Aromatics Extraction

World Market Leader in Aromatics Extraction ThyssenKrupp Industrial Solutions has always been the fi rst choice to supply the growing world aromatics demand with its Morphylane® Extractive Distillation Process by Uhde. More than 75 installed Morphylane® plants are processing all different kinds of feedstocks with a total capacity of more than 15 million t/year of highly purifi ed aromatics within a refi nery.

Aromatics 310,000 t/year plant for Japan Energy Co. in Kashima, Japan

ThyssenKrupp Industrial Solutions 2

Contents

05 ThyssenKrupp Solutions and Aromatics 06 Aromatics – Sources, Demand and Applications - Sources 07 - Demand - Applications 08 Process Conﬁ guration 09 - Aromatics from Pyrolysis Gasoline 12 - Aromatics from Reformate - P-Xylene Production 14 - Benzene Reduction in Motor Gasoline 15 - Aromatics from Coke Oven Light Oil 16 Technology - Hydrogenation Technology - Hydrogenation of Pyrolysis Gasoline - Selective Hydrogenation 17 - Full Hydrogenation 18 - Hydrogenation of Reformate 19 - Hydrogenation of Coke Oven Light Oil 20 - Fractionation Technology - Conventional Distillation - Divided Wall Column Distillation 22 - Morphylane® Extractive Distillation - Conventional Morphylane® Process - Nitrogen Guard Bed 23 - Single-Column Morphylane® Extractive Distillation 25 Hydrodealkylation and Toluene Disproportionation Technology 26 Toluene/C9+ Transalkylation and Para-Xylene Adsorption Technology 27 Xylenes Isomerisation Technology 28 Operating Results of Extractive Distillation Plants 30 Laboratory, Analytical and R&D Services - Analytical Facilities - Gas chromatography - Physical and chemical methods - Other analytical methods - Determination of thermo-physical properties 31 - Pilot Plant Tests - Separation techniques - Absorption/adsorption techniques 32 Services for our customers 34 Main references 3 Engineering Excellence3 – Think globally, act locally

Having erected several thousand plants, ThyssenKrupp Industrial Solutions is one of the world's leading engineering companies. Our Business Unit Process Technologies supplies chemical plants, refineries and coking plants on the basis of tried-and-tested technologies made by Uhde, while the portfolio of the Business Unit Resource Technologies comprises complete cement plants and grinding systems of the Polysius brand, as well as machines, plants and systems for mining, extraction, preparation, processing or transshipment of commodities.

With many years of experience in the EPC business, we offer our customers concepts, market studies, plant layouts, design engineering, supplies, manufacturing services, erection and commissioning – all from a single source. Our employees on all continents use their knowledge and engineering competence to create innovative solutions and to look for ways to conserve natural resources.

Over 40 locations in 25 countries – divided into six regions – form a close-meshed network that allows us to align our services to local conditions consistently. Thanks to this on-site expertise and global networking, we are able to set standards that offer our customers a true competitive edge.

Our comprehensive service concepts take the entire life cycle of a plant into account. We offer OEM spare parts service and complete maintenance management, as well as servicing, modernisation projects and conversions. 4

Erection of the 60 meter high benzene extractive distillation column for Titan Petrochemicals, Pasir Gudang, Malaysia. Capacity: 168,000 t/year benzene and toluene from pyrolysis gasoline. 5 ThyssenKrupp Industrial Solutions and Aromatics Remarkably long experience

Benzene Toluene Para-Xylene

ThyssenKrupp Industrial Solutions’ exten- The superior quality of these aromatics made The process has undergone continuous im- sive knowledge in extractive distillation tech- it impossible for the aromatics distilled from provements and optimisation and its cost- nology and its excellent laboratory facilities coke oven light oil to compete. In addition, the effectiveness has led it to replace liquid- have led it to develop the most advanced improved purification process using azeo- liquid extraction in all applications. Further- process configurations for recovering aromat- tropic distillation was linked with high invest- more, by optimising the combination of all ics and other products, such as butenes, ment costs and inefficient energy utilisation. the processes involved, such as hydrogena- a-olefins, cumene, isoprene and phenols, tion, fractionation and aromatics extractive from different feedstocks. The liquid-liquid extraction process could distillation, the complete process line for not be used for coke oven light oil with recovering aromatics from all possible feed- Our history in aromatics goes back to the an aromatics content of 95% as separable stocks was able to be improved to such an first decades of the 20th century when phases are not able to form when the aro- extent that competitive processes were left Heinrich Koppers developed the Koppers matics content is this high. At the request standing. coke oven technology for the production of of the German coal and steel industry, coke for the steel industry. Right up to the ThyssenKrupp Industrial Solutions initiated Up to now, ThyssenKrupp Industrial fifties, coke oven light oil, which is recov- intensive R&D activities and developed a Solutions has been awarded contracts for ered as a by-product of crude coke oven new process for coke oven light oil to ob- more than 60 Morphylane® plants world- gas in coke oven plants, was the world’s tain aromatics of a similar or better quality wide for recovering aromatics from pyroly- main aromatics source. than those from refineries. sis gasoline, reformate and coke oven light oil. Leading aromatics producers, such as Due to the large quantity of impurities The process developed by Uhde and Chevron Phillips, Dow, BASF, Total, Shell (diolefins, olefins, nitrogen, oxygen and now offered by ThyssenKrupp Industrial and SK Corp., selected the Morphylane® pro- sulphur compounds) the coke oven light Solutions was based on a new solvent cess on the strength of its outstanding per- oil had to be purified before the aromatics called N-formylmorpholine and used a formance figures and its optimised process could be recovered. In those days, the lower different separation principle involving ex- configuration after comparing it with com- benzene quality requirements could be met tractive distillation. The process was able petitive technologies. by sulphuric acid treatment and convention- to produce all the product purities required al distillation processes. However, the large whilst reducing utilities consumption con- ThyssenKrupp Industrial Solutions provides quantity of aromatics lost during sulphona- siderably as compared to liquid-liquid its customers with the following services in tion and the relatively high sulphur content extraction processes. the field of aromatics production: in the benzene product were the driving force in the development of a hydrogenation pro- The first commercial plant based on this • Consulting services ® cess which was worked on together with extractive distillation process (Morphylane • Analytical services BASF AG, Ludwigshafen, Germany and which process) went on-stream in 1968 and pro- • Licensing solved the problems caused by unsaturated duced excellent results with regard to prod- and inorganic impurities in the feedstock. uct quality and utility consumption figures. • Engineering The final purification of aromatics continued • Procurement to be achieved by distillation only. Based on the outstanding performance of • Construction this plant, the Morphylane® process was • Plant operation At the beginning of the fifties, high-purity subsequently adapted to other feedstocks, aromatics recovered by liquid-liquid extrac- such as pyrolysis gasoline and reformate. • Maintenance services tion in refineries came on to the market. • Plant optimisation services 6 Aromatics – Sources, Demand and Applications

World Aromatics Sources World Benzene Sources

ReformateReformate 68%68% PyrolysisPyrolysis Gasoline Gasoline 47% 47% PyrolysisPyrolysis Gasoline Gasoline 29% 29% ReformateReformate 33%33% CokeCoke Oven Oven Light Light Oil Oil 3% 3% HDA/TDPHDA/TDP 15%15% CokeCoke Oven Oven Light Light Oil Oil 5% 5%

Fig. 3-01 Source: HPP Science Fig. 3-02 Source: HPP Science HDA: Hydrodealkylation of heavier aromatics TDP: Toluene disproportionation

Aromatics (benzene, toluene and xylenes) rank amongst the most important intermediate products in the chemical industry and have a wide range of applications.

