected] · Internet: http://www.samson.de