Technology Handbook
Value through technology
To all our customers, We are pleased to share with you our most recent Technology Handbook. It provides a comprehensive overview of our portfolio of advanced technologies – some 64 of them, each designed to provide sustainable solutions to your business. Our ambition is to be the partner of choice for the design, engineering and construction of state-of the-art production units worldwide. We work continuously to increase the value of our technologies and expand our knowledge to serve our customers better. Innovation is vital, and our internal technology experts and research networks work closely with our development teams and plant operators to develop ideas and new approaches that meet our clients’ needs. We stay close to the markets and customers we serve, allowing us to develop our technological leadership for our customers’ benefit. A fundamental goal at Air Liquide Engineering & Construction is to provide our customers with competitive Domenico D’Elia solutions that are safe and reliable. Our aim is to make sure that our customers can secure the best possible Senior Vice President Sales and Technology performance from their operations and make the most efficient use of natural resources. Air Liquide Engineering & Construction We encourage you to contact us through our regional offices or one of our technology groups. Our experts and project leaders will be at your disposal and ready to offer additional information to help your business grow and prosper.
Technology Handbook Air Liquide Engineering & Construction 3 Air Liquide
The world leader in gases, technologies and services for Industry and Health
We are present in 80 countries with approximately 65,000 employees, serving more than 3.5 million customers and patients.
Oxygen, nitrogen and hydrogen have been at the core of the company’s activities since its creation in 1902. They are essential small molecules for life, matter and energy. They embody Air Liquide’s scientific territory.
Air Liquide’s ambition is to lead its industry, deliver long-term performance and contribute to sustainability. The company’s customer-centric transformation strategy aims to achieve profitable growth for the long term. It relies on operational excellence, selective investments, open innovation and a network organization implemented by the Group worldwide. Through the commitment and inventiveness of its people, Air Liquide is helping to deliver a transition in energy and the environment, provide changes in healthcare and digitization, and deliver greater value to all its stakeholders.
4 Air Liquide Engineering & Construction Technology Handbook Air Liquide Engineering & Construction
A technology partner of choice
Air Liquide Engineering & Construction, the engineering and construction business of the Air Liquide Group, builds the Group’s production units – mainly air gas separation and hydrogen production units – and supplies external customers with its portfolio of technologies. Its industrial gas, energy conversion and gas 3 15 purification technologies enable customers to optimize the use of natural Manufacturing Operating centers centers and front-end offices resources.
We cover the entire project life-cycle: from license engineering services / proprietary equipment, high-end engineering and design capabilities, as well as project management, commissioning and execution. Its exclusive and innovative technologies are contributing to the transition of the energy sector.
With more than 1,600 patents we are at work, connecting people and ideas everywhere to create advanced technologies to solve customer issues. 300 1,600 New patents Patents filed in 2017
Technology Handbook Air Liquide Engineering & Construction 5 At the heart of innovation
Innovation is one pillar of the Air Liquide Group’s strategy
Inventiveness, open-mindedness, sharing, agility and entrepreneurial mindset are fundamental features of our innovation approach.
Our Group innovation network is built on science, technologies, and dedicated investments. It is focused on developing new approaches and services for customers and patients, accelerated by digital transformation. It is part of an open ecosystem in which advances are rapidly shared across Air Liquide and with our external scientific partners and start-ups.
Innovation improves our customers’ experience, contributes to growth and to the creation of a more sustainable world.
We innovate across all our areas of activity, balancing its drive for innovation with a commitment to preserve and maintain core products. By combining this pragmatic approach with technical creativity, our teams deliver unique solutions that make a real difference to our customers. Here are just a few examples of recent innovations.
6 Air Liquide Engineering & Construction Technology Handbook Innovation in action
Cryocap™, CO₂ cold capture system A full portfolio of solutions for the LNG market Cryocap™ enables the capture of CO₂ released during hydrogen production via a cryogenic process. We offer customers a suite of highly efficient and proven The first industrial deployment of this technology was LNG technologies based on our own proprietary made in Port-Jérôme, France, at the largest steam processes using plate fin heat exchangers technology. methane reforming hydrogen production unit operated by Air Liquide. World’s largest plants for industrial gas production Cryogenic Technology Center We have designed and assembled the largest single train air separation unit ever built. With a total capacity of 5,800 At our Cryogenic Technology Center in Vitry-sur-Seine, tons of oxygen per day (at mean sea level), the unit will France, innovations related to cryogenic technology supply industrial gases to the Secunda site for Sasol in topics are developed, tested and demonstrated in an South Africa. We have also designed and built units for accelerated innovation cycle, thus being ready for early the global-scale hydrogen production site in Yanbu industrialization. Industrial City in Saudi Arabia with a total capacity of 340,000 Nm3 per hour.
SMR-X, a zero steam Gas POx contributing to clean air hydrogen plant solution Our natural gas partial oxidation technology (GasPOx) SMR-X enables zero steam hydrogen production, with enables the reduction of carbon, NOx and CO emissions 4% natural gas fuel savings and 4% reduced CO₂ compared to conventional syngas solutions. emissions compared to conventional installations. The technology has been successfully proven in a first reference project in Germany.
Technology Handbook Air Liquide Engineering & Construction 7 Our commitment to safety
We have one goal with respect to health, safety, the environment and security: to achieve zero accidents and zero environmental incidents. We ensure that every action we undertake, from initial design to construction, reflects our goal of ensuring safety and protecting the environment.
In pursuit of this goal, we strive to: • Provide a safe and secure work environment • Prevent all injuries, damage to the environment and damage to property • Identify and reduce risks and exposure to hazards in a sustainable way • Improve our Health, Safety, Environment and Security performance continuously • Enforce Air Liquide Life Saving Rules
Embodying a safety-first culture
• Our safety commitment applies not only to our employees, but also to our contractors, customers, adjacent facilities and local communities. • We ensure that safety is the responsibility of everyone and is a part of the Air Liquide Engineering & Construction culture driven by our behavioral-based ACT (Actively Caring Together) program. In this way, we are all safety leaders, and all share a commitment to the golden rule of safety first. • We will not hesitate to stop an activity of whatever nature (design, engineering, construction execution, or manufacturing) if it is not safe or if there is any suspicion that it may result in an accident or incident, now or in the future.
8 Air Liquide Engineering & Construction Technology Handbook Our commitment to sustainability
We strive to contribute to a more sustainable world. In line with Air Liquide's Corporate Sustainability Program and in order to contribute to a cleaner industry, transportation and enabling cleaner production, we offer a comprehensive portfolio of environmentally-optimized, efficient and easy-to-use solutions for our customers:
• Cryogenic CO2 capture technology. • Methanol production from CO2 rich feedstock and hydrogen. • Wide experience in the use of LNG, deployed as clean fuel. Our Liquefin™ technology offers 10% efficiency gain vs. state-of-the-art. • Our SMR-X for export steam free H2 production reduces natural gas use and CO2 emissions by about 5% compared to conventional steam reforming. • Our vast oleochemicals portfolio is a key-enabler to produce clean chemicals.
Supporting sustainability also involves actions in our own activities in engineering, manufacturing or on our sites to minimize environmental impact, leveraging new ways of digital transformation.
Technology Handbook Air Liquide Engineering & Construction 9 TABLE OF CONTENTS
10 Air Liquide Engineering & Construction Technology Handbook AIR GASES ...... 12 CHEMICALS ...... 44 OLEOCHEMICALS ...... 82 Yango™ – Standard Air Separation Unit ...... 13 Overview ...... 45 Overview ...... 83 Sigma – Standard Air Separation Unit ...... 14 Lurgi™ Methanol ...... 46 Seed Crushing and Extraction-Lurgi Sliding Cell Extractor . 84 Vacuum Swing Adsorption (VSA) Lurgi MegaMethanol™ ...... 47 Natural Oil Refining ...... 85 On-Demand Oxygen Generation ...... 15 Lurgi MTP™ – Methanol-to-Propylene ...... 48 Lurgi Biodiesel ...... 86 Nitrogen Generation System ...... 16 G2G™ – Gas-to-Gasoline ...... 49 Fatty Acid Methyl Ester Distillation/Fractionation ...... 87 Large Air Separation Unit ...... 17 Lurgi / Nippon Kayaku Acrylic Acid ...... 50 Methyl Ester Hydrolysis ...... 88 Methyl Acrylate (Synthomer Licensed) ...... 51 Glycerin Distillation and Bleaching ...... 89 Ethyl Acrylate (Synthomer Licensed) ...... 52 RARE GASES ...... 18 Fatty Acid ...... 90 Butyl Acrylate (Synthomer Licensed) ...... 53 Fatty Alcohol “LP3” ...... 91 Krypton/Xenon ...... 19 2-Ethylhexyl Acrylate (Synthomer Licensed) ...... 54 Bio Propylene Glycol (BASF Licensed) ...... 92 Helium Extraction and Liquefaction ...... 20 Butene-to-crude Butadiene (Mitsubishi BTcB Process) . . 55 Sorbitol ...... 93 Butadiene Extraction (BASF NMP Licensed) ...... 56 CO₂ CAPTURE ...... 22 Distapex™ – Aromatics Extractive Distillation ...... 57 CUSTOMER SERVICES ...... 94 Lurgi/Edgein Melamine ...... 58 Overview ...... 23 Overview ...... 95 Cryocap™ H₂ – Cryogenic CO₂ Separation ...... 24 Engineering Services ...... 96 NATURAL GAS TREATMENT ...... 60 Cryocap™ Oxy – Cryogenic CO₂ Separation Remote Support Services ...... 97 for Oxycombustion ...... 25 Overview ...... 61 On-Site Services ...... 98 Acid Gas Removal - Amine Wash ...... 62 Spare Parts Services ...... 99 Acid Gas Removal - Omnisulf™ ...... 63 HYDROGEN & SYNGAS GENERATION . . . 26 Customer Service Agreements ...... 100 Acid Gas Removal - Purisol™ ...... 64 Overview ...... 27 CO₂ Removal - Cryocap™ NG ...... 65 CONTACTS ...... 102 Steam Methane Reforming ...... 28 CO₂ Removal - Membranes ...... 66 Small-Scale Standard Hydrogen Plant ...... 29 Natural Gas Liquids Recovery – Turbo-booster ...... 67 LIST OF ABBREVIATIONS AND ACRONYMS . . 104 SMR-X™ – Zero Steam Hydrogen Production ...... 30 Natural Gas Liquids Recovery – Membranes ...... 68 ATR – Autothermal Reforming ...... 31 Nitrogen Rejection Unit ...... 69 Gas POX – Natural Gas Partial Oxidation ...... 32 Lurgi MPG™ – Multi-Purpose Gasifier ...... 33 SULFUR ...... 70 Lurgi FBDB™ – Fixed Bed Dry Bottom Coal Gasification . . 34 Oxynator™ / OxyClaus™ for Sulfur Recovery Units (SRU) . 71 Rectisol™ – Syngas Purification ...... 35 Sulfur Recovery Unit ...... 72 Emission-Free Sulfur Recovery Unit ...... 73 HYDROGEN & SYNGAS SEPARATION . . . 36 Overview ...... 37 LNG ...... 74 Pressure Swing Adsorption (PSA) – Hydrogen Purification 38 Overview ...... 75 CO Cold Box – Methane Wash ...... 39 Turbofin™ (Nitrogen Refrigerant Cycle) ...... 76 CO Cold Box – Partial Condensation ...... 40 Smartfin™ (Single Mixed Refrigerant Cycle) ...... 77 Liquid Nitrogen Wash ...... 41 Liquefin™ (Dual Mixed Refrigerant Cycle) ...... 78 Hydrogen Separation Membranes ...... 42 Boil-Off Gas Reliquefaction Units ...... 79 Hydrogen Liquefier ...... 43 Bunkering Stations ...... 80
Technology Handbook Air Liquide Engineering & Construction 11 AIR GASES
We have the experience, flexibility and capacity to provide a wide range of air separation units through standard plants, customized offerings and other cryogenic liquefaction technologies. Our strength lies in our ability to adapt our plants performances, safety and construction design philosophy to each project/customer specifics.
12 Air Liquide Engineering & Construction Technology Handbook AIR GASES Yango™ – Standard Air Separation Unit
Air Com- Precooling Air Cold pression & Front End Boosting Production Heat Exchange & Distillation Application Description Purification Steel making (basic oxygen furnaces, blast The Yango™ air separation unit is based furnaces, electric arc furnaces), chemicals on air compression, adsorption purification, Nitrogen HP GAN (ethylene oxide, ammonia, etc.) vent ➁ cryogenic distillation of main components and HP GOX Feedstock internal compression of high pressure products. LP GAN Air + Energy (electrical or steam) Yango is a standardized, highly packaged ASU ➂ ➃ solution to support short-time-to-start-up Product projects. ➆ ➀ Oxygen from 99.6% to 99.8% purity Several process schemes are available to and up to 50 bar optimize both Capex and Opex depending on ➇ Co-product customer product requirements, energy cost ➅ and customer process integration potential. ➄ Nitrogen, liquid oxygen, liquid nitrogen, liquid Air Liquide Engineering & Construction offers argon, compressed dry air optimized solutions in terms of construction Capacity strategy, operating philosophy and reliability. LOX To Storage 330 to 770 tpd References LIN To Storage
Economics >20 400 to 600 kWh/t ➀ Main Air Compressor ➄ Expander booster Specific energy: ➁ Adsorbers ➅ Main exchanger Contact ➂ Aftercooler ➆ Distillation Column Capex: 22 to 30 mm USD ➃ Booster Air Compressor ➇ Sub-cooler [email protected]
Technology Handbook Air Liquide Engineering & Construction 13 AIR GASES Sigma – Standard Air Separation Unit
Precooling Air Com- Air Cold pression & Front End Boosting Production Heat Exchange & Distillation Application Description Purification Steel making (oxygen boosting, electric arc Sigma units are based on air separation furnace), chemicals (ethylene oxide, etc.), with the following steps: air compression, Nitrogen HP GAN glass, non-ferrous metals, waste water vent ➁ adsorption, purification, cryogenic distillation treatment, pulp and paper HP GOX of main components, internal compression. LP GAN ➃ Feedstock Several process schemes are available ➂ Air + Energy (electrical) to optimize both Capex and Opex depending on customer product requirements. ➆ ➀ Product The Sigma units are designed to reduce Oxygen up to 99.8% purity construction and time to production with a highly ➇ Co-product packaged architecture. ➅ Some liquid co-production could be available to ➄ Nitrogen, liquid oxygen, liquid nitrogen, refill backup liquid storages. liquid argon, compressed dry air References Capacity LOX To Storage 110 to 380 tpd >40 LIN To Storage Economics Contact Specific energy: 280 to 460 kWh/t ➀ Main Air Compressor ➄ Expander booster [email protected] ➁ Adsorbers ➅ Main exchanger ➂ Aftercooler ➆ Distillation Column Capex: 5 to 9 mm USD ➃ Booster Air Compressor ➇ Sub-cooler
14 Air Liquide Engineering & Construction Technology Handbook AIR GASES Vacuum Swing Adsorption (VSA) On-Demand Oxygen Generation
Application Description Air compression Oxygen compression & Vacuum generation Adsorption & Backup Steel making, glass, pulp and paper, waste VSA uses the process of air separation ➂ water treatment, mining by adsorption. The basic principle of air Feedstock separation by adsorption relies on the use ➆ of specific zeolite adsorbents for the selective ➅ Air + Energy (electrical) ➀ ➁ adsorption of nitrogen over oxygen and argon. Gaseous Product ➂ Oxygen Main features: Oxygen from 90% to 93% purity • Compact design layout • Fully packaged and pre-tested skids Co-product ➇ • Minimized schedule, erection ➄ None and start-up times ➃ Capacity • Automatic and unattended operation 40 to 130 tpd Capitalization of more than 20 years of operating and maintenance experience. Economics References ➀ Air Filter ➄ Exhaust Specific energy: 265 kWh/t ➁ Air Blower ➅ Oxygen Booster ➂ Adsorber(s) ➆ Gas buffer Capex: 1 to 6 mm USD >100 ➃ Vacuum Pump ➇ Liquid oxygen tank Contact
Technology Handbook Air Liquide Engineering & Construction 15 AIR GASES Nitrogen Generation System
Application Description Air Compression Front End Purification Cold Production Heat Exchange Distillation LNG terminal, crude oil refinery, electronics This nitrogen generation system is based Residual on air separation with the following steps: Gaseous N₂ Feedstock rich gas LIN to backup air compression, adsorption, purification, (>35% O₂) to Customer Air + Energy (electrical) cryogenic distillation of main components. ➂ Product Several process schemes are available Nitrogen (gaseous, liquid) to optimize both Capex and Opex depending with 100 ppm to 1 ppb O₂ on customer product requirements. ➃ Co-product Some liquid co-production could be available to refill backup liquid storages. LOX high purity Systems often include backup vaporizers ➁ Capacity and storage designed as per customer’s requirements (availability and reliability). 500 Nm3/h to 70,000 Nm3/h ➅ of nitrogen These systems are safe, reliable and easy-to- ➄ operate and maintain. Economics Specific energy: 175 to 280 KWh/t References Capex: 2 to 11 mm USD > 100 ➀ Contact ➀ Air Compressor ➃ Main exchanger ➁ Adsorbers ➄ Distillation Column [email protected] ➂ Heater ➅ Expander
16 Air Liquide Engineering & Construction Technology Handbook AIR GASES Large Air Separation Unit
Precooling Air Com- Air Cold pression & Front End Boosting Production Heat Exchange & Distillation Application Description Purification Steel making (basic oxygen furnaces, blast Large air separation units are based on furnaces, electric arc furnaces), gas adsorption purification, cryogenic distillation Nitrogen HP GAN monetization (gas-to-methanol, -propylene, vent ➁ of main components and internal compression -liquids), coal gasification, chemicals HP GOX of high pressure products. (ethylene and propylene oxide, etc.), clean LP GAN ➃ power (IGCC, oxycombustion) From the small standard of a few hundred tonnes ➂ per day to Mega ASU complexes (multi-train) Feedstock of more than 15,000 tonnes per day, Air Liquide ➆ ➀ Air + Energy (electrical or steam) Engineering & Construction offers optimized solutions in terms of construction strategy, ➇ Product operating philosophy and reliability. ➅ Oxygen up to 99.8% purity ➄ and 100 bara References Co-product >4000 LOX To Storage Nitrogen, rare gases (Kr, Xe, He, Ne), liquid Contact oxygen, nitrogen and argon, LIN To Storage compressed dry air [email protected]
Capacity ➀ Main Air Compressor ➄ Expander booster ➁ Adsorbers ➅ Main exchanger Up to 6,000 tpd ➂ Aftercooler ➆ Distillation Column ➃ Booster Air Compressor ➇ Sub-cooler Economics Specific energy: 160 to 500 kWh/t Capex: 40 to 300 mm USD Several processes are available to optimize economics depending on product requirements, energy cost and process integration.