Sources The main sources of aromatics (benzene, Benzene, which has the highest production toluene, xylenes) are reformate from cata- rate beside xylenes and toluene, is mainly lytic reforming, pyrolysis gasoline from produced from pyrolysis gasoline, followed steam-crackers and coke oven light oil from by reformate. A significant percentage of coke oven plants (Fig. 3-01). The reformate Benzene, i.e. 15%, is also obtained from from catalytic reforming provides the basic the hydrodealkylation (HDA) of heavier aro- supply of benzene, toluene, xylenes and matics and from toluene disproportionation heavier aromatics. The majority of toluene (TDP). The smallest percentage of about and heavier aromatics from reformate is 5% of benzene is obtained from coke oven converted to benzene and xylenes and is light oil (Fig. 3-02). mainly used for p-xylene production. The remaining supply of aromatics is produced from pyrolysis gasoline and from coke oven light oil. 7

Demand Applications Worldwide, approx. 110 million tonnes of The wide range of applications involving BTX aromatics are currently produced per the main aromatics, benzene, toluene and year. An increase in demand of almost xylenes (Fig. 3-04), illustrates the impor- 4% p.a. is predicted for benzene due to the tance of these intermediate products to the growth of end-use markets such as poly- chemical industry. styrene, polycarbonate, phenolic resins and nylon (Fig. 3-03). Fig. 3-04 Main Applications of BTX Aromatics In the case of xylenes the increase in demand is determined by p-xylene, the big- Ethylbenzene Styrene Polystyrene, ABS Resins, SBR gest isomer in terms of quantity. Growth in consumption of this isomer is expected Phenol Aniline, Phenolic Resins, Epoxy Resins, Surfactants to well exceed 5% p.a. in the near future. Cumene Para-xylene is used almost exclusively for the production of polyester via purified α-Methylstyrene Adhesives, ABS Resins, Waxes

terephthalic acid. Caprolactam Polyamide 6

Benzene Cyclohexane Adipic Acid Polyamide 66 and atics Dem Cyclohexanone rom World A (Million metric tons/year) Nitrobenzene Aniline

50 Alkylbenzene LAB e Benzen Chlorobenzenes 40 Xylenes Toluene Diisocyanate Polyurethane Foams Nitrotoluenes 30 Toluene Explosives, Dyes Solvents

Toluene 20 o-Xylene Phthalic Anhydride Alkyd Resins, Methylacrylate

10 Xylenes m-Xylene Isophthalic Acid Polyesters, Alkyd Resins

2009 p-Xylene Terephthalic Acid/ Polyesters 0 Dimethylterephthalate 2007 Fig. 3-03

2005 Source: HPP Science

The estimated growth in overall toluene consumption is less than 3% p.a. Its major direct chemical use is toluene diisocyanate (TDI), a raw material for the production of polyurethane. Toluene extraction will increase as toluene is converted into benzene and xylenes via disproportionation. 8 Process Configuration Aromatics from Pyrolysis Gasoline, Reformate & Coke Oven Light Oil

Aromatics (benzene, toluene, xylenes) are The type of aromatics recovered and the mainly recovered from the following three process configuration are dictated by the feedstocks: feedstock used, as the composition of these • Pyrolysis gasoline from steamcrackers feedstocks differs with regard to the content of paraffins, olefins, naphthenes and aro- • Reformate from catalytic reformers matics (Fig. 4-01) and the amount of im- • Light reformate from aromatics production purities, such as chlorine, oxygen, nitrogen • Coke oven light oil from coke oven plants and sulphur components.

Typical Composition [wt.%] Component Pyrolysis Gasoline Reformate Light Reformate Coke Oven Light Oil

Benzene 30 3 24 65 Toluene 20 13 46 18 Xylenes 4 18 < 0.5 6 Ethylbenzene 3 5 < 0.5 2

C9+ Aromatics 3 16 0 7 Total Aromatics 60 55 70 98 Naphthenes High Low Low High Oleﬁns High High Low High Paraﬃns Low High High Low Sulphur Up to 1000 ppm wt. < 1ppm wt. Low Up to 1 wt.%

Fig. 4-01

Benzene

C5- Fraction Off-Gas Non-Aromatics H2 to Gasoline Pool H2 to Steamcracker to Steamcracker

Crude Pyrolysis Gasoline from n Steamcracker Selective Full Extractive Hydrogenation Hydrogenation Distillation T Colum Stabilizer B/ Depentanizer Deheptanizer

C8+ Fraction Toluene to Gasoline Pool

Fig. 4-02 Aromatics from Pyrolysis Gasoline 9

Aromatics from Pyrolysis Gasoline If, however, the C5- fraction is sent back to tillation column and sent to the extractive

Pyrolysis gasoline is mainly used to recover the steamcracker as feedstock, it should distillation. The C7+ or C8+ fraction is sent to benzene as well as benzene and toluene be fully hydrogenated and separated with the gasoline pool as feedstock. together. Producing mixed xylenes from the non-aromatics downstream of the full pyrolysis gasoline is uneconomical due to hydrogenation unit in a combined depen- Benzene or benzene and toluene are sepa- the low xylene content and the high ethyl- taniser/stabiliser or an extractive distillation rated from the non-aromatics in the extrac- benzene content in the pyrolysis gasoline. stage. This dispenses with the need for a tive distillation unit which comprises a simple complete depentaniser system. two column system. The non-aromatics are A typical process route for recovering sent back to the steamcracker as feedstock. benzene and toluene, starting from crude Olefins as well as impurities, such as nitro- In the case of combined benzene and tolu- pyrolysis gasoline, is illustrated in Fig. 4-02. gen, sulphur and other components, are ene recovery, both products have to be sepa- In the first step, the selective hydrogena- completely hydrogenated in the full hydro- rated downstream in a benzene/toluene col- tion, diolefins are saturated at a relatively genation unit. The off-gas containing H2S umn system. low temperature to avoid polymerisation. is separated in the stabiliser and then re-

The C5- fraction is usually separated from turned to the steamcracker. In some cases it can be more economical the selectively hydrogenated pyrolysis gaso- to convert the C7+ aromatics into benzene line in a depentaniser upstream of the full In order to extract the required aromatics, a to maximise the benzene output. In this hydrogenation stage and sent to the gaso- specific aromatics cut has to be separated case, a thermal hydrodealkylation unit is line pool as an octane-blending component. from the pretreated pyrolysis gasoline. In integrated in such a way that the extracted

Thereby, hydrogen consumption is mini- the case of benzene recovery, a C6- cut is toluene and xylenes from the predistillation mised and the size of the full hydrogenation separated, in case of benzene and toluene stage are dealkylated to form benzene unit can be reduced. recovery, a C7- cut is separated in a predis- (Fig. 4-03).