Technology Handbook Air Liquide Engineering & Construction 17 RARE GASES
Our technologies for rare gases use the most efficient, safe and reliable processes to achieve optimal production or extraction of products. Our solutions are fully integrated into existing plants providing optimal cost and energy efficiencies.
18 Air Liquide Engineering & Construction Technology Handbook RARE GASES Krypton / Xenon
Application Description Extraction cold box Krypton-Xenon upgrader Production of Krypton & Xenon mixture Oxygen return Liquid oxygen from ASU(s) is first treated to ASU concentrated at > 98% in a primary module, named “Extraction cold Liquid Oxygen Hydrocarbons Cryogenic Cryogenic & contaminants Hydrocarbons box,” which aims to remove contaminants such purge from ASU Separation Purification Separation Feedstock purification primary secondary as N₂O and partially CnHm before entering in a Liquid oxygen stream from a large first set of cryogenic separation to produce a Air Separation Unit (>3,000 tpd) KrXe mixture pre-concentrated mixture. storage Product The secondary module, named “Krypton-Xenon Krypton + Xenon Mixture at > 98% upgrader,” treats the pre-concentrated mixture Filling station through a hydrocarbons purifier before entering Co-product into the final concentrated cryogenic separation None in order to produce a krypton-xenon mixture Compression enriched at > 98% (rest is oxygen). & Vaporisation Cylinders Capacity unit This concentrated cryogenic mixture (typically From 4,000 Nm3 /annum Kr 91%, Xe 7%, O₂ 2%) is then compressed and up to 20,000 Nm3 /annum vaporized to fill gas cylinders at 150 barg. Economics Final separation (pure Kr, pure Xe) is done Opex : small size outside the ASU plant in a dedicated laboratory. - Power: depending on the ASU integration : Note: Krypton-Xenon production is 500 kWh/h - 1000 kWh/h economically favored for large ASU (>4000 tpd) or for multi ASUs due to the low - Cooling water + gaseous nitrogen Krypton and Xenon content in the air (negligible quantity compared to ASU (resp. 1.1 ppm, 0.086 ppm). utilities) Capex: small size Main features: References 5 - 15 mm USD (EP) • Integration with ASU • Low power consumption > 10 • Pre-assembled packages Contact or skid units to ease the erection [email protected]
Technology Handbook Air Liquide Engineering & Construction 19 RARE GASES Helium Extraction and Liquefaction
Application Description Helium Purification Helium Liquefaction Pure liquid helium production and loading N₂ purge Air The impure helium feed gas is purified in a first into ISO containers section, where N₂, CH4, H₂, CO, Ar, O₂, water and Helium Rich Feedstock CO₂ are separated from helium. Feed Gas It is composed of a cryogenic partial Natural gas or impure helium gas extracted condensation unit, a hydrogen removal system as non-condensable side-product from LNG and a Pressure Swing Adsorber (PSA) unit. units or impure helium gas extracted from nitrogen rejection units Then, the pure gaseous helium is cooled and liquefied via a helium cycle and the use Product of cryogenic expanders with a highly optimized Helium Storage and Loading Liquid helium cryogenic exchanger arrangement. Expanders are based on a proprietary technology using Co-product static gas bearing, ensuring high reliability and None efficiency. Capacity Liquid helium is continuously produced and stored in tanks. The unit is equipped with loading Up to 20 tpd (one train) bays to fill ISO containers. All helium vapors from Vapor Recovery System Economics the containers are collected and recycled within the unit. The highly efficient process combined with Pure liquid helium the vapor recovery system allows for a very Contact high helium recovery Compressor He Cycle Compressor Cryogenic Upgrader Helium Storage (> 99%). [email protected] H₂ Removal Loading Bays PSA Liquid Nitrogen Capex: 40 to 300 mm USD Dryers Gasbag Offgas Recycle Vapor Recycle He Liquefier
20 Air Liquide Engineering & Construction Technology Handbook Technology Handbook Air Liquide Engineering & Construction 21 CO2 CAPTURE
Cryocap™ is a technological innovation for CO₂ capture using a cryogenic process involving low temperatures, around -50°C, combined with membranes separation, that is unique in the world. It can be adapted to specific applications combining a variety of Air Liquide technologies: the capture of CO₂ produced by thermal power plants (Cryocap™ Oxy), or hydrogen production units (Cryocap™ H₂).
22 Air Liquide Engineering & Construction Technology Handbook Overview
H2 or Syngas Hydrogen & Syngas Cryocap™ H2 #24 Generation CO2 for CCS
Carbon free Flue Gas
Oxycombustion Cryocap™ Oxy #25
CO2 for CCS
Technology Handbook Air Liquide Engineering & Construction 23 CO CAPTURE 2 Cryocap™ H2 – Cryogenic CO2 Separation
Application Description H Product CO₂ capture from The offgas is compressed, dried and sent Natural H₂ production plants SMR Schift H - PSA to a cryogenic unit, where the CO₂ is separated gas Feedstock from the other components by a combination of partial condensation and distillation. A pure and Fuel Offgas from H₂ plant Cryocap™ H pressurized CO₂ flow is produced from the cold Product box. CO₂ The non condensed gases are recycled through Membranes a membrane system to recover H₂ and CO₂. Co-product Residual gas is sent to the burners of the H₂ reformer. Capacity The CO₂ product is compressed up to supercritical pressure or liquefied and stored Cold Co Product From 500 to 2,000 tpd Box in liquid storage. Economics Food-grade quality can be achieved by
Opex + Capex: an additional purification on a catalytic bed Residue - 45 USD/tonne of CO₂ where all remaining hydrocarbons and alcohols to fuel gas are destroyed. - Increase H₂ production by 13% to 20% Cryocap™ H₂ can be installed for greenfield as well as brownfield H₂ plants. - Cryocap™ H₂ offers the lowest costs for CO₂ production from H₂ plant Main feature: (20% less capex than amines) • More than 98% of CO₂ recovery from syngas Reference
1 (100 000 t/y) Contact
24 Air Liquide Engineering & Construction Technology Handbook CO2 CAPTURE Cryocap™ Oxy – Cryogenic CO2 Separation for Oxycombustion
Application Description Non condensable CO₂ capture from power plants to vent The flue gas issued from the boiler plant is first Feedstock treated in a pre-treatment unit, which aims to cool the gas and remove the SOx, HF, HCl, most of the Oxycombustion flue gas NOx, and the dust. Then the gas is compressed Product and dried before entering the cryogenic Flue Gas CO₂ purification unit. Cold Box In the cold box, CO₂ is recovered by combination Low Pressure Co-product of partial condensation and distillations, which Pre-Treatment None allow the removal of the heavy compounds such as NOx and the light elements such as O₂, Ar, N₂, Capacity NO and CO. From 1,000 to 15,000 tpd CO₂ Product The CO₂ product is compressed, condensed Economics and pumped up to supercritical pressure. Cryocap™ Oxy allows very high CO₂ Main feature: recovery and near zero-emission to • More than 98% of CO₂ recovery from syngas the atmosphere (SOx, particulate matters, NOx, Hg). References Capex: 40 to 300 mm USD 3 (from 25 000 to 1.2 million t/y) Contact
Technology Handbook Air Liquide Engineering & Construction 25 HYDROGEN & SYNGAS GENERATION
We are pushing technology limits in design and delivery of syngas plants, including the world’s largest units. Our plants meet the needs of large, medium, and small customers with a wide range of possible steam export rates.
26 Air Liquide Engineering & Construction Technology Handbook Overview
Steam Methane #28 Reformer #29 #30
Natural gas Autothermal #31 LPG Reformer Naphtha
CO2 Capture Gas POX #32
Chemicals
Liquid residue Hydrogen Lurgi MPG™ #33 from oil refining & Syngas Separation Rectisol #35
Coal Lurgi FBDB™ #34
Technology Handbook Air Liquide Engineering & Construction 27 HYDROGEN & SYNGAS Steam Methane Reforming (SMR) GENERATION
Application Flue Gas HP Steam Description Generation of syngas by steam reformation of methane rich hydrocarbon Feedstocks are desulfurized, mixed with steam Process Steam and pre-heated. Heat Feedstock Recovery Optionally a catalytic pre-reforming step may be Flue Gas LPG, naphtha, natural gas, refinery off-gas Fuel Gas foreseen to convert the feed/steam mixture to a Tail Gas Product methane rich gas to improve efficiency of the SMR. Hydrogen, carbon monoxide, The main reforming reaction takes place in the Natural Pre- syngas or a combination thereof Gas Syngas proprietary top-fired steam reformer in which the Reformer Co-product feed/steam mixture is converted while passing Syngas Hydro- Reformer Cooling Steam, optionally carbon dioxide catalyst filled and heated tubes at temperatures H2 desulfurization Pre-Treatment Boiler Feed of 800 to 940 °C and pressures of 15 to 45 barg. Water Capacity Reformed gas leaving the reformer contains H₂, Per SMR train: CO, CO₂ and unreacted components. - 15,000 - to 200,000 Nm3/h H₂ plant Efficiency of the process and composition of the - 3,500 - 40,000 Nm3/h CO plant reformed gas can be adjusted via the process Main features: - Up to 350,000 Nm3/h syngas parameters reforming pressure, temperature and • Flexibility in process design to optimize steam to feed ratio. for best efficiency, lowest Capex or lowest total Economics In case H₂ yield should be increased or cost of ownership Opex: maximized a catalytic shift reactor may be added • Optimized integration of refinery off-gases H₂ plants (based on nat. gas feed & fuel): and fed with reformed gas to convert CO and for H₂ production and recovery 3 Steam co-export ratio: 0.4 to 1.1 kg/Nm H₂ steam to additional H₂ and CO₂. • Best in class plant reliability and operability Feed+Fuel: 14.5 to 15.3 MJ/Nm3 H₂ through operational feedback from Air Liquide’s In case a high CO yield is targeted CO₂ may be own plants. HyCO plants (based on nat. gas feed & fuel): separated from reformed gas and recycled to the H₂/CO product ratio: 2.6 to 4.2 SMR. Additional import CO₂ may be added if 3 References Steam co-export ratio: 0.3 to 0.7 kg/Nm available. [H₂+CO] (> 40 in last 20 years) Suitable product purification technologies > 140 Feed+Fuel: 14.2 to 14.8 MJ/Nm3 [H₂+CO] include: PSA and membrane for H₂, amine wash Contact Capex: (aMDEA) for CO₂ removal and methane wash H₂ and HyCO plants (incl. purification): Cold Box for CO. [email protected] 25 to 370 mm USD
28 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS Small-Scale Standard Hydrogen Plant GENERATION
Application Description Flue Gas HP Steam Hydrogen production by steam reforming in The small-scale standard H₂ plant product a highly standardized and modularized plant is based on hydrogen production via steam Process Steam Heat Recovery Feedstock reforming of hydrocarbon feedstocks. Flue Gas Additionally a CO-shift and PSA unit are included Fuel Gas Natural gas, refinery off-gas, Tail Gas to maximize the H₂ yield and purify the H₂. For LPG, naphtha more details regarding the process technology Product reference is made to the description of Steam Hydrogen Methane Reforming (SMR). Natural H₂ Gas Co Shift Product The small-scale standard H₂ plant product Co-product includes four different plant sizes with pre- Hydro- Reformer Steam defined equipment, piping arrangement and desulfurization Pre-Treatment Boiler Feed PSA lay-out. Water Capacity Its design is optimized for minimum total Recycle 15,000 - to 45,000 Nm3/h H₂ cost of ownership, but nevertheless allows for Hydrogen Economics considerable process flexibility. The product is suitable for receiving different Opex: types of feedstocks, its configuration may be Feed+Fuel: 14.5 to 15.0 MJ/Nm3 H₂ (Figures selected for high or low steam co-product ratios based on nat. gas feed & fuel) with an option for high export steam quality. A Capex: pre-reformer may be included as well, particularly 25 to 60 mm USD in combination with liquid feedstocks.
Main features: References • Design of standard plant allows for considerable process flexibility >20 (6 in last 10 years) • High degree of modularization to limit exposure during construction Contact • Compact plant layout and small foot-print [email protected] • Delivery time < 15 month FOB from project award
Technology Handbook Air Liquide Engineering & Construction 29 HYDROGEN & SYNGAS SMR-X™ – Zero Steam Hydrogen Production GENERATION
Application Description Flue Gas Production of hydrogen in a radiative heat SMR-X technology is based on a new generation exchange steam methane reformer (SMR) steam methane reformer furnace with additional without co-export of steam heat recovery of the reformed gas leaving the Process Steam Heat Recovery Feedstock reaction zone back to the catalyst bed. Flue Gas To achieve this, the reformed gas passes Fuel Gas Natural gas, refinery off-gas, Tail Gas via heat exchange tubes, located inside the main LPG, naphtha reformer tubes, before leaving the reformer. Product Geometry and material of the internal heat Natural Pre- Co Shift H₂ Hydrogen exchange system is optimized for high efficiency Gas Reformer SMR-X Product and reliability. Consequently, utilization of SMR-X Co-product allows for a H₂ plant design with balanced steam H₂ Hydro- None (optionally steam at low co-export production and consumption at superior overall desulfurization Boiler Feed PSA Pre-Treatment ratio) process efficiency compared to conventional Water SMR technology. Also, highly efficient H₂ plant Capacity designs with very low steam co-export ratios are Up to 100,000 Nm3/h hydrogen possible. Economics Furthermore, the plant’s steam system is simplified and the reformer size of SMR-X is Opex: reduced compared to a conventional furnace, Feed+Fuel: Appr. 13.6 MJ/Nm3 H₂ because approximately 20% of the required (Figures based on nat. gas feed & fuel) process heat is supplied by internal heat Capex: exchange. 25 to 135 mm USD Main features: Contact • H₂ plant de-coupled from steam host [email protected] • Highest efficiency of all available zero steam solutions • >5% reduction of CO₂ emissions compared to conventional SMR based zero steam design • Attractive plant Capex due to compact reformer design
30 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS ATR – Autothermal Reforming GENERATION
Feed Application Description Production of syngas by partial oxidation of Desulfurized feed gas is preheated and gaseous hydrocarbon feed followed Desulfurization optionally pre-reformed prior to entering the ATR by a catalytic reforming conversion. reactor. The gas is fed via the proprietary burner The syngas can be used as feedstock for into a refractory lined reactor operating at 30 to different synthesis processes such as 100 barg, where it reacts with oxygen and steam Fired Heater Steam methanol or Fischer-Tropsch synthesis. to form syngas. The syngas is further reformed Syngas components can be also separated via a Ni-based catalyst bed located in the same to pure products (H₂, CO, CO₂) reactor. The syngas is cooled in a waste heat Pre-Reforming Feedstock boiler producing high pressure steam. Depending on the needed syngas properties of Natural gas, refinery offgas, pre- reformed the downstream process this technology can be gas, Fischer-Tropsch tail-gas, LPG, Naphtha ATR O₂ applied as stand-alone ATR or as a combination Product of SMR and ATR known as Combined Syngas (H₂+CO) Reforming. Main Features: Heat Recovery Syngas Co-product • Provide large quantities None of H₂-rich gas at lowest cost Capacity • Compact reactor • High pressure (up to 100 bar) Up to 1,000,000 Nm3/h (dry) per reactor References
Economics >30 Yield: 2.5- 4.0 Nm3 syngas / Nm3 natural gas (including fuel for fired heater) Contact Oxygen consumption: [email protected] 0.15 - 0.25 kg O₂ / Nm3 syngas Capex: 160 to 280 mm USD
Technology Handbook Air Liquide Engineering & Construction 31 HYDROGEN & SYNGAS Gas POX – Natural Gas Partial Oxidation GENERATION
Application Description Feedstock Production of CO, oxogas and syngas by Feed gas is desulfurized, mixed with steam and partial oxidation of hydrocarbon feed in a preheated in a fired heater. Fired refractory lined reactor Feed, steam and oxygen are fed from the HP Steam Heater / HDS CO₂ Feedstock proprietary burner to a refractory lined reactor operating at up to 100 barg, where H₂, CO and Natural gas, refinery offgas CO₂ are produced via partial oxidation. PSA / Reformed gas is cooled down producing high Gas WHR / Gas Amine Product WHB Cooling Wash CO Coldbox Product pressure steam. CO₂ is removed from the syngas O₂ POX Membrane Syngas (H₂/CO < 1), oxogas, in an amine wash unit. carbon monoxide In case a high CO yield is targeted CO₂ may be Co-product separated from syngas and recycled to the POx. Additional import CO₂ may be added if available. Steam Suitable product purification technologies Capacity include: PSA and membrane for H₂, oxogas, Waste ASU Waster Up to 150,000 Nm3/h syngas amine wash (aMDEA) for CO₂ removal and partial condensation Cold Box for CO. Economics Main Features: Air Oxygen consumption: • Efficient technology for products with low 0.32 to 0.38 kg/Nm³ syngas (dry) H₂/CO ratio or for pure CO production Capex: • Revamp of residue POx reactors allows 10 to 100 mm USD for switching to more economic nat. gas feed • Low CO₂ footprint References
6 Contact
32 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS Lurgi MPG™ – Multi-Purpose Gasifier GENERATION
Application Description Residue Value Utilization of all kinds of liquid hydrocarbon The feedstock together with oxygen and steam residues from refinery or chemical Steam LP-Steam Pure CO₂ High BTU is fed via the proprietary MPG-burner into the Low Sulfur processes for the production of syngas by refractory lined entrained flow reactor operating Fuel Gas non-catalytic partial oxidation at 30 to 100 barg, where it reacts in a non- Feedstock MPG™ Raw Gas Gas Rectisol™ PSA Hydrogen Feedstock catalytic partial oxidation at typically 1,200 to (Quench) Shift Cooling 1500 °C to form syngas. The syngas leaving the Typical feedstocks are residue from oil O₂ H₂S+CO₂ bottom of the reactor is cooled by quench or in a refining like: asphalt, bitumen, tar, visbreaker waste heat boiler, depending on feedstock Process Quench Sulfur residue, hydrocracker residue, FCC residue, Water water O₂ characteristics and downstream usage. OxyClaus™ vacuum residue, coal tar, oil sand tar, etc Claus Off-Gas The proprietary MPG-burner design allows a Product wide variety of feedstock properties to be Soot Water ASU Filtration Syngas (H₂ + CO) handled safely and reliably, covering high viscosity and even occasional particles Co-product up to millimeter size. The pressurized water Air Filter cake MPG based H₂ Production None cooling of the burner insures safe operation under all conditions. The technology may also be Capacity adapted to the usage of slurries with solid Up to 200,000 Nm3/h dry syngas content or bio-based syncrude. Contact per gasifier Main Features: Economics • Valorization of residues [email protected] capable of converting almost Individual costs vary significantly depending any liquid feedstock on feedstock, size, location, integration in • Highly tolerant to impurities refinery, etc. • High pressure Oxygen consumption: 0 .7 Nm3 O₂/kg feed Capex: 180 to 400 mm USD
Technology Handbook Air Liquide Engineering & Construction 33 HYDROGEN & SYNGAS Lurgi FBDB™ – Fixed Bed Dry Bottom GENERATION Coal Gasification
Application Description Sulphur ASU Elemental Sulphur Gasification of coal to produce syngas Recovery Unit Coal is converted into syngas by reacting in a GOX FBDB Feedstock counterflow fixed bed with oxygen and steam. CO₂ Rich Gas The raw syngas will be further processed Lumpy coal, especially suited for low-rank Coal (CO-shift, Rectisol™) to meet the downstream FBDB™ (CO Shift) & Gas Syngas DRI Ammonia (high ash, high water) coal Gasification Gas Cooling Purification SNG Liquid Fuel requirements of the processes. Side streams are (Rectisol™) HP Steam Product further treated using proprietary technologies to produce valuable co-products, as well as to Rectisol Naphtha Syngas (H₂+CO), due to high CH₄ content Ash particularly suited for the production of SNG meet environmental specifications. Special water (synthetic natural gas) or DRI treatment allows for zero liquid discharge while Gas Liquor Phenosolvan® (direct reduction of iron ore) minimizing water consumption. Separation CLL™ ZLD / Water reuse GLS Process™ WW Treatment Main Features: Co-product • Robust technology that can be fed with coarse Liquid Ammonia Crude tar acids (phenols), sulfur, lumps, avoiding the need for grinding and drying Phenols tar, oil, naphtha, ammonia • Higher cold gas efficiency than entrained flow Tar / Oil gasification Capacity • Wide variety of coal possible 40,000 to 120,000 Nm3/h dry syngas per • Lower water consumption than entrained gasifier, typically more than 5 reactors per flow gasification plant, largest plant 40 reactors at one site. References Economics Individual costs depend strongly >100 gasifiers on location, coal quality, etc. Contact Yield: 2000 Nm3 dry syngas / ton dry coal [email protected] Capex: 420 to 650 mm USD (cost base: 7 Mk+ in China)
34 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS Rectisol™ – Syngas Purification GENERATION
Application Description Lurgi Rectisol® - The “5 in 1” Solution: Feedstock 1 Trace contaminant removal Selective removal of acid gases Gasification Acid gases in raw gases from any gasification are 2 Deep Desulfurization (total S < 80 ppb) (CO₂ and H₂S+COS) and of nearly all trace 3 Bulk CO2 removal (up to 100%) removed by absorption with a physical solvent 4 CO2 purification (total S < 5 ppmv) components (carbonyls, mercaptans, COS Dry CO Capture Ready (> 98.5 vol%) (cold methanol). The rich solvent leaving the 2 HCN...) from syngas of any gasification (coal, Hydrolysys 5 Acid Gas Enrichment (S > 25 vol%) contactor is regenerated by flashing and petcoke, residue, heavy oil,...) to meet highest stripping. Different process configurations are specification reqirements for catalytic available to deliver a tailored solution optimized Trace processes. Removal for Capex and Opex for a given syngas Acid gas suitable for sulfur recovery processes Feedstock specification.
Raw syngas deriving from gasification Rectisol™ is the leading process when it comes Sulfur Acid Gas H2S Sulfur Removal Enrichment CO Recovery of any carbon containing feedstock to the purification of gasification-based syngas 2 for catalytic applications (production of SNG, Product Syngas suitable for methanol, ammonia, or Fischer-Tropsch) as well catalytic synthesis Clean/high purity syngas (H₂+CO) as hydrogen processes CO2 CO2 CO CO2 Removal Treatment 2 Compressor for catalytic processes, clean hydrogen Using inexpensive solvent in combination with CO₂ suitable for optimized heat integration, the Rectisol process compression, synthesis Co-product or venting has extremely low operating costs and high H₂S rich gas for SRU, CO₂ offgas availability. ready for storage/utililization Main Features: Capacity • Highest level of purity for all contaminants 100,000 to 1,000,000 Nm3/h per train • Low Capex and Opex when compared to other purification process Economics • Low cost solvent Individual costs vary significantly depending • CO₂ offgas meeting most stringent emissions on feedstock, size, purity request, etc. requirements References Capex: 90 to 290 mm USD > 110 (> 35 since 2005) Contact
Technology Handbook Air Liquide Engineering & Construction 35 HYDROGEN & SYNGAS SEPARATION
Leveraging on our vast technology portfolio, we have the means to combine various patented processes to address any Hydrogen & Syngas separation challenge. Our customers benefit from continuous improvements due to Air Liquide’s own track record in its operational experience of such processes - from cryogenics to permeation to adsorption.
36 Air Liquide Engineering & Construction Technology Handbook Overview
Pressure Swing Adsorption PSA #38 H2 Offgas (Refineries, Pure H2 Crackers, PHD...)
H2 Membrane #42
Liquid Nitrogen Ammonia Syngas N H Wash #41 2 2
Hydrogen Liquefier #43 Liquid Hydrogen
CO Cold Box Pure CO Methane Wash #39 Hydrogen & Syngas Generation CO Cold Box #40 O ogas Partial Condensation
Hydrogen
Technology Handbook Air Liquide Engineering & Construction 37 HYDROGEN & SYNGAS Pressure Swing Adsorption (PSA) SEPARATION Hydrogen Purification
PRODUCTION Application Description Recovery and purification of pure hydrogen Pure H₂ product is delivered at a pressure close from different H₂-rich streams to feed pressure (pressure drop across PSA Feedstock could be as low as 0.5 bar) and impurities are removed at a lower pressure (typical PSA offgas Raw hydrogen from SMR, POX, cryogenic pressures range from 1.1 to 10 bara). purification, methanol plant purge gases, ethylene off-gas, styrene offgas, gasification, The PSA tail-gas, containing impurities, can be ammonia plant, CCR, and other offgases or sent back to the fuel system (SMR burners any combination of the above or refinery fuel network) with or without the need of a tail-gas compressor. Operation is fully Product automatic. Hydrogen up to 99.9999% purity PSA units use the most advanced adsorbents Co-product on the market and patented high efficiency cycles to provide maximum recovery and FEED OFF None productivity. Typical on-stream factors are GAS DRUM >99.9%. Capacity OFF GAS 5,000 to 200,000 Nm3/h Turndown can be as low as 25%. PSA units are compact, fully skid- mounted Economics and pre-tested units designed for outdoor and H₂ recovery rate: 60 to 90% unmanned operation. 3 Opex: Feed+Fuel: Appr. 13.6 MJ/Nm H₂ References (Figures based on nat. gas feed & fuel) Capex: 1 to 5 mm USD >70 (in operation or under construction) Contact
38 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS CO Cold Box – Methane Wash SEPARATION
Heat Application Description Exchanger Carbon monoxide (CO) production Fuel Methane Wash process is based on cryogenic H₂ or ratio-adjusted synthesis gas production separation technology using the difference in COCH4 from synthesis gas for use in chemical Column boiling points of the main components from the industry synthesis gas. Wash Stripping Feedstock Feed gas is pretreated to remove impurities Column Column which will freeze at cryogenic temperatures Synthesis gas from natural gas, naphtha or CH4 coal/residue. encountered in the process. It is then cooled Pumps down in heat exchangers and washed with liquid Product methane before being purified step by step CO up to 99.99% purity through distillation columns. Co-product Every cryogenic process is tailor-made to fit the customer’s specifications and other Hydrogen, oxogas, methane, LNG requirements on co-products. CO CO Expander Capacity Main Features: Compressor Up to 34 000 Nm3/h (1 020 tpd) CO • Greatest number of references in CO/N₂ separation CO Economics • Highest safety standards for all Cold Boxes Opex: Specific energy: • In-house technology for highly safe, highly Syngas 300 to 600 kWh/tonne reliable & highly efficient CO expander Capex: Economics are highly dependent on • High CO recovery the type and quality of feedstock (coal, References Naphtha or natural gas), as well as the required CO purity and pressure (MDI/TDI, 32 (latest 2016) PC, AcAc, MEG, etc.) and of the required scope of supply Contact
Technology Handbook Air Liquide Engineering & Construction 39 HYDROGEN & SYNGAS CO Cold Box – Partial Condensation SEPARATION
Heat Exchanger
Fuel Application Description H₂ rich Carbon monoxide (CO) production COCH4 Partial Condensation process is based Column or ratio-adjusted synthesis gas production on cryogenic separation technology using the from synthesis gas for use in chemical difference in boiling points of the main industry Stripping components from the synthesis gas. Column Feedstock Feed gas is pretreated to remove impurities Syngas Drum Synthesis gas from natural gas/naphtha or which will freeze at cryogenic temperatures coal/residue gasification. encountered in the process. It is then partly condensed in heat exchangers and flashed in a Product syngas drum before being purified step by step CO up to 99.99% purity through distillation columns. Every cryogenic process is tailor-made to fit the Co-product customer’s specifications and other Hydrogen, oxogas, methane, LNG CO requirements on co-products. Compressor Capacity Main Features: CO Up to 55 000 Nm3/h (1 650 tpd) CO • Greatest number of references in CO/N₂ separation Syngas Economics • Highest safety standards for all cold boxes Opex: • Low specific energy consumption for wide Specific energy: 18 to 100 kWh/tonne range of feedstock Capex: References Economics are highly dependent on the type 17 (latest 2017) and quality of feedstock (coal, Naphtha or natural gas), as well as of the required Contact CO purity and pressure (MDI/TDI, PC, AcAc, [email protected] MEG, etc.) and of the required scope of supply
40 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS Liquid Nitrogen Wash SEPARATION
MP GAN Application Description Synthesis gas Production of pure synthesis gas Raw hydrogen and high pressure nitrogen are Product 3H₂=N₂ for ammonia plants fed to the liquid nitrogen wash unit. LNW Offgas Feedstock Both streams are cooled down against product gas. Raw hydrogen (from Amine Wash / Rectisol ™) Raw hydrogen is fed to the bottom of the nitrogen wash column and condensed nitrogen Product liquid is fed to the top. Trace impurities, like Pure ammonia synthesis gas with methane, argon and carbon monoxide, are GN₂ a stoechiometric N₂/H₂ ratio of 1:3 removed and recycled as fuel gas. To establish the desired H₂/N₂ ratio, high Front End Syngas Purification Co-product pressure nitrogen is added to the process Methane, LNG stream. Capacity Main Features: Up to 230 000 Nm3/h (2 100 tpd) • Highest safety standards for all Cold Boxes LIN • Low specific energy consumption Economics for Methane / LNG co-production Opex: References - LIN: 0 to 0.02 tonne/tonne of syngas - Power: 0 to 900 kWh/tonne of LNG 49 (latest 2015) (if LNG co-production) Contact Capex: [email protected] Economics are highly dependent on the co-product requirements and required scope of supply
Technology Handbook Air Liquide Engineering & Construction 41 HYDROGEN & SYNGAS Hydrogen Separation Membranes SEPARATION
Application Description Coalescing Filter Recovery of hydrogen in refinery Our membranes operate on the basis of or chemical plants purge gas selective permeation. Each membrane is H₂ / CO ratio adjustment Preheater composed of millions of polymeric hollow fibers Hydrogen Feed Gas Hydrogen Feedstock similar in size to the diameter of a human hair. The Rich Permeate Lean Residual “fast gases,” or gases with a higher permeation Permeator Any purge gas streams with hydrogen rate, permeate through the membrane into the concentrations >20 % (vol). hollow interior and are channeled into the Product permeate stream. Simultaneously, the “slower Hydrogen (>99% vol achievable) gases” flow around the fibers and into the residue stream. As a result, the fibers have the ability to Co-product selectively separate a fast gas like hydrogen from Main Features: None carbon monoxide, methane, heavier hydrocarbons and other slower gases • No moving parts Capacity • Skid mounted systems cartridge The process begins when pressurized feed gas design for simple installation Membrane systems are truly scalable with is routed to the coalescing filter to remove virtually no upper capacity limit Largest • Estimated payback period of less contaminants and protect the membranes’ fiber than a year system referenced by Air Liquide: 124 from liquid aerosols and particulates. Feed gas is membrane cartridges • High permeability membranes for compact, low then preheated before entering the membranes. capital system design Economics The membranes then separate the feed into the • Unrestrained turndown capabilities hydrogen-rich permeate and hydrogen-lean Opex: • Linear scale up for all size systems residue. The separation of permeate and residual • Hollow fiber membranes offer higher area to - Dependant on feedstock quality gas is driven by the hydrogen partial pressure volume efficiency resulting in better packing - Hydrogen recovery > 98% difference between the feed gas and permeate efficiency, smaller footprint and reduced weight - 50% + turndown capabilities gas, as well as our advanced polymer material. and module count. Capex: The non-porous hollow fiber membranes 1 mm to 10 + mm USD selectively allow faster molecules to permeate Contact the membrane wall while slower, bulkier molecules remain on the high pressure side. [email protected]
42 Air Liquide Engineering & Construction Technology Handbook HYDROGEN & SYNGAS Hydrogen Liquefier SEPARATION
H2 cycle Pure H Application Description H Purification 2 2 (if required) Liquefaction of all kinds of H₂ stream for the Hydrogen to be treated may come from different filling of H₂ liquid storages which ease sources. Accordingly, source warm purification transportation of H₂ molecules upstream cold purification and liquefier by itself Feedstock may be required. Many sources : natural gas, coal, Hydrogen is precooled thanks to N₂/MR cycle or electrolyse and the use of turbo-expander together with cryogenic exchangers. Product The liquefier uses BAHX (widely used in Liquid hydrogen cryogenic gas liquefaction). Co-product Then it is cooled and liquefied thanks to a H₂ cycle and the use of cryogenic expanders None together with a highly optimized cryogenic Capacity exchangers’ arrangement. The particularity of hydrogen liquefaction is the use of catalyst to Up to 50 TPD convert ortho-hydrogen into para-hydrogen in Economics order to reduce boil-off in storage. LH to storage Boil o from storage Opex: Boil-off from LH₂ storage is sent back into H₂ 2 Less than 10kWh/kg LH₂ cycle, in order to recover molecules. Downstream infrastructure (storages, loading bays, etc.) can also be supplied. Contact
Technology Handbook Air Liquide Engineering & Construction 43 CHEMICALS
Using our expertise and patents in catalytic conversion and purification techniques, we provide technology to produce or to separate valuable intermediate chemicals from syngas and other feedstock. Our experience and continuous development of our products ensures well referenced safe and reliable technology for our customers that can be tailored to meet their specific needs.