Benzene Non-Aromatics to Steamcracker

C5- Fraction Off-Gas H2 to Gasoline Pool H2 to Steamcracker Extractive Aromatics Crude Pyrolysis Distillation n Gasoline from Steamcracker Selective Full T Colum B/ Hydrogenation Hydrogenation Off-Gas Stabilizer Depentanizer Deheptanizer

Hydro- dealkylation Deoctanizer

Fig. 4-03 C9+ Fraction H2 Heavy Aromatics Maximum Benzene Recovery to Gasoline from Pyrolysis Gasoline Pool 10

Aromatics complex for BASF in Mannheim/Germany. Capacities: 405,000 t/year aromatics extraction, 340,000 t/year hydrodealkylation

The full range: Consisting of pyrolysis gasoline full hydrogenation, pyrolysis gasoline separation, reformate separation, benzene extractive distillation, toluene/xylene extractive distillation and hydrodealkylation. 11 12

The off-gas produced can then be used Aromatics from Reformate as fuel gas. The toluene does not necessar- As a result of its relatively low benzene con- ily have to be extracted before being fed to tent and relatively high toluene and xylenes the hydrodealkylation stage. However, if the content, reformate is mainly used to pro- toluene fraction is fed directly from the pre- duce p-xylene. Another application for aro- distillation stage, more hydrogen has to be matics recovery is the reduction of benzene

consumed to crack the C7 non-aromatics in motor gasoline by extracting benzene from and consequently more off-gas is pro- the catalytic reformate. duced. P-Xylene Production Depending on the feedstock available and The typical process route for the production the products required, individual process of p-xylene from reformate is illustrated in configurations and heat integration of the Fig. 4-04. individual units can be optimised whilst tak- ing into account local conditions such as In this case catalytic reformate is split into

specific utility availability and costs. We find a C7- fraction and a C8+ fraction. The C7- frac- the most cost-effective solutions with regard tion is then sent to the extractive distillation to investment and operating costs for its stage, where benzene and toluene are sepa-

customers. rated from the C7- non-aromatics.

Fig. 4-04 Non-Aromatics Aromatics from Reformate to Gasoline Pool

Benzene

Extractive

C7– Distillation n n

H2 Light Ends Reformate from Catalytic Reformer luene Colum

Toluene Dis- To Benzene Colum proportionation Reformate Splitter

p-Xylene

H2 Light Ends

C8+ p-Xylene Xylenes Adsorption Isomerisation n o-Xylene n Xylene Colum o-Xylene Colum C9+ Aromatics to Gasoline Pool 13

The C8+ fraction is sent directly to the p-xylene loop without the xylenes being extracted. The non-aromatics content in this fraction is very low and can therefore be easily handled in the p-xylene loop. Conse- quently only benzene and toluene have to be extracted and not full-range BTX.

The toluene is fed to the toluene disproportionation stage where it is converted into benzene and xylenes.

The benzene produced is separated as a high-purity product together with the extracted benzene, whilst the unconverted toluene is recycled back to the disproportionation.

After separation, the mixed xylenes fraction from the disproportionation, the xylenes fraction from the reformate splitter and the recycled xylenes from the isomerisation are sent to the p-xylene adsorption, where p-xylene is separated from the xylenes. The remaining xylenes (m-xylene, o-xylene and ethylbenzene) are sent to the isomerisation to be converted into p-xylene.

If o-xylene is also to be obtained as a product, it must be removed as a pure product by distillation in a separate column system before the xylenes enter the p-xylene isomerisation loop.

If maximum p-xylene production is required, a toluene and C9+ aromatics transalkylation is integrated into the process configuration (not illustrated). With respect to an optimised heat integration, vapours from the xylenes separation can be used to heat the benzene and toluene columns and other consumers.

Half a million tonnes of benzene from reformate for Chevron Phillips Chemical Company, Pascagoula, MS, USA 14

Benzene Reduction in Motor Gasoline The pretreated reformate is fractionated

In order to comply with the latest regula- and the C6- fraction is sent to the extrac- tions limiting the benzene content in motor tive distillation where high purity benzene gasoline, the refining industry has to adjust is removed from the non-aromatics in a its operations to either convert or recover simple two column system. One of the benzene and other aromatics. advantages of the Morphylane® extractive distillation process is that both dissolved ThyssenKrupp Industrial Solutions has hydrogen and light hydrocarbons can be developed an optimised Morphylane® easily removed with the overhead prod- extractive destillation process for recover- uct thereby saving on investment for an ing benzene from reformate with lower upstream depentaniser system. investment and operating costs (Fig. 4-05) compared to aromatics saturation, liquid- Another advantage of the process is the ex- liquid extraction and other processes. cellent benzene purity. A very low benzene content in the non-aromatics (< 0.1 wt%) The reformate from the catalytic reformer can be achieved in the optimised extractive is fed to the selective hydrogenation stage distillation configuration. to saturate the diolefins which influence the acid wash colour (AWC) of the benzene Determined by the specific requirements product. of the refiners, ThyssenKrupp Industrial Solutions also provides other process con- The selective hydrogenation unit consists figurations, e.g. a combination of reformate of a small reactor which is operated at low fractionation (producing several blending temperatures and pressure in a trickle phase. cuts) and benzene extractive distillation or a The small amount of off-gas is separated combined benzene and toluene extraction. in the reactor using only phase separation. This upstream hydrogenation of diolefins eliminates the necessity for a downstream clay treating and subsequent product distillation thus saving considerably on investment and operating costs.

Fig. 4-05 Benzene from Reformate (Benzene Removal from Motor Gasoline)

Non-Aromatics

H2 Off-Gas to Gasoline Pool

Reformate from Catalytic Reformer Benzene Selective Extractive Hydrogenation Distillation Reformate Splitter

C7+ Fraction to Gasoline Pool The C benzene andtoluene. split intohigh-purity a singleextractive distillationbefore being relativelyof non-aromatics smallamount in benzene andtolueneare separated from the is senttotheextractive distillationinwhich contains for instance H contains for instance to thestabiliserwhere which theoff-gas, The hydrogenated coke oven lightoilissent purpose. a two stagereaction system isusedfor this a specificheating/evaporation system and ated. Aspecialhydrorefiningprocess with tent ofolefinsanddiolefins,ishydrogen- high contentofimpuritiesandacon- In afirst step,thefeedstock, whichhasa coke oven lightoilisillustrated inFig.4-06. process line for recovering aromatics from veryaromatics high content.Thegeneral xylenes andhigheraromatics asithasa feedstock for recovering benzene,toluene, Coke oven lightoilisgenerally usedasa Aromatics from Coke Oven LightOil aromatics are recovered by distillation. systemtionation where xylenesandhigher sent toanotherfracdeheptaniser isusually - Aromatics from Coke Oven LightOil Fig. 4-06 to adeheptaniser. Theoverhead C The stabilisedcoke oven lightoilisthensent Light Oil Cok e Ov 8+ fraction ofthe leaving wthebottom en the entire aromatics recovery complex for ARSOL Aromatics inGelsenkirchen/Germany, consisting of hydrorefining, benzene extractive distillation ThyssenKrupp IndustrialSolutionsengineered and distillationofthebenzenehomologues (Toluene, XylenesandC H Hydr 2 2 S, isseparated. or efining from coke oven lightoil. Ta r 7- 9+ fraction aromatics) Of

Stabilizer Gas

Deheptanizer C 7- C 8+ Non-A Distillation Extr C ro acti 8-

C8 Column matics ve C 9+ Xylenes Benzene T oluene B/T Column 15 16 Technology Hydrogenation Technology

Hydrogenation Technology Selective Hydrogenation If pure aromatics are to be obtained, the (see Fig. 5-01) feed must undergo a pretreatment before In this process step, crude pyrolysis gas- the non-aromatics and aromatics can be oline is sent to the hydrogenation reactor separated by extractive distillation. Catalytic after having been mixed with hydrogen. The hydrogenation processes have become the reaction takes place in the trickle phase or most appropriate technologies for eliminat- in the liquid phase on nobel metal catalysts ing impurities such as diolefins, olefins, (palladium on aluminium oxide carrier) or sulphur, nitrogen and oxygen components. on nickel catalysts.