44 Air Liquide Engineering & Construction Technology Handbook Overview
Lurgi Methanol #46 Methanol Lurgi MegaMethanol™ #47
Lurgi MTP™ #48 Pro ylene
Any Acrylic Acid carbonaceous Syngas Acrylic Acid #50 feedstock Generation Methyl Acrylate Ethyl Acrylate Acrylates #51 #52 #53 #54 utyl Acrylate 2 EH Acrylate Gas to Gasoline Gasoline (G2G™) #49
Raffinate-2 C4 stream from Butene to Crude Butadiene #55 FCC or MTO/MTP
Butadiene utadiene Crude C4 Extraction #56
Pyrolysis Gasoline Distapex™ #57 en ene Toluene ylene
Urea Melamine #58 Melamine
Technology Handbook Air Liquide Engineering & Construction 45 CHEMICALS Lurgi™ Methanol
Application Description Saturated Steam Drum Steam Medium-scale production (< 1 million tpa) of Interchanger In the LP methanol unit (either with integrated BFW methanol from synthesis gas derived from all gas generation based on natural gas or kinds of carbonaceous material downstream of a coal gasification unit) syngas is Feedstock converted over a copper catalyst in water- cooled reactor to produce raw methanol. Synthesis Gas Recycles Gas Natural gas or synthesis gas (H₂+CO) Compressor Compressor Unconverted synthesis gas is recycled back to Product Product the synthesis loop to enhance yield and carbon Separator Final Make Up Gas Cooler Methanol in the required specification (AA, efficiency. Water IMPCA, etc.) Cooled Raw methanol leaving the synthesis loop is Reactor further distilled to meet the required specification. Co-product Cooling Water Main Features: Purge Gas None Crude Methanol Blow Down • Simple to operate over full catalyst life time Capacity • Optimized heat transfer preventing temperature Note: scheme represents only the methanol synthesis unit Up to 3,500 tpd peaks in the methanol reactor • Flexible integration with any syngas generation Economics Natural gas consumption: References 29 MMBTU (LHV)/tonne (this includes >40 energy for the process, all utilities and the ASU that produces 0.4 - 0.5 tonne O₂/tonne Contact methanol) Capex: [email protected] 250 to 500 mm USD
46 Air Liquide Engineering & Construction Technology Handbook CHEMICALS Lurgi MegaMethanol™
Gas Cooled Water Cooled Application Description Reactor Reactor Large scale production (> 1 million tpa) In the Lurgi MegaMethanol™ unit (either with of methanol from synthesis gas derived from integrated gas generation based on natural gas 40 bar Steam all kinds of carbonaceous material or down-stream of a coal gasification unit) Feedstock syngas is converted over a copper catalyst in a two-stage reactor system (water-cooled Natural gas or synthesis gas (H₂+CO) followed by gas-cooled) to produce raw Synthesis Gas Recycle Gas Compressor Compressor Product methanol. Unconverted synthesis gas is recycled Methanol in the required specification back to the synthesis loop to enhance yield and carbon efficiency. Make Up Gas (AA, IMPCA, etc.) Final Cooler Raw methanol leaving the synthesis loop Co-product is further distilled to meet the required None Trim Heater specification. Cooling Water Due to high energy integration of the unit and the Capacity Purge Crude Boiler Feed low recycle ratio in the synthesis loop, Lurgi Gas Methanol Water 2,500 to 7,000 tpd MegaMethanol™ yields the lowest production 10,000 tpd (GigaMethanol) cost. Note: scheme represents only the methanol synthesis unit Economics Our most recent design (GigaMethanol) can Natural gas consumption: produce up to 10,000 tpd in one single train. 29 MMBTU (LHV)/tonne (this includes Main Features: energy for the process, all utilities and the • Methanol loop with minimized recycle ratio References ASU that produces 0.4 - 0.5 tonne O₂/tonne resulting in reduced piping and equipment methanol) in operation (5 gas based, 4 coal based), • Process intensification through interstage 9 in construction (2 gas based, 2 coal based). Capex: condensation possible 4 400 to 1100 mm USD • Best referenced technology in the 5000 mtpd Contact class [email protected]
Technology Handbook Air Liquide Engineering & Construction 47 CHEMICALS Lurgi MTP™ – Methanol-to-Propylene
Application Description MTP Reactors Fuel Gas This on-purpose production of propylene Internal Use In a first step, methanol is converted into 2 Operating from methanol is a way to produce 1 Regeneration Ethylene dimethyl-ether (DME) which is, together with 60 t/d propylene independently from crude oil and/ recycled hydrocarbon streams, the feedstock for or natural gas liquids. Hence, it supports the Propylene the fixed-bed MTP reactor filled with proprietary Product 1410 t/d utilization of land-locked coal or natural gas Conditioning zeolite catalyst. The effluent from the MTP DME Product reserves as feedstock for petrochemical reactor is cooled and enters a separation Pre-Reactor Fractionation processes sequence similar to the one applied in steam- Feedstock crackers. During this sequence, the effluent is separated into different hydrocarbon streams Methanol which are partially recycled to the reactor in order LPG 109 t/d Product to maximise the propylene yield. The last step of Polymer-grade propylene the separation sequence yields polymer-grade propylene. Co-product Compared to crude-based processes (naphtha Gasoline and LPG cracking, metathesis, PDH) the MTP process has Water Recycle the lowest cash cost. Olefin Recycle Capacity Gasoline 500 to 1,500 tpd Main Features: 540 t/d • Focus on propylene product Process Water Economics • Lowest cash cost Yield: • High integration potential with methanol 3.5 tonnes methanol/tonne propylene and other technologies Capex: References 250 to 500 mm USD 3 in operation (all coal based), first natural gas based plant in engineering stage. Contact
48 Air Liquide Engineering & Construction Technology Handbook CHEMICALS G2G™ – Gas-to-Gasoline
Application Description Natural Gas Syngas Lurgi MTG ~ 16.100bpd Lurgi MegaMethanol™ and ExxonMobil 160 MMSCFD Plant Methanol Plant G2G™ technology presents an opportunity to Gasoline MTG technologies are licensed in an monetize low cost feedstock into transportation integrated approach to monetize low cost 5.000 mtpd fuels either for domestic use or for export feedstock, usually natural gas or coal, to high Methanol markets. Projects are driven by the spread Air Liquide Lurgi Technologies value oil products. Air Liquide can also between the price of feedstock and oil products. ASU leverage its global network of ASUs and Low cost gas or stranded gas can enhance Exxon Mobil Technologies syngas facilities to provide synergistic profitability even at low-moderate oil price solutions for G2G™ projects. scenarios. The gasoline product from G2G™ is Feedstock low in benzene and has no sulfur compounds. Product can be used as on-spec gasoline that Natural gas (NG), coal, heavy hydrocarbons, meets or exceeds any typical (stringent) biomass environmental standards or as a refinery Product blending stock. Sulfur free gasoline/petrol Profitability is driven by low feedstock prices relative to market value of wholesale oil products. Co-product LPG (optional) Contact Capacity [email protected] 1,000 to 32,000 bpd Standardized design: 16,100 bpd Economics Yield: 9,100 scf natural gas/barrel Opex: 8.5 USD/barrel Capex: 250 to 2000 mm USD
Technology Handbook Air Liquide Engineering & Construction 49 CHEMICALS Lurgi / Nippon Kayaku Acrylic Acid
Application Description Reactor 1 Reactor 2 Demin The combined Lurgi/Nippon Kayaku Water Reaction: Acrylic acid (AA) is produced by Recycle Gas technology produces ester-grade acrylic Steam Offgas catalyzed oxidation of propylene in a two-stage Propylene to Incineration acid (EAA). Main uses are adhesives, paints tubular fixed-bed reactor system. Air and coatings (acrylic esters) The reactors are cooled by circulating molten heat transfer salt. The heat of reaction is used to Solvent Crude AA Feedstock Extraction Recovery produce steam. MP MP Steam Steam Quench / Propylene Absorber Quench: The AA is recovered from the reactor Final Raffinate Acrylic Acid EAA Product product gas in a quench tower. MP Stripping Purification Product Steam Ester-grade acrylic acid The AA solution is routed to an extractor. MP Steam Waste Organic Uncondensed gases are sent to an offgas treater Water Waste Co-product to recover the remaining AA. A side draw from None the offgas is sent to incineration. Overhead gas is recycled to the first reactor. Capacity Solvent extraction: Liquid-liquid extraction is Up to 20 t/h (single train) used to separate water and AA. The solvent is with an optimized process. With low raw material Economics recovered and recycled. In a first step, water and and energy consumption, low environmental acetic acid are removed to achieve a crude AA to impact and high onstream time, this technology Capex: 200 to 300 mm USD be further purified in the next process steps. The exhibits competitive production costs. extractor bottom is sent to the raffinate stripper to Acrylic acid purification: Crude AA is purified in recover remaining solvents. the ester grade AA column. To maximize AA Crude AA recovery: In this section, solvent and recovery, dimer is converted to AA in a acetic acid are removed from crude AA using dedimerizer. two columns. References Raffinate stripping: The raffinate stripper recovers solvents from the wastewater streams. 1 The Lurgi/Nippon Kayaku technology combines Contact high performance catalysts with highest acrylic acid yields and outstanding catalyst longevity [email protected]
50 Air Liquide Engineering & Construction Technology Handbook CHEMICALS Methyl Acrylate (Synthomer Licensed)
Application Description Production of methyl acrylate (MA) by the The reaction is catalyzed in a fixed bed reactor by MA esterification reaction of acrylic acid with means of a strong acid solid catalyst (ion- methanol (MeOH). The methyl acrylate is exchange resin). used mainly for adhesives, paints and The reactor effluents are routed to the coatings column AA recovery fractionation section to separate unreacted Feedstock acrylic acid from crude methyl acrylate, process Reactor Acrylic acid, methanol water and methanol. Further purification of the Alcohol Extractor crude methyl acrylate takes place in the alcohol Ends Column Light Column Final Product Product extractor and the light ends column where Methyl acrylate process water and methanol, as well as other Decomposer light ends, are removed. The final product column AA Co-product separates high boiling components to be routed MeOH Catalyst None
to the AA recovery section and the purified MA Column Alcohol Recovery product can be send to storage. Capacity In the AA regeneration section acrylic acid is Up to 4 t/h recovered to be recycled to the reactor. Economics The high boiling components are routed to the Organic Residue Waste Water decomposer where they could partly be Process configuration is optimized resulting converted back to methanol, methyl acrylate in low raw material consumption, optimized and acrylic acid to be recycled. Remaining energy integration and low utility unconverted components are discharged to requirements. Environmental impact battery limit for further treatment. minimized. On stream times exceeding 8,000 hours per year could be achieved The bottom product of the alcohol extractor is routed to the methanol regeneration section to recover methanol to be recycled to the reactor. References The water is partly reused in the process as well as routed to battery limit for further treatment. 1 Methyl acrylate is prone to polymerization. Contact In order to minimize polymerization effects, an inhibitor injection system is foreseen at critical [email protected] locations in the plant.
Technology Handbook Air Liquide Engineering & Construction 51 CHEMICALS Ethyl Acrylate (Synthomer Licensed)
Application Description Production of ethyl acrylate (EA) by the The reaction is catalyzed in a fixed bed reactor by esterification reaction of acrylic acid with means of a strong acid solid catalyst (ion- ethanol (EtOH). The ethyl acrylate is used exchange resin). mainly for adhesives, paints and coatings The reactor effluents are routed to the Feedstock fractionation section to separate unreacted AA Recovery Column AA Recovery Acrylic acid, ethanol acrylic acid (AA) from crude ethyl acrylate, process water and ethanol. Further purification Alcohol Extractor EA
Product of the crude ethyl acrylate takes place in the Ends Column Light Reactor Ethyl acrylate alcohol extractor and in the light ends column where process water and ethanol as well as Co-product other light ends are removed. The final product None column separates high boiling components to be AA routed to the AA recovery section and the Heavy End Column Decomposer Capacity purified EA product can be sent to storage. EtOH Final Product Column Final Product Alcohol Recovery Column Alcohol Recovery Up to 4 t/h In the AA regeneration section the acrylic acid is Catalyst Economics recovered and recycled to the reactor. The high boiling components are routed to the Process configuration is optimized resulting Organic Residue Waste Water decomposer where they are partly converted in low raw material consumption, optimized back to ethanol, ethyl acrylate and acrylic acid to energy integration and low utility be recycled. Remaining unconverted requirements. Environmental impact components are discharged to battery limit for minimized. On stream times exceeding further treatment. 8,000 hours per year could be achieved The bottom product of the alcohol extractor is routed to the EtOH regeneration section to recover ethanol to be recycled to the reactor. References The water is partly reused in the process as well as routed to battery limit for further treatment. 1 Ethyl acrylate is prone to polymerization. In order Contact to minimize polymerization effects, an inhibitor injection system is foreseen at critical locations in [email protected] the plant.
52 Air Liquide Engineering & Construction Technology Handbook CHEMICALS Butyl Acrylate (Synthomer Licensed)
Application Description Production of butyl acrylate (BA) by the The reaction is catalyzed by means of para- esterification reaction of acrylic acid (AA) toluene sulphuric acid (PTSA). A four stage with butanol (BuOH). The butyl acrylate is reactor system ensures the conversion. The BA used mainly for adhesives, paints and process water generated by the reaction is coatings NaOH continuously removed from the reactor system. BuOH Feedstock Process water, unconverted butanol and acrylic
acid leaving the reactor system are separated in Column Removal Water
Acrylic acid, butanol Column Alcohol Recovery the dehydration columns. The organic phase Product (mainly butanol and AA) is recycled. The liquid Waste Water
Butyl acrylate crude BA and the catalyst are routed to the Ends Column Light Column Final Product catalyst extraction column where the catalyst is Column Neutralisation Decomposer Co-product extracted by means of process water and is Waste Water recycled to the reactors. Residual acrylic acid in None Catalyst the crude BA is neutralized in the neutralization Organic Capacity column by means of a caustic soda solution. AA Residue Up to 20 t/h In the purification section light ends are removed Catalyst
Economics from the crude BA and recycled back to the Column Extractor Catalyst reactor system. In a second step high boiling Process configuration is optimized resulting components are separated and the final pure BA in low raw material consumption, optimized product is generated to be sent to storage. The energy integration and low utility high boiling components are transferred to the requirements. Environmental impact decomposer where they could partly be minimized. On stream times exceeding converted back to mainly BA to be recycled to 8,000 hours per year can be achieved the reactor section. Remaining unconverted References components are discharged to battery limit for further treatment. 1 Butyl acrylate is prone to polymerization. Contact In order to minimize polymerization effects, an inhibitor injection system is foreseen at critical [email protected] locations in the plant.
Technology Handbook Air Liquide Engineering & Construction 53 CHEMICALS 2-Ethylhexyl Acrylate (Synthomer Licensed)
Application Description 2EHA Production of 2-ethylhexyl acrylate (2EHA) The reaction is catalyzed by means of para- by the esterification reaction of acrylic acid toluene sulphuric acid (PTSA). with 2-ethylhexanol (2EHOH). The 2EHA 2EHOH A three stage reactor system ensures the produced is used mainly for adhesives, conversion. The process water generated by the paints and coatings Toluene reaction is removed continuously by an Extractor Feedstock azeotropic distillation step with a carrier agent. Final Product Column Final Product Acrylic acid, 2-ethylhexanol The reactor effluent which contains the reacted Column Alcohol Recovery 2EHA, non-reacted 2EHOH and PTSA is routed Catalyst Regeneration Column Regeneration Catalyst Product to the extraction section where the PTSA Reactor Coalescer Decomposer 2-ethylhexyl acrylate catalyst is extracted by means of process water AA and recycled to the Catalyst Regeneration Catalyst Co-product Column.
None Additional 2EHOH is introduced via this column Organic into the process and the extraction water is Catalyst Residue Capacity separated. The recovered PTSA catalyst and the Water Drum Up to 5 t/h preheated 2EHOH is routed to the first reactor. Waste Water Economics In the coalescer section water is removed from the extracted crude 2EHA. Process configuration is optimized resulting In order to minimize polymerization effects, The following purification section separates in low raw material consumption, optimized an inhibitor injection system is foreseen unreacted alcohol which is recycled to the energy integration and low utility at critical locations in the plant. reaction section. Furthermore, high boiling requirements. Environmental impact components are removed and the final pure References minimized. On stream times exceeding 2EHA product is generated to be sent 8,000 hours per year could be achieved to storage. The high boilers are discharged 1 to the heavy end decomposer where they are Contact partly converted back to 2EHA and 2EHOH and recycled to the reactor section. Remaining [email protected] unconverted components are discharged to battery limit for further treatment. 2EHA is prone to polymerization.
54 Air Liquide Engineering & Construction Technology Handbook CHEMICALS Butene-to-crude Butadiene (Mitsubishi BTcB Process)
Application Description The BTcB process produces crude BTcB The butene rich feedstock is oxidatively Water butadiene by oxidative dehydrogenation of dehydrogenated in a fixed bed reactor using air Butenes butenes. Ogas and steam. After quenching the reactor effluent, Air The process offers the option for an remaining oxygen, oxygenates and other on-purpose production of 1,3-butadiene in impurities are removed. grassroot plants as well as an enhancement The produced crude butadiene is routed to a of 1,3-butadiene yield in existing naphtha crude BASF NMP butadiene extraction unit for further Oxidative Butadiene cracker or refinery facilities. Dehydrogenation Quench NMP Final purification to generate the final high purity Absorption Butadiene 1,3-Butadiene Reaction Degassing Extraction Product Feedstock 1,3-butadiene product. section Raffinate 2 from naphtha cracker The Mitsubishi BTcB process combines high Butene rich C4 from FCC units conversion rates and high selectivity while C4 by-product of MTO/MTP units operating at mild reaction conditions. Product References 1,3-butadiene Waste Water 1 pilot plant Co-product Contact None chemicals @airliquide.com Economics Contact us for more information
Technology Handbook Air Liquide Engineering & Construction 55 CHEMICALS Butadiene Extraction (BASF NMP Licensed)
Application Description C3/C4 - HC Ranate Recovery of 1,3 butadiene from a crude C4 In the pre-distillation tower methyl acetylene, C4 Acetylene stream from olefins plants by extractive propadiene and other light components are distillation separated from the C4 cut feedstock which then Water Feedstock enters the bottom section of the main washer NMP column while NMP solvent enters at the top. C4 Crude C4 NMP raffinate consisting of butanes and butenes is Butadiene Product drawn off as overhead product. The loaded C4-HC 1,3 butadiene solvent is sent to the rectifier. In the first compartment of the divided wall column, the less Co-product soluble butenes are separated and recycled to None the main washer while C4 acetylenes are separated from crude butadiene in the second C4/C6 - HC Capacity compartment. The solvent from the rectifier is NMP to heat recovery 6 to 35 t/h sent to the degassing tower where hydrocarbons are stripped from the solvent and C3 - Predistilation Extractive Distilation Degassing BD Distilation Economics than recycled to the rectifier by a compressor. Utility consumption: The side stream of the degassing tower (per tonne butadiene) containing diluted C4 acetylenes is fed into Ecology: NMP biodegrades readily and has low - Steam: 1.7 t/t a scrubber to recover NMP solvent. toxicity to aquatic life. Compared to other - Electricity: 150 kWh/t After further dilution with raffinate or other technologies, this process is much more - Water, cooling: 150 m3/t suitable materials, the C4 acetylene stream eco-friendly. Capex: 80 to 110 mm USD is discharged to battery limits for further In addition the BASF SELOP selective processing. The crude butadiene withdrawn hydrogenation process can be offered for further as overhead product from the second treatment of the C4 Acetylene stream to compartment of the rectifier is sent to the increase the 1.3 Butadiene yield. butadiene column for final purification. References The butadiene product is withdrawn as liquid side product. >36 Contact
chemicals @airliquide.com
56 Air Liquide Engineering & Construction Technology Handbook CHEMICALS Distapex™ – Aromatics Extractive Distillation
Application Description CW Recovery of aromatics from a heart-cut Combined The aromatics in the feedstock are separated by Ranate and Ranate feedstock by extractive distillation Extractive extractive distillation using N-methylpyrrolidone Distillation Column CW Feedstock (NMP) as a solvent. The raffinate product containing the non-aromatics leaves the Pyrolysis gasoline extractive distillation column via the top. The Solvent Benzene Product loaded solvent is routed to a stripper column Stripper Benzene where the final aromatic product is recovered at CW the column top and routed to battery limit. The Aromatics Cut Co-product lean solvent is recycled to the extractive None distillation column. Ecology: Due to the unique properties of NMP, Capacity the process has an excellent ecological footprint Up to 40 t/h and requires medium pressure steam only. MP Steam MP Steam Economics The Distapex™ process requires a minimum Rich Solvent number of equipment items and is especially Lean Solvent Recovery rate: > 99.5% renowned for reliability and availability as well as Utility costs: 8.8 USD/tonne low operating costs. Utilities (per tonne benzene): - Steam, tonne: 0.7 References - Electricity, kWh: 8 >27 - Water, cooling, m3: 19 - Solvent loss, kg: 0.01 Contact Capex: 40 to 80 mm USD chemicals @airliquide.com
Technology Handbook Air Liquide Engineering & Construction 57 CHEMICALS Lurgi/Edgein Melamine
Circulation Gas Application Description Blower The Lurgi/Edgein low pressure technology Molten urea is fed to a fluidized bed reactor using produces melamine from urea in a catalytic Urea a silica/aluminum oxide catalyst. Scrubber Gas Cooler Filter vapor-phase reaction. Main uses are Product The fluidization is accomplished with an Cyclone laminates, adhesives and coating. ammonia /CO₂ mixture to process off-gas. Feedstock The required heat for the reaction is provided by circulating molten salt through internal heating Reactor Catalyst Fines Urea Urea Ammonia & Melem coils. The gaseous reactor effluent is cooled to a Cooler Molten Product level that the by-products and the catalyst fines Urea Salt Melt can be removed in a filtration step. The solid Melamine Bed melamine particles are generated by Compressor Melanine Co-product desublimation in a crystallizer and are finally Urea Crystallizer Product Pump separated by a cyclone. The off-gas is recycled None Gas Heater to a urea washing tower where it is scrubbed with O-Gas to Treatment Capacity molten urea before being partially recycled as fluidizing gas to the reactor and as quench gas to Up to 7,5 t/h in a single train Gas Scrubbing Reaction and Filtration Crystallization and Separation the crystallizer section. Surplus on off-gas can be Economics recycled to the upstream urea plant or a separate Consumption per metric ton of melamine: off-gas treatment unit. - Urea melt: 3.15 tons, net value 1.5 tons The melamine produced with the Lurgi/Edgein - Ammonia: 0.3 tons technology is characterized by an excellent - Catalyst: 4 kg quality, with small particle sizes and a uniform - HP steam: 0.5 tons particle size distribution exceeding the standard - Electrical power: 1300 kWh requirements for the downstream applications. - Natural gas: 15.5 GJ (ca. 397 Nm³) References - Cooling water: 33 tons >13 - No quench water required (no waste water) Contact Capex: 185 mm USD chemicals @airliquide.com
58 Air Liquide Engineering & Construction Technology Handbook Technology Handbook Air Liquide Engineering & Construction 59 NATURAL GAS TREATMENT
Raw natural gas needs to be treated to meet pipeline and liquefaction specifications. We offer a full range of technologies to remove any kind of contaminant, offering clients a reliable and cost-effective solution tailored to their needs.
60 Air Liquide Engineering & Construction Technology Handbook Overview
CO2
CO2 Removal Cryocap #65 Membranes #66 LNG
NGL Recovery Turbobooster #67 Well NRU #69 Natural Gas Acid Gas (Sulfur, Membranes #68 Mercaptans) Removal
Amine Wash #62 Helium #20 Liquid Helium Omnisulf #63 Purisol #64
NGL Nitrogen
Sulfur
Sulfur
Technology Handbook Air Liquide Engineering & Construction 61 NATURAL GAS TREATMENT Acid Gas Removal – Amine Wash
Application Description Absorption Regeneration Acid Gas Sweet Removal of acid gases (CO₂, H₂S, COS, light HP-Flash Acid gases contained in raw gases are removed Natural Gas mercaptans) from natural gas, associated Flash Gas by absorption with a chemical or a mixture of gases and unconventional gas sources chemical and physical solvent. The rich solvent Demin Feedstock leaving the contactor is regenerated by flashing Water and stripping. Natural gas The process configuration and solvent selection Product will be tailored according to feedstock and sweet Sweet natural gas gas application. Co-product Air Liquide Engineering & Construction can offer very energy-efficient processes such Acid gases as the BASF OASE® purple or formulated MDEA Capacity for pipeline or liquefied natural gas specifications. This process presents the advantage Natural Up to 1,500,000 Nm3/h Gas of very low hydrocarbon co-absorption. Economics References Economics are highy dependent on feedstock and requirements > 50 (high efficiency or low Capex). Contact us for more information Contact [email protected]
62 Air Liquide Engineering & Construction Technology Handbook NATURAL GAS TREATMENT Acid Gas Removal – OmniSulf™
Application Description Regeneration Gas Sweetening and processing of natural gas The OmniSulf™ technology encompasses the by removing CO₂, H₂S, COS, mercaptans, Sweet Gas following proprietary key processes: Raw Gas Acid Gas Removal (RSH, HO) Dehydration water and mercury to pipeline or LNG (CO, HS, COS, (AGR - BASF OASE®) and Mercaptan Dry, Sweet Gas RSH, HO) Removal(DMR) specifications as well as production of liquid Acidic components are removed using BASF’s OASE® technology and the cleaned gas is elemental sulfur while minimizing SO₂ Regeneration Gas emissions to the atmosphere to meet most routed to a dehydration and mercaptan removal (RSH, HO) unit (DMR) that removes moisture and stringent environmental regulations Acid Gas mercaptans with multi-layered bed of specialized (CO, HS, COS) Mercaptan Recovery Regeneration Feedstock zeolitemolecular sieves. If necessary, mercury is (MRU - Purisol™ ) Gas Raw natural gas, associated gas removed from the sweet gas with impregnated activated carbon. Mercaptans are recovered Sulfur Recovery Unit Mercaptan Rich Gas (RSH) Product from the regeneration gas with the Lurgi Purisol™ Acid Gas Dry sweet gas, sulphur (99.9+% purity) technology. All gas streams containing sulfur are Enrichment (AGE) Semi-Lean / Rich solution routed to a sulfur recovery unit (SRU). Elemental Co-product sulfur is produced in the Claus process AGE O gas (CO, COS) None (equipped with a Lurgi Multi-Purpose Burner) Rich Acid followed by a Lurgi tail gas treatment (LTGT™) Gas (HS) Tail Gas O gas Capacity Claus Treatment Incineration (CO, SO) unit combined with an acid gas enrichment Claus (LTGT™) O gas 3 Tail Gas Up to 1,500,000 Nm /h system to boost sulfur recovery and reduce SO₂ Sulfur (HS, Sx) Economics emissions. The liquid sulfur product is degassed to H₂S concentrations below 10 ppm by applying Sulfur Degassing Economics are highly dependent on the Aquisulf™ or DegaSulf™ technology. (Aquisulf™ / DegaSulf™) Vent Gas (HS) feedstock and requirements (high efficiency Offgases are incinerated before being released or low Capex). to the atmosphere. Contact us for more information The OmniSulf™ technology can be tailored for Sulfur Product (Sx) gas reinjection. Contact
Technology Handbook Air Liquide Engineering & Construction 63 NATURAL GAS TREATMENT Acid Gas Removal – Purisol™
Application Description Clean gas Highly selective removal of acid gases The Purisol™ process uses a highly selective, (H₂S, mercaptans, etc.) from natural gas Clean Solvent non-toxic, non-corrosive, easily available solvent and process gases Clean Water S-rich gas (N-Methyl-2-Pyrrolidone, NMP) for the physical absorption of the undesired acidic components Feedstock Absorption Regeneration of a feed gas or process gas, like H₂S and Process water Natural gas, regeneration gas, mercaptans. The process requires very low Laden solvent process gas Raw gas Steam Opex due to several features. Taking advantage Product of the very high selectivity towards H₂S and Condensate Clean sulfur free gas mercaptans compared to CO₂ and hydrocarbons allows a low circulation rate. Co-product The process is operated at ambient temperature Sulfur rich gas for SRU and thus does not need high cooling duty. Regeneration of the solvent is done by flashing Capacity and heating. Because of the high boiling point of 50 000 - 500 000 Nm3/h the solvent, losses are extremely low. Economics A typical application is the cleaning of periodically released regeneration gases of Individual costs vary significantly depending natural gas treatment to a clean fuel gas. Here an on capacity and purity request additional feature is to provide a continuous flow Opex: This process has typically very low of sulfur rich gas to the Claus process by using Opex due to the high selectivity and easy the buffering function of the set up. regeneration as well as a stable solvent with The process can be modularized and also easily low losses due to high boiling point be integrated into existing plants. Capex: 3 to 40 mm USD Main Features : • Non-toxic, non-corrosive solvent, easily available solvent • Smooth and peakless gas to Claus process Contact
64 Air Liquide Engineering & Construction Technology Handbook NATURAL GAS TREATMENT CO2 Removal – Cryocap™NG
Application Description Removal of CO₂ from natural gas, associated The CO₂ rich natural gas is first dried and sent to NG to Pipeline gases and unconventional gas sources ➂ a cold box where it is cooled down and sent to a ➁ Feedstock distillation column. Natural gas with high CO₂ content High CO₂ partial pressure favors the CO₂ partial (> 35%) condensation and thus makes its separation from natural gas even easier. Product The non-condensable gas is enriched in ➀ Natural gas methane and sent to a membrane for final ➃ purification. Co-product Raw NG The CO₂ purity of the product corresponds to CO₂ (under pressure) pipeline specifications, generally 1 to 10 mol%. ➄ NGL (possible) The permeate stream of the membrane enriched CO₂ to EOR in CO₂ is sent back to the cold box. The CO₂ and Capacity ➀ Simple Pre-treatment (Dehydration, Mercury removal) heavy hydrocarbons condense in the cold box Up to 1,000,000 Nm3/h ➁ Cold Box and are collected at high pressure. NGL recovery ➂ Membrane stage ➃ is possible with almost no additional cost. Recycle Compressor Economics ➄ CO2 product Compressor Separation cost: Cryocap™ NG is tolerant to a few % H₂S. less than 1 USD/MMBTU Cryocap™ NG also allows for H₂S bulk removal from NG. Capex savings: > 50% vs. amine absorption Contact (at high CO₂ content) Contact us for more information. [email protected]
Technology Handbook Air Liquide Engineering & Construction 65 NATURAL GAS TREATMENT CO2 Removal – Membranes
Application Description NG CO₂ removal from natural gas to pipeline Air Liquide Engineering & Construction offers a ➂ ➀ Feedstock vast portfolio of gas separation membranes for ➁ natural gas treatment: the natural gas product is Natural gas with moderate Raw Acid gas recovered as a high-pressure retentate while the to high acid gas content impurities are concentrated in the low pressure
Product permeate. This includes bulk CO₂ removal with CO2-rich ➀ Filter-coalescer permeate Sweet natural gas the highly selective MEDAL™ NG, as well as HC ➁ Heater dewpointing, bulk CO₂ removal and dehydration ➂ MEDAL™NG membrane Co-product with PEEK-SEP™ suite of products. Acid gases Main Features: Capacity The hollow-fiber type offers more compact and Up to 500,000 Nm3/h robust membrane solutions to meet pipeline specifications. Air Liquide membrane technology Economics is characterized by higher resistance to Economics are highly dependent hydrocarbons and higher selectivity, compared on feedstock and requirements to cellulose acetate products, offering higher (high efficiency or low Capex). methane recovery, lower investment and operating costs. Contact us for more information. Contact
66 Air Liquide Engineering & Construction Technology Handbook NATURAL GAS TREATMENT Natural Gas Liquids Recovery – Turbo-booster
Option Application Description ➀ NGL (C2+) recovery from natural gas, Offgas Air Liquide Engineering & Construction offers associated gases and unconventional gas NRU open-art or proprietary natural gas liquids Sales Gas sources Cold Box technologies (NGL) for high efficiency C₂ Feedstock recovery (>98%), high propane recovery (99+%) and low energy consumption. Air Liquide Lean or Rich Natural gas ➁ know-how and operational expertise of key Product technology components (heat exchangers, ➂ Ethane, LPG, condensates, natural gas turbo-expander) allow for robust and reliable solutions. Additionally, Air Liquide can combine Co-product NGL recovery with its nitrogen rejection LNG, crude helium technology and expertise in cryogenics to provide overall optimized NGL/ NRU plants. Capacity Natural Gas Up to 1,000,000 Nm3/h Contact Feed [email protected] ➀ Main Heat Exchanger Economics ➁ Turbo-Booster Natural Gas Liquids Increased NGL recovery with significant ➂ Separation Column reduction in capital and/or operating costs as compared to open-art technologies. Contact us for more information.