Hydrogenation of Pyrolysis Gasoline The selectively hydrogenated pyrolysis Due to its high diolefin content, crude pyro- gasoline leaves the reactor and is sent to a lysis gasoline from steamcrackers has a separator where the remaining hydrogen is tendency to polymerise and to form gum separated from the liquid phase. Depending even when stored in tanks under nitrogen on the catalyst selected, the gas phase is blanketing. In view of the fact that polymer- sent either to the fuel gas unit or to the full isation is encouraged at higher tempera- hydrogenation stage in which the remaining tures, the diolefins have to be hydrogenated hydrogen is utilised as a make-up agent. at relatively low temperatures by highly active catalysts in the so-called selective hydro- After cooling, part of the liquid phase is re- genation process. Once the diolefins have cycled to the reactor to control the reactor been subjected to selective hydrogenation, temperature. The selectively hydrotreated other impurities can be hydrogenated in the product is fed to a fractionation column or full hydrogenation stage at high tempera- is sent directly to the full hydrogenation. tures.

Crude Pyrolysis Gasoline from Steamcracker Reactor

H2 Off-Gas

Liquid Recycle

Separator Selectively Hydrogenated Fig. 5-01 Pyrolysis Gasoline Selective Hydrogenation of Pyrolysis Gasoline 17

Full Hydrogenation The remaining hydrogen is mixed with (see Fig. 5-02) fresh make-up hydrogen and fed back to Impurities such as sulphur, nitrogen and the reactor. oxygen components and olefins are hydrogenated in the full hydrogenation stage. The The liquid reactor product, fully hydrogen- reactions take place in the gaseous phase ated pyrolysis gasoline, is sent to a stabiliser on nickel/molybdenum and/or cobalt/molyb- system in which the off-gas containing H2S denum catalysts at reactor inlet tempera- is separated from the product. The off-gas tures of between 240°C and 320°C. is normally recycled back to the steam cracker, whilst the stabilised reactor product To this end, the selectively hydrogenated is sent either to a fractionation column or pyrolysis is fed to the reactor via feed/efflu- directly to the aromatics recovery unit. ent heat exchangers and a process heater after having been mixed with recycled hydro- Various optimised process designs are gen. After cooling, the reactor product is provided depending on the specific criteria, sent to a high pressure separator where the such as feedstock specification, hydrogen hydrogen, which has not been consumed, quality, etc. In this respect some of the is separated from the liquid phase. most cost-effective solutions with regard to investment and operating costs include reactor-side intermediate quenching by cooled liquid product recycle, steam gen- eration and additional reactive catalyst layers for difficult feedstocks.

Make-up H2 Off-Gas

Reactor Separator Selectively Hydrogenated Pyrolysis Gasoline High Pressure Separator

Recycle H2

Fig. 5-02 Full Hydrogenation of Fully Hydrogenated Pyrolysis Gasoline Pyrolysis Gasoline 18

Hydrogenation of Reformate long service life and can usually be regen- The typical process scheme is illustrated Although high quality benzene containing erated several times. The maintenance in Fig. 5-03. less than 30 ppm non-aromatics is pro- savings are thus quite remarkable. In addi- duced by extractive distillation, even a small tion, disposing of clay has become more The benzene-rich cut upstream of the ex- quantity of diolefins (around 5 ppm) can and more difficult due to the enforcement tractive distillation stage is passed to the result in an acid wash colour (AWC) speci- of environmental protection laws in an in- selective hydrogenation reactor once the fication higher than that which is actually creasing number of countries. required inlet temperature has been reached. required. If diolefins are present, especially Hydrogen is added to the benzene-rich cut. those of a naphthenic nature the reformate The essential features of the catalyst can must be subjected to an additional treat- be summarised as follows: Selective hydrogenation takes place in the ment stage. trickle bed of the reactor at low tempera- • high conversion rate with regard tures and pressures. The product, which is As the most common unsaturated com- to diolefins free of diolefins, is then passed directly to ponents, such as olefins and diolefins, are • reduction of olefins the extractive distillation stage. Separation mostly removed by clay treating combined • low benzene losses of the gas phase takes place in the reactor with a conventional liquid-liquid extraction (as compared to clay treating) bottom. Additional stripping of the product plant. One alternative is to install a selec- is not necessary. • long cycle length between regeneration tive hydrogenation stage for the olefins and diolefins upstream of the extractive distil- • long service life lation process. The catalyst used for the • mild operating conditions selective hydrogenation of reformate has a

Fig. 5-03 Reformate Selective Hydrogenation

Reactor

Reformate Fraction Off-Gas

Reformate Fraction 19

Hydrogenation of Coke Oven Light Oil fouling whilst achieving high on-stream sent to the high pressure separator to dis- In a similar way to crude pyrolysis gasoline, factors without the addition of fouling in- engage the hydrogen from the liquid phase. coke oven light oil also has to be hydrogen- hibitors. ated. Impurities, such as organic sulphur, The separated hydrogen is mixed with nitrogen and oxygen components, have to be The coke oven light oil is mixed with make- make-up hydrogen, recompressed and removed and diolefins and olefins have to be up hydrogen and recycle hydrogen and returned to the coke oven light oil feed. saturated to stabilise the coke oven light oil passed through a system of feed/effluent and to assure high-quality final products. exchangers which are combined with the The fully hydrogenated raffinate from the stage evaporator (Fig. 5-04). With the ex- high pressure separator is sent to a conven- The “BASF-Scholven” process meets all the ception of a small quantity of heavy hydro- tional stabiliser system. Off-gas containing above requirements. The reactions take place carbons which are withdrawn at the bottom H2S and NH3 is separated from the raffinate in the gas phase on a nickel/molybdenum of the multi-stage evaporator, almost all product. The stabilised raffinate is sent to a catalyst in the prereactor and on a cobalt/ the feedstock is evaporated. fractionation and aromatics recovery unit. molybdenum catalyst in the main reactor. After being subjected to additional heating, ThyssenKrupp Industrial Solutions offers Special emphasis is placed on the evapo- this material is fed to the prereactor where a variety of process configurations adapted ration of the coke oven light oil feed. most of the diolefins are converted. The to the feedstock conditions and customer ThyssenKrupp Industrial Solutions has effluent from the prereactor is then heated requirements. The heavy hydrocarbon re- developed a proprietary system which per- further by a process heater. In the main sidue can, for example, be subjected to mits smooth evaporation in a specialmulti- reactor the olefins are saturated and the further treatment in a tar distillation unit to stage evaporator thereby minimising remaining sulphur, nitrogen and oxygen enhance BTX aromatics recovery or to pro- compounds are hydrogenated. After cool- duce valuable tar-derived products. ing, the effluent from the main reactor is

Fig. 5-04 Hydrorefi ning of Coke Oven Light Oil

H2 Off-Gas

Pre-Reactor Main Reactor

Recycle Stage Compressor Evaporator

High Pressure Separator Tardistillation Column

Coke Oven Light Oil Tar Hydrogenated Coke Oven Light Oil 20 Fractionation Technology

Fractionation Technology Conventional Distillation This has resulted in the development of en- For many decades, distillation has been one ThyssenKrupp Industrial Solutions’ exper- gineering tools which permit the application of our key areas. From hydrocarbon C2 and tise includes distillation systems which use of the divided wall technology and which

C3 distillation to C9 and C10 distillation, from conventional tray technology as well as ran- make use of the thermodynamic advan- crude distillation to pure component distil- dom and structured packing technologies. tages. lation, we can provide fractionation tech- We have designed columns up to 10 metres nology for virtually any hydrocarbon sys- in diameter and as high as 100 metres. These advantages are reflected in: tem. • up to 20% less investment costs Divided Wall Column Distillation • up to 35% less energy costs Our extensive experience is very efficiently Whenever more than two fractions have to backed up by our laboratory and pilot plant be separated by distillation, the question • up to 40% less plant space facilities. Hydrocarbon equilibrium data can arises as to which is the most efficient con- requirements be measured in our laboratories and then figuration (Fig. 5-05). implemented in conventional standard pro- ThyssenKrupp Industrial Solutions success- cess simulators. Configurations involving columns which fully introduced this technology to aromat- are fully thermodynamically coupled have ics applications. Two commercial-scale Pilot testing may also be used to confirm or certain energetic advantages over conven- divided wall columns have recently been demonstrate these adapted models. Special tional fractionation technologies. Latest commissioned for aromatics recovery. In feedstocks can be tested in our pilot plants technological developments have, however, addition, ThyssenKrupp Industrial Solutions allowing distillation processes to be opti- laid the foundation for adequate calcula- has installed divided wall column test facili- mised to meet customer requirements. tion techniques and established the generic ties in its own laboratories to work on fur- guidelines for thermodynamic simulations. ther improvements.

The divided wall column technology is an excellent tool for revamping plants, enhanc- ing their capacity and improving product qualities and yields. Existing hardware can be modified within one week resulting in a short shut-down time and low production losses.

Plant converted to the divided wall technology in just five days.

Our team at the Ruhr Oel GmbH refinery in Münchsmünster in Bavaria had just five days to convert a distillation column to a divided wall column using one of our new developments. The ThyssenKrupp Industrial Solutions team managed to complete the task in the allotted time despite inclement weather. The divided wall column saved Ruhr Oel having to build a second column for removal of benzene so that the more stringent benzene specifications in gasoline could be met.

Old section of the existing column 21

New divided wall section before installation of packings

Reformate or Pyrolysis Gasoline C5 Fraction

C6/C7 Fraction

Fig. 5-05 C Fraction Divided Wall Column 8+ 22

® Solvent: Morphylane Extractive Distillation N-formylmorpholine (NFM)

Morphylane® Extractive Distillation The solvent is recovered from the overhead Nitrogen Guard Bed Due to lower capital cost and utilities con- product in a small column with sectional The Morphylane® process withholds the sol- sumption, the Morphylane® extractive distil- reflux, which can be either mounted on vent in the unit almost completely. The con- lation process, developed by Uhde, has the main column or installed separately. centration of NFM in the extract is typically replaced the former liquid-liquid extraction The bottom product from the ED column is less than 1 wt.-ppm, which corresponds to technology. fed to a distillation stage, i.e. the stripper, <0.15 wt.-ppm basic nitrogen. Therefore to separate the pure aromatics and the losses are of no importance to the eco- Conventional Morphylane® Process solvent. After intensive heat exchange, the nomics of the process. However, market In the extractive distillation (ED) process lean solvent is recycled to the ED column. demands have increased: Due to the inven- (see Fig. 5-06), the solvent alters the va- tion and spread of zeolithe catalysts for pour pressure of the components to be The product purity is affected by a number alkylation processes the requirements for separated. The vapour pressure of the of different parameters including solvent the extract of the Morphylane® process have aromatics is lowered more than that of the selectivity, the number of separation stages, become stricter. The nitrogen concentration less soluble non-aromatics. The ED process the solvent/feedstock ratio and the internal is required to be as low as possible. Our is relatively simple. The solvent is supplied reflux ratio in the ED column. The solvent answer to this market demand is the Nitro- to the head of a distillation column via a properties needed for this process include gen Guard Bed. This adsorption bed is able central feed inlet. The non-aromatic vapours high selectivity, thermal stability and a suit- to capture even traces of basic nitrogen, leave the ED column with some of the sol- able boiling point. The solvent used in the such that the product concentration is in the vent vapours. The internal reflux is con- Morphylane® process is a single compound, ppb-range, below the detection limit. There- trolled by the solvent feed temperature. namely N-formylmorpholine (NFM). No fore aromatics from the Morphylane® units agents or promoters are added to the sol- can safely be fed to zeolithe-catalysts reac- vent. The salient features of NFM are sum- tors, producing alkyl-aromatics in world-scale. marised in Fig. 5-07.

Non-Aromatics Fig. 5-06 Morphylane® Extractive Distillation

Aromatics

Extractive Aromatics Distillation Fraction Column Stripper Column

Solvent + Aromatics

Solvent 23

Single-Column Morphylane® Packings 3 and 4 are separated by a divid- over 99.99%. The column has proved easy Extractive Distillation ing wall forming two chambers. The cham- to operate, even under varying feed condi- Uhde’s new Single-Column Morphylane® ber containing packing 4 is closed at the tions and product specifications. extractive distillation process uses a single- top side. column configuration which integrates the ThyssenKrupp Industrial Solutions supplied extractive distillation (ED) column and the The aromatics-solvent mixture draining from the licence for the plant, provided engineer- stripper column of the conventional Mor- the two chambers is fed to the stripping sec- ing services and was on hand in a consult- phylane® design. It represents a superior tion (packing 5) where the aromatics are ing capacity during commissioning. process option in terms of investment and stripped off from the solvent. The lean sol- operation (Fig. 5-08). vent is returned to the top of the column. In- In 2005, ThyssenKrupp Industrial Solutions tensive stripping is crucial to the aromatics was presented with the 'Kirkpatrick Honor In the Single-Column ED process, the aro- yield. Award for Chemical Engineering Achieve- matics are removed from the vaporised feed ment', a biennial award for innovative prod- by the solvent (NFM) in packing 2. Residual The first industrial realisation of the new con- ucts or processes by the journal Chemical non-aromatics are stripped off by aromatics cept has been a toluene recovery plant for Engineering. A vital prerequisite for submis- vapours in packing 3. Solvent traces in the ARSOL Aromatics GmbH in Gelsenkirchen, sion of an innovation is that its first-time column head are washed back with the non- Germany, commissioned in October 2004. industrial-scale implementation was within aromatics reflux in packing 1, while solvent the past two years. Our technology met this traces in the aromatics vapours are removed Based on the Single-Column Morphylane® condition with the successful commissioning by aromatics reflux in packing 4. process by Uhde described above, the plant of the aromatics plant based on the inno- produces pure toluene from fully hydrogen- vative single-column concept for ARSOL ated coke oven light oil. Aromatics GmbH in 2004. An international team of experts ranked the process among The plant has a toluene capacity of the five best process innovations of the last 30,000 t/year and it achieves purities of two years.

Fig. 5-07 Fig. 5-08 ® ® Single-Column Morphylane Extractive Distillation

ocess es of the Morphylane es: eatur 1 Main F ent featur Solvent active Distillation Pr ) 2 Extr es: t Non-Aromatics Feed Process featur N-formylmorpholiney solv

Simple plant arrangemen High selectivit y Low number of equipment (2 columns High solvent efficiency wash system required Little spacefinate required High purity products even from 3 raf No Feedstocks with high paraffinic contents 4 Low solvent filling High permanent thermalt stabilit y Aromatics Low investment High heat transfer rate t Low energy consumption No corrosive effec Easy to operate High chemical stabilit 5 No chemical agents required Negligible solvent consumption High on-stream time Low solventxicity regeneration cos No to Low price 24

525,000 t/year of pyrolysis gasoline extractive distillation for Rayong Olefi ns Corp., Thailand 25 Hydrodealkylation and Toluene Disproportionation Technology

Hydrodealkylation Technology A major technological break-through was the downstream para-xylene recovery and Hydrodealkylation, commonly known as achieved when the zeolite catalyst geometry xylene isomerisation stages are smaller and HDA, is a well-established process for con- was developed to maximise para-xylene more efficient. verting C7 and C8 (even up to C9+) alkylben- selectivity. The TDP with improved selectiv- zenes to high purity benzene. Very few new ity produces a xylene fraction which con- Fig. 5-10 shows a typical process plants are being built, however, as the huge tains up to 90% para-xylene. Consequently, configuration for a TDP. hydrogen consumption makes the benzene quite expensive.