Technology Handbook Air Liquide Engineering & Construction 67 NATURAL GAS TREATMENT Natural Gas Liquids Recovery – Membranes
Application Description Rich gas NGL recovery from rich gas and fuel gas Lean gas Thanks to outstanding mechanical properties of conditioning (including dewpointing and ➂ the PEEK-SEP™ membranes, liquid C3+ can be BTU value adjustment) ➀ ➁ recovered at high pressure whereas the residual Feedstock gas is produced as a low pressure permeate. The membrane system is simple and reliable, and Natural gas, associated gases, does not require extensive feed gas pre- unconventional gas sources, refinery treatment beyond an inlet coalescing filter. Liquid C3+ off-gas, flared gas PEEK-SEP™ membranes can also be used as a ➀ Feed Compressor Product pretreatment stage upstream of MEDAL™ NG ➁ Air Cooler Treated natural gas, NGL (CO₂ removal units) to optimize the performance ➂ Peek-Sep™ Membranes and reduce overall footprint and weight as Co-product compared to traditional pre-treatment schemes. Fuel gas Other applications of the PEEK-SEP™ membranes include hydrocarbon dewpointing Capacity (the treated gas is produced at high-pressure) Up to 100,000 Nm3/h and nitrogen removal for BTU value adjustment Economics purposes. Air Liquide’s membrane solutions represent a Air Liquide membrane solutions are robust and compact option to unlock the use of Contact characterized by low investment and low quality fuel gas and the monetization of operating costs that can translate into short [email protected] valuable Natural Gas Liquids (NGL) contained in payback periods. rich gas sources such as flared gas, refinery Contact us for more information. off-gases or fuel gas networks. When the feed gas is rich in heavy hydrocarbons, typical refrigeration plants can be attractive when sufficient NGL liquid product can be recovered. Air Liquide POROGEN PEEK-SEP™ membranes provide alternative solutions to recover NGLs even when the amount of NGLs is too low to allow for economic recovery by traditional means.
68 Air Liquide Engineering & Construction Technology Handbook NATURAL GAS TREATMENT Nitrogen Rejection Unit
Application Description ➂ Removal of nitrogen from natural gas, Natural gas feed is partially condensed, then ➀ associated gases and unconventional gas methane and nitrogen are separated into a sources system of distillation column(s). Depending on Nitrogen Offgas Feedstock the feed composition and pressure, the system can include one to three distillation columns. The Natural gas with high nitrogen content process scheme selection is done according to ➄ ➃ Product project-specific parameters such as feed Sales Gas Natural gas, nitrogen evolution with time and product specifications. Air Liquide Engineering & Construction offers a ➁ Co-product wide range of solutions, such as the ability to treat LNG, liquid nitrogen, crude helium any N₂/CH4 mixtures (5-90%), high efficiency, flexibility and recovery (>99% methane), Raw Capacity minimization of greenhouse gas emissions to the Natural Gas Up to 1,000,000 Nm3/h atmosphere (methane in N₂ vent << 1%). Capex optimization and operation flexibility are Economics allowed thanks to proprietary design and Air Economics are highy dependent on Liquide operational feedback. feedstock and requirements (high efficiency or low Capex). References ➀ Main Heat Exchanger ➁ High Pressure Column Contact us for more information. >15 ➂ Low Pressure Column ➃ Condenser/Reboiler ➄ Contact Sales Gas Product pump
Technology Handbook Air Liquide Engineering & Construction 69 SULFUR
Hydrogen sulphide removed in the Natural Gas Cleaning or Crude Oil Refining can be converted into pure sulfur product using proven Claus technology. Over the years, we have developed a highly efficient and reliable burner system and further technologies to boost this traditional process, making it more efficient, less costly and more environmentally friendly.
70 Air Liquide Engineering & Construction Technology Handbook SULFUR Oxynator™ / OxyClaus™ for Sulfur Recovery Units (SRU)
Application Description SWS Gas Oxygen enriched SRU operation for In a conventional Sulfur Recovery Unit ambient Acid Gas • Capex / plot space savings for new SRU air is used to oxidize part of the hydrogen sulfide Claus Tail Gas • SRU debottlenecking and revamps Oxygen (H₂S) in the acid gases to sulfur dioxide (SO₂). By Feedstock enriching the combustion air to the Claus unit with pure oxygen more feed gas can be Thermal Catalytic Catalytic Acid gases, Oxygen processed in the SRU without violation of Stage Stage I Stage II Product pressure drop or residence time constraints. Bright yellow sulfur, up to 99.9% purity Air Liquide Engineering & Construction provides the most suited oxygen enrichment technology Co-product depending on client’s requirements. None Oxynator™ for low-level enrichment Sulfur Capacity (<28% O₂ in air) Low-level oxygen enrichment is a very cost Up to 600 tpd sulfur effective option to increase SRU capacity up to Economics 125% as there is usually no modification required on existing SRU equipment. Air Liquide uses its Opex : patented Oxynator™, a compact swirl type mixer, Pure oxygen requirement: for safe and efficient oxygen mixing. Approx. 0.15 - 0.4 ton O₂ / ton sulfur The oxygen is injected into the combustion air (depending on enrichment level and feed upstream of the Claus burner. Main Features: gas composition) OxyClaus™ for high-level enrichment • Integration with ASU (<60% O₂ in air) Capex : • Low power consumption Oxynator™: less than 0.5 mm USD Capacity increase to 200% can be achieved by • Pre-assembled packages using the well known Lurgi OxyClaus™ process OxyClaus™ : up to 35% less than or skid units to ease the erection that can safely handle high levels of oxygen. In conventional SRU with same capacity the specially designed Lurgi OxyClaus™ burner References the oxygen is directly injected into the flame via dedicated oxygen lances. The hot oxygen flame >40 is surrounded by a cooler acid gas – air flame Contact shielding the refractory from exposure to high temperature. [email protected]
Technology Handbook Air Liquide Engineering & Construction 71 SULFUR Sulfur Recovery Unit
Application Description Acid Gas SWS Gas Recovery of sulfur from acid gas streams Flue Gas The acid gases are burnt sub-stoichiometrically containing hydrogen sulfide (H₂S) with air in a refractory lined furnace. Resulting Claus Tail Gas Offgas Feedstock mixture of H₂S and SO₂ reacts to form elemental sulfur which is removed from the process Acid gases from sweetening units through condensation. In subsequent catalytic and sour-water strippers stages, typically two or three, the conversion to TGT Claus Incineration Product sulfur is promoted further yielding a sulfur (LTGT™ or Sulfreen™) Bright yellow sulfur with recovery of 94.5% – 97.5% for the Claus unit. up to 99.9% purity Two tail gas treatment (TGT) options are available to boost the sulfur recovery further. Co-product Sulfur Offgas 1) Sulfreen™: A sub-dewpoint; catalytic None purification of the Claus tail gas for an overall Degassing sulfur recovery of up to 99.5%. (Aquisulf™ Capacity or DegaSulf™) Up to 1,000 tpd 2) LTGT™: Claus tail gas is purified in a wet- scrubbing process. Due to the recycling of the Economics H₂S rich stream to the Claus unit, total sulfur Sulfur recovery: >95% recovery can be increased to 99.9%. Sulfur Operating costs can be considered In the degassing section, the H₂S content of the negligible if credit is given for steam liquid sulfur is decreased to less than 10 ppm. produced in SRU. For this the catalytically promoted Aquisulf™ Capex: 10 to 100 mm USD technology or the catalyst free DegaSulf™ technology can be employed. Offgas from tail gas treatment and degassing is incinerated and released to the atmosphere. References >170 Claus plants (4 to 1,000 tpd) >60 tail gas treatment processes >50 Aquisulf™ in operation Contact
72 Air Liquide Engineering & Construction Technology Handbook SULFUR Emission-Free Sulfur Recovery Unit
Application Description AGR Recovery of sulfur from acid gas streams Raw Gas Raw gas is desulfurized in an AGR and the (Purisol™ or Rectisol™) Purified Gas containing hydrogen sulfide (H₂S) with 100% removed acid gas is sent to the emission-free sulfur recovery SRU for sulfur recovery. The oxygen based Claus process is employed to recover sulfur from the Feedstock Acid Gas Tail Gas Recycle acid gas in elemental form. The recovered Acid gases from acid gas removal unit and sulfur is degassed and is then available as a sour-water strippers Claus Tail Gas Tail Gas sellable product. Product Claus tail gas is hydrogenated and cooled before Hydrogenation Tail Gas Bright yellow sulfur with being compressed and routed back to the AGR. OxyClaus™ Quench Compression up to 99.9% purity Here it is desulfurized and the H₂S is recycled together with the acid gas back to the Claus unit. Co-product Other valuable components inside the tail gas, None like H₂ and CO end up in the purified gas. With this recycle a sulfur recovery rate of 100% is Capacity achieved. The sulfur emissions to the Up to 1,000 tpd atmosphere in the overall complex are Degassing Sulfur Economics significantly reduced. OxyClaus™ is used in this concept because this Capex: 25% less than conventional reduces the process gas volume and therefore amine-wash tail gas treatment lowers not only investment cost plus operating Sulfur recovery: 100% cost but also the amount of inert gas sent to Contact us for more information. AGR. References
3 emission-free SRUs have been designed, two are in operation. Contact
Technology Handbook Air Liquide Engineering & Construction 73 LNG
As an expert in cryogenics and a pioneer in the field of Liquefied Natural Gas, we have extensive experience in equipping plants of all sizes with LNG technology. Our modularized designs are easy to construct and our robust liquefaction technology based on cold boxes helps reduce costs.
74 Air Liquide Engineering & Construction Technology Handbook Overview
Liquefaction
Small Large
Downstream Nitrogen Cycle Turbofin™ #76 Bunkering Stations #80
Natural Gas Treatment Single Mixed Refrigerant Smarfin™ #77 BOG Reliquefaction #79
Dual Mixed Refrigerant Liquefin™ #78
Technology Handbook Air Liquide Engineering & Construction 75 LNG Turbofin™ (Nitrogen Refrigerant Cycle)
Application Description Liquefaction of natural gas for small scale The process consists of three main modules: plants serving power applications (peak Feed Gas C E C C E pre-treatment of natural gas (NG), liquefaction shaving, remote power) or fuel (marine, Gas Treatment and LNG storage and loading (truck, trailer, truck, rail, etc.) bunkering barge, etc.). Feedstock 1) The pre-treatment consists mainly of CO₂ and Natural gas H₂O removal. It is either a simple Temperature Scrubber Swing Adsorption (TSA) cycle or a combination Product of amine wash with TSA depending on the CO₂ Brazed Aluminium Heat Exchanger LNG content in the feed gas. HC Condensates Co-product 2) The liquefaction process is based on a nitrogen cycle (closed loop): N₂ is first NGLs, depending on feedstock composition compressed and boosted. After being cooled Capacity down through a Brazed Aluminum Heat Exchanger, it is expanded releasing N₂ at low Up to 0.25 Mtpa pressure and low temperature. Cold N₂ E C Turbo Expander C Compressor Cooler LNG Storage Economics (T<-165°C) is then re-injected into the main Heat Exchanger to cool down the NG and convert Opex: Typically 450 kWh/ton of LNG it to LNG which is sent to storage. Warm N₂ is then recycled through the cycle compressor. Main Features: 3) Storage can either be fabricated for small • Cost effective especially volumes (vacuum insulated) or site erected flat for small scale plant bottom tanks for larger needs, depending on the • Non-hydrocarbon refrigerant applications considered. improving safety The loading station can be adapted to truck, • Simplicity of operation trailer, or maritime. Regasification is added References downstream of the storage for peak shaving facilities. 90 Contact
76 Air Liquide Engineering & Construction Technology Handbook LNG Smartfin™ (Single Mixed Refrigerant Cycle)
Application Description Liquefaction of natural gas for mid scale Smartfin™ is a single mixed refrigerant type plants serving LNG for mid-size export Feed Gas of process optimized with the use of Brazed terminals and peak shavers Aluminium Heat Exchangers (BAHX). Gas Treatment C Feedstock The refrigeration cycle is filled with a mixture of Natural gas hydrocarbons and nitrogen. The refrigerant is compressed and separated in Product liquid and gaseous streams. Lightest fractions of LNG the refrigerant are sent to the cold end of the Scrubber Co-product main heat exchanger, cooled down and sent back to the compressors after being vaporized NGLs, depending on feedstock composition through the main BAHX. Heaviest fractions are Capacity let down and vaporized at an intermediate level in HC Condensates the main BAHX. Up to 1.5 Mtpa The optimization of the mixed refrigerant cycle Brazed Aluminium Economics consists of taking advantage of the vaporization Heat Exchanger Opex: Typically 350 kWh/ton of LNG temperature difference between generated refrigerant streams to optimize the natural gas liquefaction heat exchange profile. In addition, the LNG Storage C Compressor Cooler heavy hydrocarbons removed from the process can be recovered and sold as NGL. Main Features: • Efficient Process • Reduced number of rotating machines References • Flexibility of Operation 17 Contact
Technology Handbook Air Liquide Engineering & Construction 77 LNG Liquefin™ (Dual Mixed Refrigerant Cycle)
LMR
Application Description Feed Gas HMR Liquefaction of natural gas for mid and Liquefin™ is a Dual Mixed Refrigerant type Gas Treatment C large scale plants serving LNG export of process optimized with the use of Brazed terminal Aluminium Heat Exchangers (BAHX). Each of the two refrigeration cycles is using a Feedstock dedicated mixture of refrigerant. Natural Gas The first cycle is filled with a fluid composed of Scrubber Product relatively heavy components (HMR, an ethane and propane mixture). The second cycle uses a LNG fluid made of lighter components (LMR, a HC Condensates Co-product nitrogen, methane and propane mixture). Each HMR and LMR fluid is compressed through a Natural Gas Liquids compressor, cooled and introduced in the Cold C Box under a single phase. The HMR is then let Brazed Aluminium Capacity Heat Exchanger down in several stages, generating the cooling 1 to 5+ Mtpa duty that pre-cools the Natural Gas (NG) and condenses the LMR at about -70°C. Economics No phase separation of LMR is necessary which C Compressor Cooler LNG Storage Opex: Less than 300 kWh/ton of LNG means a simpler scheme and a better operability. The LMR is then also let down, generating the cold duty that allows for NG liquefaction and sub-cooling at about -160°C. The proprietary Main Cryogenic Heat Exchanger Main Features: is a Cold Box mainly composed of compact • The most efficient liquefaction process multi-fluid BAHX and vessels. • Low capital cost • Modular design, lowering construction risk. Contact
78 Air Liquide Engineering & Construction Technology Handbook LNG Boil-Off Gas Reliquefaction Units
Application Description Boil o gas C Reliquefaction of Boil-Off Gas (BOG) A boil-off gas (BOG) reliquefaction unit allows on import & bunker terminals recovery of BOG emitted from LNG storage by reliquefying it. Feedstock Several systems are proposed, either using liquid Boil-Off Gas nitrogen or nitrogen expansion cycle as cooling Brazed Aluminium agent. Heat Exchanger Product E C Typical reliquefaction capacity is in the range Reliquefied Boil-Off Gas 2-40 tons per hour. Capacity Such units avoid BOG flaring, and debottlenecking of LNG export terminals. They 2 to 40 T/h can also reduce the cost of terminal by avoiding Economics investment in BOG compressors Typical power consumption Contact 400 to 800 kWh/ton [email protected]
LNG Storage
E C Turbo Expander C Compressor Cooler
Technology Handbook Air Liquide Engineering & Construction 79 LNG Bunkering Stations
Application Description LNG as bunker fuel LP BOG A distribution hub is used to import small compression Flare LNG for truck distribution quantities of LNG and distribute them to various LNG for remote power generation downstream users such as ships, trucks, or BOG recondenser LNG regas power plant. LNG STORAGE Feedstock A set of several vacuum insulated tanks with a Liquid natural gas maximal capacity of 1000 m3 each are used, HP LNG LNG Gas Pumps vaporizer supply Product minimizing site work and allowing phasing of the LP LNG capacity. Liquid natural gas / natural gas Loading arms Truck loading A proprietary boil-off gas management (BOG) station Integrated ASU Co-product system ensures that no gas is lost during LNG (Optional) transfer None operation of the hub and that the fuel remains as dense and low pressure as possible during the Capacity Trucking storage. LNG carrier 500 to 10,000m3 storage capacity Equipments ensuring the interface with ship Economics (loading arm) and trucks (proprietary Turbo-Bay) are included in the scope of supply. LNG pumps, Opex: N/A transfer lines, metering device and regasification system (if needed) are also provided. Downstream infrastructure (LNG trucks, refueling station, regas satellite station) can also be supplied.