The preferred technology uses non-catalytic Benzene C8+ Aromatics thermal reactor systems which have a high from Predistillation benzene yield, extremely high on-stream factors and lower operating costs as com- Make-up pared with catalytic systems. A typical pro- Hydrogen B/T Aromatics n cess configuration is shown in Fig. 5-09. from Extraction Vent ator Several options, e.g. to enhance benzene HDA Reactor Benzene Colum Separ yield or to minimise hydrogen consump- n tion are available, depending on the quality of the feedstock treated in the HDA. Recycle Colum Co-processing C8 and even C9+ aromatics Stabilizer will enhance benzene output but will also increase hydrogen consumption consider- Heavy Aromatics Purge ably. An upstream extraction stage reduces Fig. 5-09 the content of non-aromatics to such an Hydrodealkylation (HDA) Unit extent that the amount of hydrogen consumed in the cracking reaction is minimised.

Toluene Disproportionation Technology Benzene Toluene Disproportionation Technology (TDP) converts toluene to benzene and mixed xylenes in approximately equimolar quantities. The reaction is carried out in the vapour phase on a variety of acidic zeolite Make-up catalysts. Conventional TDP produces a Hydrogen xylenes fraction in which the xylene-isomer equilibrium is reached. The para-xylene Light Ends TDP Reactor concentration is therefore limited to 24%. n to Fuel

Further processing is required to increase ator

the para-xylene yield. Separ Deheptanizer Benzene Colum This involves separating the para-xylene Fresh Toluene isomer by selectively adsorbing or by Stabilizer crystallising and isomerising the remaining meta-xylenes and ortho-xylenes (optionally) Mixed Xylenes to to form para-xylene. Since the para-xylene Para-xylene Recovery concentration in isomerisation is only 24% ry

as well, a large recycle loop is required to n vove completely convert the undesired isomers to para-xylene. Colum Xylene Re C9+ Aromatics to Gasoline Pool Fig. 5-10 Toluene Disproportionation Unit 26

Toluene/C9+ Transalkylation and Para-Xylene Adsorption Technology

Toluene/C9+ Transalkylation Technology Para-Xylene Adsorption Technology At the heart of the adsorption process are

In contrast to the TDP, toluene and C9+ aro- Para-xylene can practically not be sepa- the adsorption columns in which the fol- matics are converted to mixed xylenes in rated from meta-xylene by conventional lowing steps occur in a sophisticated semi- the transalkylation technology. The xylenes- distillation due to the closeness of their continuous operation: to-benzene ratio increases if more C9+ aro- boiling points. In contrast, ortho-xylene can matics are mixed with the toluene feed and be recovered by conventional distillation • feeding in mixed xylenes if the transalkylation reaction rate increases. because its boiling point is considerably • diluting out extract (para-xylene) Similar catalysts to those used in TDP units higher than that of the other isomers. with a desorbent are used. The most common para-xylene separation • diluting out raffinate (ethylbenzene, technology used today involves adsorption meta-xylene and ortho-xylene) using molecular sieves. with a desor bent • feeding in recycled desorbent Crystallisation technology is also widely used, especially in North America and in The diluted extract and raffinate streams Western Europe. However, one of the main are fractionated in an extraction column and advantages of adsorption over crystallisa- a raffinate column to recover the desorbent tion is its high recovery rate per pass (up to which is recycled back to the adsorbers. 97%). In contrast, crystallisation units have a eutectic limitation of 65%. All commer- Any residual toluene contained in the mixed cialised para-xylene adsorption processes xylenes feed and carried over with the para- use isothermal, liquid phase adsorption. xylene extracted is separated in a finishing The adsorbent’s selectivity, capacity and column. The concentrated raffinate, meta-, reversibility are the key properties relevant ortho-xylene and ethylbenzene, is sent to to desorption. the isomerisation stage. A simplified process configuration is shown in Fig. 5-11.

Light Ends n

Block scheme of the Adsorption System n Finishing Colum

Para-Xylene

Mixed Xylenes from act Colum (Extract) Xylene Splitter Extr

C8 -Aromatics to Isomerisation (Raffinate) finate Column Raf

Fig. 5-11 Desorbent Para-Xylene Adsorption Unit 27 Xylenes Isomerisation Technology

CH3 CH3

CH3

CH3 CH3

CH3 meta-Xylene para-Xylene ortho-Xylene

Xylene Isomers

Xylenes Isomerisation Technology The method of EB conversion is influenced Xylene feedstocks containing high EB con-

Once the C8 aromatics stream has been by the catalyst type. Xylene isomerisation centrations, such as pyrolysis gasoline feed- depleted of para-xylene (and optionally of catalysts can be categorised according to stocks, are particularly suitable as the EB is ortho-xylene as well), the stream is sent their ability to isomerise EB into additional converted to naphthenes thereby producing to an isomerisation unit to re-establish the xylenes or their ability to dealkylate EB. Both the naphthene concentration required. The equilibrium of the xylene mixture. This oc- types of catalyst isomerise the xylenes to EB isomerisation conversion rate typically curs by converting the meta-xylene (and form a close equilibrium xylene isomerisate amounts to 30 - 35%. ortho-xylene, if present) and the ethyl- mixture. benzene (EB) to para-xylene by isomerisa- EB dealkylation is not limited to equilibrium tion until the equilibrium is reached. The EB isomerisation catalysts result in the conditions and permits EB conversion rates isomerisate is then returned to the xylene highest para-xylene yield from a given feed- of up to 65%. EB dealkylation catalysts gen- fractionation section in which valuable par- stock due to the conversion of EB to addi- erally contain a shape-specific molecular axylene, and optionally ortho-xylene, are tional xylenes. EB isomerisation is more sieve with a given pore size, which minimises recovered. Meta-xylene and EB are returned difficult than xylene isomerisation and re- xylene loss caused by xylene disproportion- to the recycle loop. quires a bifunctional acid-metal catalyst. ation, transalkylation or hydrocracking.

EB isomerisation occurs using C8-naphthene Alternatively, EB can be dealkylated to intermediates. This type of catalyst must be form benzene and ethane. operated with a substantial concentration of

C8-naphthenes in the reactor recycle loop to allow efficient conversion of EB to xylenes. 28 Operating Results of Extractive Distillation Plants

ED column and stripper, aromatics complex at the Kashima refinery, Japan

Reformate feed with Reformate feed with high aromatics content high aromatics content Plant for Japan Energy, Kashima Repsol, Spain Typically, reformates which contain large quantities of aromat- Year of commissioning 2007 2007 ics are processed in aromatics Benzene in ED-feed 30% 75% complexes in which a high Toluene in ED-feed 49% 0% aromatics yield reformer is in- Benzene production 136,000 mtpy 221,000 mtpy stalled. The C6 core cut contains aromatics levels which well in Toluene production 223,000 mtpy - excess of 50%. The operating Benzene quality max. 400 wt.-ppm non-aromatics 400 wt.-ppm non-aromatics results of four plants are sum- Toluene quality 99.0 wt.-% - marised in Tables 7-01 and 7-02. Solvent loss max. 0.007 kg/t aromatics max. 0.010 kg/t aromatics Steam consumption 480 kg/t ED-feed 470 kg/t ED-feed Yield Benzene: 99.92% Benzene: 99.7%

Table 7-01 29

Reformate feed with high aromatics content Plant for BASF Antwerp, Belgium SPC, PR China

Year of commissioning 2000 1999 Benzene in ED-feed ~ 65 wt.% ~ 75 wt.% Toluene in ED-feed - ~ 85 wt.% Benzene production 258,000 mtpy 135,000 mtpy Toluene production - 65,000 mtpy Benzene quality max. 100 ppm wt. non-aromatics max. 80 ppm wt. non-aromatics Toluene quality - max. 600 ppm wt. non-aromatics Reformate feed with low aromatics content Solvent loss max. 0.005 kg/t benzene max. 0.08 kg/t aromatics Reformates processed in gas- Steam consumption 450 kg/t ED-feed 680 kg/t ED-feed *) oline-based refineries generally Table 7-02 *) including the benzene/toluene splitter contain smaller quantities of benzene. Reformers are often operated at lower severity levels. If the benzene content of gasoline is to be reduced, the ben-

zene content of the C6 core cut Reformate feed with low aromatics content fed to the extractive distillation Plant for Holborn Reﬁnery, Germany Tonen, Kawasaki, Japan stage needs to be well below 50 wt%. In this type of applica- Year of commissioning 2003 1999 tion, the energy consumption of Benzene in ED-feed ~ 27 wt.% ~ 30 wt.% extractive distillation processes is lower than that of reformate Benzene production 66,000 mtpy 100,000 mtpy streams with a higher aromatics Benzene quality max. 10 ppm wt. non-aromatics max. 50 ppm wt. non-aromatics (benzene) content. Table 7-03 Solvent loss max. 0.002 kg/t benzene max. 0.001 kg/t benzene shows the operating results of two plants recently commis- Steam consumption 450 kg/t ED-feed 380 kg/t ED-feed sioned for benzene reduction.

Table 7-03

Reformate and pyrolysis gasoline feed with high aromatics content Pyrolysis gasoline feed Pyrolysis gasoline from steam- Plant for PKN Orlen, Poland Shell Moerdijk, The Netherlands crackers has a relatively high Year of commissioning 2006 2002 aromatics content which is dictated by the cracker feedstock Benzene in ED-feed 33% 65 wt.-% and the severity of the cracker. Toluene in ED-feed 41% - The results obtained from an Benzene production 178,000 mtpy 550,000 mtpy aromatics distillation process Toluene production 222,000 mtpy - in a typical naphtha-based Benzene quality 70 wt.-ppm non-aromatics max. 200 wt.-ppm non-aromatics steam-cracker are shown in Table 7-04. The two examples Toluene quality 470 wt.-ppm non-aromatics - are based on a benzene ED, Solvent loss 0.006 kg/t aromatics max. 0.003 kg/t benzene which was started up in the Steam consumption 540 kg/t ED-feed 400 kg / t ED-feed Netherlands at the end of 2002, and a benzene/toluene ED, Yield Benzene: 99.9; Toluol: 98.2 % - which went into operation in Table 7-04 Poland in 2005. 30 Laboratory, Analytical and R&D Services

Gas-phase chromatographs used in the separation and quantitative analysis of liquid and gaseous samples

ThyssenKrupp Industrial Solutions operates The analytical facilities permit standard DIN/ • hydrogen/oxygen combustion laboratory and pilot plant facilities in Enni- ISO or ASTM analyses of virtually any type • water determination (Karl Fischer) gerloh, Germany. The facilities are used for of fuel and refinery/petrochemical feedstock, • solidification point acc. to ASTM D 852 ongoing developments to new processes as well as a variety of inorganic analytical and for optimising established processes. methods and water analysis methods. Some • boiling range acc. to In conjunction with their colleagues in the of the main methods are summarised below. ASTM D 850 and D 1160 central R&D division, a highly qualified team • total sulphur acc. to ASTM of 30 employees is committed to providing Gas chromatography D 5453 and D 7183 R&D services for our customers. This team Our laboratory uses gas chromatographs • total nitrogen acc. to ASTM includes: to categorise all types of hydrocarbon feed- D 6069 and D 7184 stocks, products and intermediate products. • 12 chemists and chemical engineers The samples are separated analytically Other analytical methods • 10 chemical technicians and mechanics in capillary, widebore or packed columns In addition to the standard analytical meth- • 4 administrative staff is committed to of suitable polarity. Standard analytical ods mentioned above, our laboratory is providing R&D services for our customers. methods using flame ionisation detectors able to develop other analytical methods to (FID) and thermal conductivity detectors cater to special customer requirements, or Using the latest state-of-the-art equipment, (TCD), are enhanced by special detection to support troubleshooting in our customers’ our R&D staff is dedicated to: methods which use selective sulphur detec- plants. This means that we can measure: tors (S-CLD) or nitrogen detectors (NPD and • improving Uhde processes • thermal stability of chemicals N-CLD). Additionally, a powerful GC-MSD sys- • searching for new processes tem enables us not only to identify unknown • corrosion of materials in chemicals and process opportunities components in a complex matrix, but also to • 2-liquid phase separation abilities • improving analytical methods and quantify components of special interest even • polymer content in solvents preparing analytical instructions and when present as trace amounts. • foaming tendencies manuals • chemical stability • providing a wide range of analyses for Physical and chemical methods feedstocks and products Hydrocarbon components are completely broken down and other properties and im- Determination of • providing analytical support during the purities are also of interest. We use various thermo-physical properties commissioning of our plants analytical methods to analyse these prop- Simulation models must be constantly Our process engineers in Dortmund and erties and impurities, including elemental enhanced using data gained during plant Bad Soden work closely with the laboratory analyses (CHNS), chloride content, bromine operation or in laboratory tests to ensure staff and are able to support operations index/number, acid wash colour, specific the continuous improvement of process whenever needed. The laboratory and pilot gravity, molecular weight, acidity, refraction simulation and equipment design. facilities are certified in accordance with ISO index and many more. The methods used 9001 to ensure consistently high standards. include: ThyssenKrupp Industrial Solutions has continuously developed and increased • UV-Vis spectroscopy Analytical facilities its thermo-physical property data banks • ion chromatography The laboratory consists of 5 working sections: which are used for process simulation of • atom absorption spectroscopy its separation technologies. Vapour-liquid • laboratory for inorganic • potentiometry equilibrium (VLE) or liquid-liquid equilibrium chemistry/physical analyses • coulometry (LLE) data for specific solvent/hydrocarbon • gas chromatography • viscosimetry (Hoeppler, Ubbelhohe, Engler) systems (used in ED and LLE) is measured • laboratory for fuel and coal analysis • ignition point determination in our laboratories, evaluated and linked to • laboratory for oil and wax analysis (Abel-Pensky, Pensky-Martens) our process simulators. Simulation results • test laboratory can later be verified or checked in our pilot • surface tension (DeNouy) other ThyssenKrupp sitesifrequired. plant facilitiesbeerectedvarious can on cover anoverallof 12 height ated next tothelaboratory. The3platforms plant tower isathree-storeysitu- building The Pilot PlantTests • • • • • Our laboratory to: includesequipment customers. tailor-made separation processes for our tions. Thisprocedure allows ustodevelop plant facilities under real operating condi- research centre The ThyssenKrupp IndustrialSolutions determine masstransfer coefficients measureof gasesinliquids thesolubility measure crystallisation equilibria pressures ranging from 0-5bar and temperaturesfor of20°C-160°C temperatures of-40°Cto95°Cfor 1bar, tertiary, systems andquaternary at determine theLLEdataofbinary, and pressures20°C-160°C of0-40bar systems attemperaturestertiary of and determine theVLEdataofbinary

i-Butan ThyssenKrupp IndustrialSolutionspilot n-Butan

i-Pentan

n-Pentan

2.2-Dimethylbutan

2.3-Dimethylbutan m. Larger pilot pilot m. Larger Cyclopentan

n-Hexan

2.2-Dimethylpentan 2.4-Dimethylpentan

2.2.1-Trimethylpentan • • available: A variety offractionation utilitiesis Separation techniques performed usingacomputer. processing operations andanalytical are injectors.automatic liquid Time-controlled separated systems ofrecycle pumpsand matograph isequippedwith2completely is usedforanalysis. onlineliquid Thechro- gas chromatographA 2-channel withFID ling thepilotplant. ments are usedfor measuringandcontrol- ele- Most modernDCSandinstrumentation and fastand bulk. of equipment installation every 2 beaccessed can tural components(edgelength1 madefromscaffolding Mero cuboidstruc- The pilotplantiscompletelysurrounded by Methylcyclopentan with structured packings instainlesssteelequipped ID of72mm 70 theoretical stages. Moduleswithan extractive distillationwithupto traysbubble cap structured packings(SulzerDX/EX)and stainless steelorglassfor laboratorytype of 100 theoretical stages.ModuleswithanID conventionalwith upto160 distillation