Main Features: • Proprietary BOG management technology without need for BOG compressors • Proprietary transfer systems Contact
80 Air Liquide Engineering & Construction Technology Handbook Technology Handbook Air Liquide Engineering & Construction 81 OLEOCHEMICALS
Our leading edge technologies provide complete system processing, from seed crushing and oil extraction to oil refining for a wide range of downstream applications. Air Liquide Engineering & Construction oleochemical technologies create value for the food, cosmetics, detergents, surfactants and pharmaceutical industries through our comprehensive offering.
82 Air Liquide Engineering & Construction Technology Handbook Overview
Lurgi Biodiesel #86 iodiesel
Methyl Ester Distillation / #87 Methyl Esters Fractionation
Oil / Fats Refining #85 Glycerin Distillation #89 Pharma Glycerin & Bleaching
Bio Propylene io Pro ylene Glycol Glycol #92
Methyl Ester Hydrolysis #88
Fatty Acids
Seed Crushing Fatty Alcohol Oil seeds and Extraction #84 Fatty Acid #90 Fatty Alcohol LP3 #91
Edible Oil
Glucose Sorbitol #93 Sorbitol
Technology Handbook Air Liquide Engineering & Construction 83 OLEOCHEMICALS Seed Crushing and Extraction Lurgi Sliding Cell Extractor
Cake/Flakes from Application Description pre-pressing/preparation Production of crude edible oils The oil content of different types of seeds ranges between 20-50% wt. After feedstock specific Cake Feedstock Extraction DTDC preparation steps (cleaning, drying, etc.) the oil is Meal Oil seeds (soybean, canola/ rapeseed, gained from the seeds by solvent extraction with sunflower, palm kernel...) hexane. For seeds with higher oil content (e.g. Gums (Lecithin) rapeseed, sunflower) the extraction is typically Product Miscella Crude edible oils for use in food or technical combined with a pre-pressing step to reduce the Miscella Oil load on the extraction. Water Crude Oil applications after refining Distillation Degumming Meal for animal feed The Lurgi sliding cell extractor is the core of the extraction plant. It provides high flexibility Recycle Solvent Co-product regarding feedstock changes, very reliable Solvent Crude lecithin operation and optimum extraction conditions Vent with complete counter-current flow of solvent vs. Solvent Absorption / Air Recovery Stripping Capacity cake and large contact areas. Up to 5,000 tpd The miscella (oil/solvent mixture) from extraction is separated into its components by distillation Economics Condensate and water degumming. The solvent is reused in recovery (Zero Waste option) Economics are highly dependent the extraction after removing the collected on the type of feedstock and required meal moisture. Gums can be purified to lecithin or quality. recycled to the meal. Capex: 25 to 100 mm USD The desolventized, toasted, dried and cooled (DTDC) meal is used as protein rich animal feed. References The whole process is kept under slight vacuum >300 so that emissions are controlled by absorption to fulfill environmental regulations. Contact [email protected]
84 Air Liquide Engineering & Construction Technology Handbook OLEOCHEMICALS Natural Oil Refining
Spent Bleaching Spent Filter Application Description Soapstock Earth Aid Removal of impurities from crude Crude oils and fats contain different oils and fats contaminants like free fatty acids (FFA), Feedstock phospholipids (gums), soaps, color, odor, etc. Neutralization Winterization Reesterification Their removal is called “refining” for food Crude oils and animal fats purposes to reach RBD oil quality (refined, FAD Product bleached, deodorized) and “pretreatment” to Crude Deodorizing/ RBD Oil Oil Bleaching Deacidification Pretreated and/or refined oils reach quality for further processing, e.g. for Tocopherol and fats (RBD oil) biodiesel production or oil splitting. rich distillate Technologies are available for all applications: Degumming Co-product Fractionation Olein FFA can be removed chemically by neutralization Stearin Fatty acid distillate (FAD) or thermally by deacidification. Waxes are Gums Tocopherol separated in winterization. Color and polycyclic aromatic hydrocarbons (PAHs) are removed in Capacity bleaching; odors and pesticides during Gum Drying Interesterification Hydrogenation 100 tpd to 2,800 tpd deodorization (with vitamin E as potential by-product). Economics Dried Gums Spent Catalyst Refining also includes process steps for fat Economics are highly dependent on modification like hydrogenation (saturation of application of the refined oil (technical double bonds), interesterification (to adjust the applications or edible oil), the required melting point) or fractionation (separation process steps (e.g. degumming, bleaching, according to chain length) and side processes winterization, deodorization, hydrogenation, like soapstock splitting or gum drying. fractionation and interesterification) and the type of process (batch, semi-batch or References continuous) >400 Contact
Technology Handbook Air Liquide Engineering & Construction 85 OLEOCHEMICALS Lurgi Biodiesel
Oils and Fats Application Description Production of biodiesel Biodiesel is produced from triglycerides by (Fatty acid methyl ester, FAME) transesterification with methanol under Oil Refining Feedstock presence of an alkali catalyst (sodium methylate) NaOH at 60 degrees and atmospheric pressure. Vegetable or animal oils and fats; major feedstock for fuel applications are rapeseed, Key features of Lurgi`s biodiesel technology are soya, tallow or palm oil maximum yield (1 kg feedstock = 1 kg biodiesel), closed wash water loop (no waste water from Glycerin Water Methanol Transesterification Pretreatment and Product core process units) and sediment removal for Catalyst Evaporation Biodiesel meeting all international quality palm and soya oil to remove sterol glucosides far standards, incl. EN 14214 below limits given by international quality and AS™ D6751 standards. Crude Glycerin Only NaOH and HCl are used in the process. Concentration >80% Co-product Washing and Drying Resulting sodium chloride ends up in the glycerin, HCI Sediment Removal Crude glycerin (purity > 80%) can easily be removed and does not cause Capacity fouling or side reactions during further processing (see glycerin distillation). Standard capacities 100 - 1100 tpd
References Biodiesel Economics “ready-to-use” Capex: 7 to 12 mm USD >50 (since 2000) Contact
86 Air Liquide Engineering & Construction Technology Handbook OLEOCHEMICALS Fatty Acid Methyl Ester Distillation/Fractionation
Vacuum Application Description Quality improvement of biodiesel and/or Fatty Acid Methyl Ester (FAME) is separated Steam production of fatty acid methyl ester (FAME) according to molecular chain lengths to apply fractions and metathised FAME for chemical Water specific cuts in a fractionation column. A falling industry film evaporator and vacuum pressure reduce Feedstock heat stress to FAME resulting in superior product quality suitable for surfactant or personal care FAME from transesterification applications. (see Lurgi Biodiesel process) Distilled FAME can also be sold as top-quality Fraction 1 Product water-clear biodiesel with improved cold flow FAME fractions and/or properties and 50-100 ppm residual water. Sterol distilled biodiesel glucosides and monoglycerides are removed close to detection limits. Fraction 2 Co-product Heat recovery by steam generation makes this None process very energy efficient. Capacity References 100 tpd to 1,000 tpd >10 (since 2000) Economics Contact Fatty acid Opex: 30-50 USD/tonne (feedstock) methyl ester (depending on number of fractions [email protected] and their related purities) Residue
Technology Handbook Air Liquide Engineering & Construction 87 OLEOCHEMICALS Methyl Ester Hydrolysis
Application Description Fatty Acid Conversion of methyl esters Fatty Acid Methyl ester is mixed with water and hydrolyzed Purification to fatty acids to fatty acid and methanol at 250 °C and 70 bar. Feedstock Heat recovery reduces the amount of energy used in the process. Methyl ester fractions The reaction mixture is cooled and separated Methyl ester Hydrolysis Product into an organic phase and a water phase. Both Fatty acid fractions streams are distilled and unreacted methyl ester and water are recycled. Co-product The produced fatty acid is methanol-free and Methanol Methanol can be sold without further treatment. Methanol Distillation Methanol Capacity is recovered and can be used in the methyl ester production. 60 tpd Contact Economics Low value short-chain methyl esters can be [email protected] converted to high value fatty acids
88 Air Liquide Engineering & Construction Technology Handbook OLEOCHEMICALS Glycerin Distillation and Bleaching
Application Description Technical Grade Purification of glycerin to pharma Vacuum distillation is used to separate glycerin Glycerin and technical grade from organic components and salts at Feedstock temperatures up to 175°C. The residue from the column bottom is sent to a thin film evaporator to Crude Drying Distillation Bleaching Pharma Grade Crude glycerin from biodiesel Glycerin Glycerin increase glycerin yield. Salt can be separated or oil splitting (fatty acid) plants from the residue by a decanter to reduce the Product amount of waste and to increase glycerin recovery even further. Salt Decanter Thin Film Pharma grade glycerin (purity > 99.7%) Evaporator Pharma grade glycerin as main product is Co-product polished by bleaching, i.e. adsorption at fixed Salt Residue Technical grade glycerin beds of activated carbon. Light impurities end up (purity 85-90%) in the by-product, technical grade glycerin. Capacity References 10 tpd to 600 tpd > 45 Economics Contact Opex: 35 USD/tonne [email protected]
Technology Handbook Air Liquide Engineering & Construction 89 OLEOCHEMICALS Fatty Acid
Application Description Crude Fatty Fatty Acid Acid Fractions Production of fatty acids Oil / Fat Splitting Distillation / Triglycerides are hydrolyzed catalyst-free to fatty Fractionation Feedstock acids and glycerin by addition of water at Residue elevated temperatures (250°C) and elevated Seed oils, tropical oils, animal fats pressure (55 bar) with splitting degrees up to 99.5%. The fatty acids from the splitting column Glycerin Water Hydrogenated or Product Treatment & Hydrogenation Partially Hydrogenated are dried by flashing before further processing by Evaporation Fatty Acids Fatty acid distillation/fractionation or hydrogenation. Water and glycerin are also flashed for heat recovery. Co-product Final concentration of crude glycerin is 80-88% Crude Glycerin Glycerin water (almost salt-free), which can be sold or further concentration 80-88% (25-35% glycerin content) processed to pharma grade glycerin. Fatty acids are separated from non-volatile Capacity components by vacuum distillation. Fractions of 100 tpd to 1,000 tpd different fatty acid chain lengths with high purity can be obtained with our fractionation plants. Economics The use of structured packing and vacuum in the Opex: 10 USD/tonne (feedstock) fractionation columns reduces the thermal stress and ensures high product qualities. Each fatty (depending on number of fractions acid fractionation plant will be tailor-made by our and their related purities) experts to ensure best fit to the needs of our customers. Hydrogenation of fatty acids is the saturation of fatty acid double bonds by addition of H₂ (~99.9% by vol.) under elevated temperatures and pressure (up to 200°C @ 25 bar) in the presence References of a Ni catalyst. This treatment adjusts melting points and enhances storage stability. >25 (since 2000) Continuous (for full hydrogenation and large Contact plants) and batch process variants (for full or partial hydrogenation) are available. [email protected]
90 Air Liquide Engineering & Construction Technology Handbook OLEOCHEMICALS Fatty Alcohol “LP3”
Application Description Wax Ester Route Methyl Ester Route
Improved hydrogenation process Fatty alcohols can be produced from fatty acids Fatty Acid Methyl Ester for fatty alcohol or methyl ester. Latest improvement is the use of the Fatty Feedstock Alcohol Esterification Methanol recycle hydrogenation step with LP3 features: recycle to transesterification Fatty acid or methyl ester Liquid Phase: Proven liquid phase Wax Ester hydrogenation in fixed bed reactors also suitable Fixed Bed Methanol Fixed Bed Product Hydrogenation for long chain fatty alcohols in contrast to vapor Recovery Hydrogenation Fatty alcohol phase hydrogenation.
Fatty Alcohol Distillation Hydrogen Fatty Alcohol Distillation Hydrogen Co-product Low Pressure: Comparatively low pressure Fractionation & Fractionation & (reduced from 250 bar to 75 bar) reduces energy Carbonyl Conversion Carbonyl Conversion None requirements (Opex savings approx. 5%) and Capacity Capex (savings approx. 15-20%). Fatty Alcohols Fatty Alcohols 90 tpd to 600 tpd Long Performance: Double reactor system for seamless catalyst changeovers with no Unsaturated Fatty Alcohol: Economics disruption to operations and efficient catalyst As an option, long chain unsaturated fatty alcohols can be obtained retaining 95% of C=C double bonds, based on Methyl Ester route Opex: 100 USD/tonne utilization for more profitable lifecycles (see operation steps in diagram). Contact us for more information. The temperature in the catalyst beds is controlled by hydrogen quenches to limit amount of side-products. References Traces of oxygenates are hydrogenated in a 8 polishing section (carbonyl conversion). The resulting fatty alcohol cuts can further be Contact fractionated into final fatty alcohol products. [email protected]
Technology Handbook Air Liquide Engineering & Construction 91 OLEOCHEMICALS Bio Propylene Glycol (BASF Licensed)
Application Description Production of bio propylene glycol Pharma Grade In this process, licensed from BASF, glycerin is Glycerin (1,2-propanediol, MPG) from glycerin as hydrogenated in liquid phase using a copper alternative to petrochemical route catalyst. The reaction takes place in two serial Feedstock fixed bed reactors at a temperature between 175 Pharma grade glycerin to 195 °C and pressures between 75 and 200 bar. Hydrogen Hydrogenation The crude product is purified in a two-column Product distillation unit to yield pharma grade propylene Pharma grade propylene glycol glycol. Low Boiling Co-product References (e.g. Methanol, Water) Technical Grade Technical grade propylene glycol Propylene Glycol Distillation 1 pilot plant High Boiling commercial demonstration plant (e.g. Ethylene glycol, Capacity 1 Glycerin) 2 plants in engineering phase 50 to 100 tpd Contact Economics Pharma Grade Propylene Glycol Contact us for more information [email protected]
92 Air Liquide Engineering & Construction Technology Handbook OLEOCHEMICALS Sorbitol
Application Description Sorbitol is produced by batchwise Hydrogen The glucose solution is hydrogenated in a batch hydrogenation of aqueous glucose solution. reactor using nickel or ruthenium catalysts. This technology is also suitable for different Reaction takes place at 110°C and 40 bar sugar alcohols, e.g. Mannitol, Xylitol. pressure. After reaction, the product slurry is Hydrogenation Sorbitol Slurry filtered to recover the catalyst. Makeup catalyst Glucose Reactor(s) Feedstock 50% compensates catalyst loss and deactivation. The Glucose from wet milling plants crude sorbitol solution is purified by ion exchange Product and evaporated to the final concentration. Optionally, sorbitol powder can be obtained by Recycle Catalyst Technical, food or pharma grade sorbitol Makeup Pressure Waste melt crystallization. Catalyst Filter Catalyst Co-product References None >10 Crude Sorbitol Ion Capacity Exchange 100 to 200 tpd Contact [email protected] Economics Purified Sorbitol Evaporator Sorbitol Opex: 130-165 USD/tonne w/o feedstock 70% and fixed cost. Capex: 4 to 7 mm USD
Technology Handbook Air Liquide Engineering & Construction 93 CUSTOMER SERVICES
Air Liquide Engineering & Construction now offers its many years of engineering and operational experience to Customers through a growing range of Services. Our goal is to be your one-stop service provider to make Customers gain full visibility over Total Cost of Ownership and optimize each process in the short and longer term.
94 Air Liquide Engineering & Construction Technology Handbook A growing range of services developed CUSTOMER for the plants of the group SERVICES
Our offer is organized in the following On-Site Services Contact categories: Deployment of our experts to site for issue [email protected] Engineering Services resolution, performance checks, installation Conversions, modifications, upgrades: from of components, supervision of planned conceptual and feasibility studies to project or unplanned shut-down events. execution for the improvement of operating Spare Parts Services plants; design for third parties and validation, Customers’ spares management, supply performance improvement programs. of parts through custom lists, safety stocks, Remote Support Services interchangeability studies, compliance with Customer training, safety studies and regulations. recommendations, technical assistance, Customer Service Agreements (CSA) monitoring and diagnostics from our technology To strengthen the partnership with our centers and front-end offices. Customers, Air Liquide Engineering & Construction also offers its Services through tailored CSAs. These CSAs are customized and adjusted to a Customer’s specific needs of support and can include services from the above categories as well as premium Services such as dedicated technical support, definition and optimization of maintenance plans, extension of guarantees. The CSA is the ideal tool to manage the Total Cost of Ownership.
Technology Handbook Air Liquide Engineering & Construction 95 Engineering Services: CUSTOMER pre- and post-sales solutions SERVICES
Air Liquide Engineering & Construction offers a full range of pre- and post-sales solutions, from Case Study: Unit lifetime extension feasibility studies to upgrading of operating plants for performance improvement purposes. Mission Oxygen plant – Europe -2013:
A typical, comprehensive project includes Our Customer wanted to revamp their plant to bring it up date and extend its life. detailed design work, procurement, supervision of installation and restart, performance validation Intervention: tests to verify the effectiveness of the implemented solutions. We identified the need to replace: Engineering Services are central to Customer • Front end purification Service Agreements, where regular product or • Electrical room process improvement options are evaluated. • Main heat exchanger of the cold box Revamping planned to take place during planned shutdown. Engineering Services: We supervised the re-start of the ASU. • Revampings Results: • Design validation • Debottlenecking • + 15 years’ life plant • Studies (Screening/Feasibility/Permitting) • Full compliance with more stringent safety regulations. • Process optimization studies • Excellence of Execution • Performance improvement programs (PIP) • Modifications / Conversions / Upgrades • Efficient intervention in a complex environment meeting customer requirements. • Plant life cycle assessments and extensions • Design for third party organizations • Project development and cost estimates Contact
96 Air Liquide Engineering & Construction Technology Handbook Remote Support Services: monitoring CUSTOMER and analyses for prompt assistance SERVICES
Air Liquide Engineering & Construction specialists can perform plant data analysis, Case Study: Process optimization carried out in our product/process centers of excellence to provide reliable, effective solutions Mission LNG Terminal, UK: using on-line, connectivity-based services. The needs of our client have changed. He wanted advice to re-optimize. Remotely conducted predictive analyses support: Intervention: • Prevention of potential incidents or problems; Experts mobilized in order to fully audit their processes: • Avoidance of costly unplanned downtime; • Life extension programs through plant • Detailed diagnostic with recommendations for plant optimizations in the short and long term obsolescence management • Combination of Remote On-Site Support with back office analysis To further assist operations, members of our Results: Remote Support Services team are available to hold customized training courses for your • Significant reduction of OPEX: personnel on safety, equipment, processes, Optimization of common header system 30% energy reduction, Payback < 6 months operations and maintenance (O&M). • Improved equipment lifetime Remote Support Services: Reduced stop and go operation of units
• Plant diagnoses • Vulnerability studies • Accident risk analyses • Energy efficiency assessments • Remote monitoring and diagnostic reports • Customer training (O&M, HSE) and upgrades • Health, Safety and Environment (HSE) studies • Operations and maintenance optimization studies Contact
Technology Handbook Air Liquide Engineering & Construction 97 On-Site Services: expertise in assessments, CUSTOMER operations, repairs SERVICES
Our experienced field service engineers, the same as deployed at Air Liquide Group facilities, Case Study: ASU relocation and uprating are at Customer’s disposal for site interventions, project to meet higher production troubleshooting and fixes. Prompt dispatch of experts is also provided demand to root cause incidents and restart reliable operations after unplanned shutdown events. Mission ASU – Asia - 2010: On-Site repair activities, executed by our A customer asked us to plan and complete the ASU relocation, and propose a solution to increase qualified team, will ensure reliable plant significantly gaseous nitrogen production. operations for the long term to follow. Intervention: On-Site Services: To address the uprating, we provided our Customer with two detailed proposals for increasing • Repairs production: adding a new ASU or upgrading an existing unit. • Troubleshooting and fixes • Support upon emergency call Our Customer opted for the upgrade. • Performance / Efficiency checks Results: • Supervision for: - Plant operations • Flexible approach to evolving needs - Supplier interventions Our well-structured proposals and sound technical support enabled our Customer to make a - Planned maintenance events well-informed decision with confidence. - Installation, commissioning, start-up • Cost-effective major production increase • Execution of plant relocation activities Upgrading was the best solution, in CAPEX terms, while our efficient execution made for reliability and a doubling of N production. Contact 2
98 Air Liquide Engineering & Construction Technology Handbook Spare Parts Services: competent support CUSTOMER from our supply chain SERVICES
Thanks to strong relationships with selected suppliers, our E&C specialists will support you at Case Study: Sourcing and procurement best with custom spare part lists, specifying of an update for a 30-year-old bundle everything needed to respect fit, form and function of installed parts. We insure Mission Chemical plant – South Africa – 2015: interchangeability and offer assistance related to change of suppliers, obsolescence and Our client had to change three 30+ years old bundles in order to increase plant’s reliability and comply upgrading of parts and provide assistance in with local regulations. They had no equipment documentation and the equipment was tailor made. case of certification requirements to comply with the latest regulations and local jurisdictions. Intervention:
We also carry our consultative studies on safety As the initial manufacturer didn’t exist anymore, we searched for vendors able to manufacture the and capital stocks needed to maximize the bundles based on the technical documents from our archives. availability of your plant. Several components had to be upgraded so as to comply with current local regulations. Spare Parts Services: Finally, the ready to install equipment was handed to the client’s transporter together with the requested documents to apply for local certifications. • Standard supply • Emergency supply Results: • Site inventory audits • Spare parts installation • Ready to install: the bundles were made to fit the plant’s design • Safety and capital stocks • Performance consistency: a 12 months’ performance guarantee of the equipment • Inspection and expediting • Interchangeability studies • Storage recommendations • Obsolescence management • Compliance with updated regulations • Lists for planned and unplanned maintenance Contact
Technology Handbook Air Liquide Engineering & Construction 99 Customer Service Agreements (CSA): CUSTOMER Easy ongoing access to our broad range SERVICES of services and expertise
Customer Service Agreements (CSA) are the Contact most comprehensive way to benefit from our Customer Services. [email protected] By simplifying your access to the expertise of Air Liquide, a CSA makes for a close Mission ASU plants – Middle East - 2017: partnership between your team and ours. This includes regular on-site meetings. Our customer wanted to increase its production, optimize the related energy consumption and sustain A single CSA provides you with the ongoing a good knowledge of its units. support of as many of our Customer Service as Intervention: you require, enabling you to optimize plant performance and maximize cost control over We first assessed the current status of the units and their energy consumption: time. • Off-site preparation and information gathering The CSA can be customized to fit your specific • On-site visual inspection and report-out needs and circumstances, with options to renew or modify the subscribed services. The duration Results: of the agreement is variable, keeping up with your requirements. A long term Service Agreement has been signed including ‘on demand’ specific diagnostics (feasibility studies, risk analysis, remote troubleshooting, …), site services, spare parts services, guaranteeing the Customer Service Agreements: customer the best follow-up and ensuring him with support whenever requested.
• Easy and effective access to Air Liquide specialists and expertise: - Single renewable contract - Single contact person - First reply guaranteed timing - Practical answers with clear and easy operating instructions - Regular on-site meetings • Maintenance programs • Continuous technical support • Extended performance guarantees • Customer tailored terms on any selected Service
100 Air Liquide Engineering & Construction Technology Handbook Technology Handbook Air Liquide Engineering & Construction 101 How to reach us
Vitry Champigny Frankfurt Beijing Krakow Hangzhou Kiev Shanghai Moscow Kobe Seoul AIR GASES [email protected]
RARE GASES [email protected]
CO₂ CAPTURE [email protected] New Delhi
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CHEMICALS [email protected] Singapore Calgary Kuala Lumpur NATURAL GAS TREATMENT [email protected] Montreal Houston SULFUR [email protected]
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Our other locations’ contact information can be found at www.engineering-airliquide.com Operating centers and front-end offices Manufacturing centers
102 Air Liquide Engineering & Construction Technology Handbook Africa Vitry Air Liquide Engineering & Construction, South Africa Champigny Stoneridge Office Park, 1st Floor Block E, 8 Greenstone Place Frankfurt Beijing Greenstone 1609, Johannesburg Krakow Hangzhou +27 87 288 1440 Email: [email protected] Kiev Shanghai Moscow Kobe Americas Seoul Air Liquide Engineering & Construction, USA 9811 Katy Freeway, Suite 100 Houston TX 77024 Tel: +1 713 624 80 03 Email: [email protected] Asia New Delhi Air Liquide Engineering & Construction, China A3, Cao He Jing Modern Service High-Tech Park No. 1528 Gu Mei Road Shanghai 200233 Tel: +86 21 60 91 90 00 Email: [email protected] Europe Singapore Air Liquide Engineering & Construction, France Calgary Kuala Lumpur 57 avenue Carnot, BP 313 Montreal 94503 Champigny-sur-Marne Houston Tel: +33 1 49 83 55 55 Email: [email protected] Air Liquide Engineering & Construction, Germany Olof-Palme-Str. 35 60439 Frankfurt am Main Tel: +49 69 580 80 Email: [email protected] India Air Liquide Engineering & Construction, India A24/10 Mohan Cooperative Ras Al Khaimah Industrial Estate Mathura Road Delhi 110 044 Abu Dhabi Tel: +91 11 42 59 50 50 Email: [email protected] Dubai Middle-East Johannesburg Air Liquide Engineering & Construction, United Arab Emirates Dubai Airport Free Zone, 5 East, Block A Suite 301, P.O. Box 54368 Dubai Tel: +97 1 42 05 55 00 Email: [email protected]
Technology Handbook Air Liquide Engineering & Construction 103 List of abbreviations and acronyms
2EHA 2-ethylhexylacrylate Dehydration and mercaptan Integrated gasification Nickel DMR IGCC Ni 2EHOH 2-ethylhexanol removal unit combined cycle NMP N-methylpyrrolidone AA Acrylic acid DRI Direct reduction of iron ore International methanol NO Nitrous oxide Desolventizer, toaster, dryer IMPCA producers and consumers Methanol specification per US DTDC NOx Nitrous oxides AA and cooler association federal regulation O-M-232e NRU Nitrogen removal unit Engineering and construction International Organization AcAc Acetic acid E&C ISO Opex Operating expenditures for Standardization AGR Acid gas removal EA Ethylacrylate Polycyclic aromatic Kr Krypton PAH APH Air pre-heater EAA Ester-grade acrylic acid hydrocarbon LAR Liquid argon Ar Argon EOR Enhanced oil recovery PC Polycarbonate LIN Liquid nitrogen ASU Air Separation Unit EtOH Ethanol PDH Propane dehydrogenation LNG Liquefied natural gas ATR Autothermal reformer/reforming FAD Fatty acid distillate PDP Preliminary design package LOX Liquid oxygen BA Butylacrylate FAME Fatty acid methyl ester PIMS Proprietary simulation software LP Low pressure BFD Block flow diagram FBDB Fixed bed bry bottom gasifier Performance improvement Low pressure fatty alcohols PIP BFW Boiler feedwater LP3 program FEED Front-end engineering design production BOG Boil-off gas Free fatty acid POX Partial oxidation FFA LPG Liquefied petroleum gas BTU British thermal unit Free on board PSA Pressure swing adsorbtion FOB LTGT Lurgi tailgas treatment BuOH Butanol Fischer-Tropsch Prevention of significant F-T MA Methylacrylate PSD Hydrocarbons Gas-to-Gasoline deterioration C2+ G2G MDEA Methyl diethanolamine with 2 or more carbons GAN Gaseous nitrogen PTSA Para-toluene sulfuric acid Mixture of 4-carbon Methylene diphenyl Refined, bleached and GAR Gaseous argon MDI RBD C4 hydrocarbons (butane, diisocyanate deodorized GNG Gasesous natural gas butylenes and butadienes) MEA Monoethanolamine Carbon-bonded sulfhydryl GOX Gaseous oxygen RSH Capex Capital expenditures MEG Monoetylene glycol or thiol H₂ Hydrogen CCR Continuous catalytic reforming MeOH Methanol Steam methane reforming H₂S Hydrogen sulfide SMR CDU Crude distillation unit MP Medium pressure or reformer HC Hydrocarbon CH4 Methane Multi-purpose gasifier SNG Synthetic natural gas HCl Hydrochrloric acid MPG CLS Claus Mono propylene glycol SO2 Sulfur dioxide HCN Hydrogen cyanide CO Carbon monoxide MTG Methanol-to-Gasoline SOx Sulfur oxydes HDS Hydrodesulfurization CO₂ Carbon dioxide MTP Methanol-to-Propylene SRU Sulfur removal unit He Helium COS Carbonyl sulfide NaOH Soda TDI Toluene diisocyanate HF Hydrofluric acid CSFT Cold soak filtration test Ne Neon USD United States dollar Hg Mercury Cu Copper NG Natural gas VDU Vacuum distillation unit HHC Heavy hydrocarbon CW Cooling water NGL Natural gas liquids VSA Vacuum Swing Adsorbtion HP High pressure DEA Diethanolamine NH3 Ammonia WHRS Waste heat recovery system HT High temperature DME Dimethyl ether Xe Xenon
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Gives users the ability to instantly calculate Allows users to quickly access a host of volume conversions from gaseous to liquid information on the physical and chemical state for 14 gas molecules such as nitrogen, properties of 64 gas molecules (oxygen, oxygen and hydrogen. nitrogen, hydrogen, etc.) in their solid, liquid and Available on Google Play and Appstore gaseous states. Technology Handbook
General: This Technology Handbook is intended for general information purposes only and is not intended as an offer, representation or warranty of any kind, or as a statement of any terms or conditions of sale. The information herein is believed to be correct, but is not warranted for correctness or completeness, or for applicability to any particular customer or situation.
Intellectual property: All the information contained in this document is the exclusive property of Air Liquide or one of its affiliates. Trademarks contained herein, including Yango™, Cryocap™, Lurgi MPG™, Lurgi FBDB™, Lurgi MegaMethanol™, Lurgi MTP™, MTP™, Rectisol™, Distapex™, G2G™, SMR-X™, Medal™, OxyClaus™, Oxynator™, LTGT™, Turbofin™, Smartfin™, Liquefin™, Omnisulf™, Aquisulf™, PEEK-SEP™, POROGEN PEEK-SEP™, Purisol™, Sulfreen™, Degasulf™, Lurgi Biofuels™ and MPG™ belong to either L’AIR LIQUIDE, Société Anonyme pour l’Étude et l’Exploitation des Procédés Georges Claude or Air Liquide Global E&C Solutions Germany GmbH or Air Liquide Global E&C Solutions US Inc.
Economic hypothesis and definitions: Unless otherwise specified, Opex calculations include variable operating costs (utilities, feedstock…) and fixed costs (labour…). Natural gas cost is assumed to be $4/mmBTU HHV. In addition, unless otherwise specified, Capex is calculated either: a) including all EPC costs (process units, offsite and utilities) but excluding owner’s costs for a plant built on the USGC; or, b) using 1.8xEP costs (process units, offsite and utilities). Price base is 2017. Opex and Capex are indicative and can vary according to the basis of design, such as: product(s) yield and quality, site conditions, feedstock quality, utilities, project scope and plant capacity. Units are metric. Gallons (gal) are US Gallons (3.785 liters). Barrel (bbl) refers to oil barrel (42 gal). Heating value shall be understood as Lower Heating Value (LHV). Exchange rate used is: 1 Euro = 1.1 US Dollar.
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February 2018, version 2.0
© 2015 Air Liquide Engineering & Construction
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