3.3-Dimethylpentan mm, 72 distillation, extraction andextractive distillation system for process development inthefields of Research facility withPC-basedprocess control 2-Methylhexan

2.3-Dimethylpentan mm, and50 3-Methylhexan Cyclohexan 2.2.3-Trimethylpentan

3-Ethylpentan m topermitsimple

cis 1.3-DMCP

tr 1.3-DMCP mm madeof m) and tr 1.2-DMCP n-Heptan

2.2-Dimethylhexan of random orstructured packings. adsorbers andscrubbers withavariety fitted equipment includesautoclaves, falling-film and masstransfer for gasscrubbers. This ure staticanddynamicabsorptionequilibria pilot plantfacilities allows ustotestormeas- The speciallydesignedequipmentinour Absorption/adsorption techniques mulations. reactionsto testcatalytic andcatalyst for temperatures beapplied ofupto600°Ccan kinetics. Pressures ofupto200barand bents testing,andfor measuringreaction beusedfor(CSTR) can catalyst andabsor which are jacketed, andagitatedautoclaves Severalreactors, typesoftubular someof vacuumhigh to6bar. The operating range bevaried from can a • •

2.2.3.3-Teramethylbutan section. 40 theoretical stagesinthepartition divided wallcolumnswithupto structured packings(SulzerBX) ID of40 50 theoretical stages.Moduleswithan extractorsliquid-liquid withupto

1.1.3-Trimethylhexan mm inglassequippedwith

Methylcyclohexan

Benzol - 31 - 32 Services for our customers

ThyssenKrupp Industrial Solutions is dedicated to pro- • Procurement / inspection / transportation services viding its customers with a wide range of services and • Civil works and erection to supporting them in their efforts to succeed in their line of business. • Commissioning

With our worldwide network of local organisations and • Training of operating personnel using operator experienced local representatives, as well as first-class training simulator backing from our head office, ThyssenKrupp Industrial • Plant operation support / plant maintenance Solutions has the ideal qualifications to achieve this goal. • Remote Performance Management (Teleservice) We at ThyssenKrupp Industrial Solutions place particu- lar importance on interacting with our customers at an ThyssenKrupp Industrial Solutions’ policy is to ensure early stage to combine their ambition and expertise utmost quality in the implementation of its projects. We with our experience. work worldwide to the same quality standard, certified according to: DIN / ISO 9001 / EN29001. Whenever we can, we give potential customers the opportunity to visit operating plants and to personally We remain in contact with our customers even after pro- evaluate such matters as process operability, main- ject completion. Partnering is our byword. tenance and on-stream time. We aim to build our future business on the confidence our customers place in us. By organising and supporting technical symposia, we promote active communication between customers, ThyssenKrupp Industrial Solutions provides the entire licensors, partners, operators and our specialists. This spectrum of services associated with an EPC contrac- enables our customers to benefit from the development tor, from the initial feasibility study, through financing of new technologies and the exchange of experience as concepts and project management right up to the com- well as troubleshooting information. missioning of units and grass-roots plants. We like to cultivate our business relationships and learn Our impressive portfolio of services includes: more about the future goals of our customers. Our after- sales services include regular consultancy visits which • Feasibility studies / technology selection keep the owner informed about the latest developments or revamping options. • Project management • Arrangement of financing schemes ThyssenKrupp Industrial Solutions stands for tailor-made concepts and international competence. For more infor- • Financial guidance based on an intimate mation contact one of the ThyssenKrupp Industrial knowledge of local laws, regulations and Solutions offices near you or visit our website: tax procedures • Environmental studies www.thyssenkrupp-industrial-solutions.com

• Licensing incl. basic / detail engineering Further information on this subject can be found in the following brochures: • Utilities / offsites / infrastructure • Oil & Gas • Polymers 33 34 Main references Just a few of more than 100 reference plants in the last ten years

Completion Customer Process Prod. Capacity Licensor or Plant Site Plant t/year Know-how Morphylane® Extractive Distillation 2014 Refineria Del Pacifico Benzene 143,000 Uhde Manabi, Ecuador from Reformate 2014 Petrobras S.A. Benzene/Toluene 940,000 Uhde Rio de Janeiro, Brazil from Reformate 2013 Atyrau Refinery Benzene/Toluene 289,000 Uhde Kazakhstan from Reformate 2012 Sasol Technology Benzene from 106,000 Uhde Secunda, South Africa Coal tar nawphthta SCC Gasoline 2012 Rabigh Refining and Petrochemical Co. Benzene/Toluene 881,000 Uhde Rabigh, Saudi Arabia from Reformate 2012 Total Jerp Benzene 140,000 Uhde Al-Jubail, Saudi Arabia from Reformate 2011 Tianjin Binhai Tiansheng Coal Chemical Co. Benzene/Toluene/Xylenes 87,300 Uhde Tianjin, China from Coke Oven Light Oil 2011 S-Oil Corporation Benzene/Toluene 680,000 Uhde Ulsan, South Korea from Reformate 2011 Tabriz Oil Refining Co. Benzene 33,600 Uhde Tabriz, Iran from Reformate 2010 Xingtai Risun Coal&Chemical Company Benzene/Toluene/Xylenes 88,000 Uhde Xingtai, China from Coke Oven Light Oil 2010 Baosteel Chemical Co. Benzene/Toluene 80,800 Uhde Baoshan, China from Coke Oven Light Oil 2010 Tangshan Risun Chemical Company Benzene/Toluene/Xylenes 173,000 Uhde Tangshan, China from Coke Oven Light Oil 2010 Qatar Petroleum Benzene/Toluene 762,000 Uhde Qatar from Reformate 2010 Yunnan Dawei Group Co. Ltd. Benzene/Toluene/Xylenes 89,000 Uhde Yunwei, China from Coke Oven Light Oil 2010 Shell Eastern Petroleum Ltd. Benzene 210,000 Uhde Singapore from Pyrolysis Gasoline 2009 China Steel Chemical Corporation Benzene/Toluene 27,000 Uhde Kaohsiung, Taiwan from Coke Oven Light Oil 2009 Wuhan Iron and Steel Co. Ltd. Benzene/Toluene/Xylenes 94,000 Uhde Wuhan, China from Coke Oven Light Oil 2009 Xingtai Risun Coal & Chemical Company Benzene/Toluene/Xylenes 88,000 Uhde Xingtai, China from Coke Oven Light Oil 2009 GCW Anshan I&S Group Co. Benzene/Toluene/Xylenes 128,000 Uhde Anshan, China from Coke Oven Light Oil 2009 Oman Oil Company Benzene/Toluene 350,000 Uhde Sohar, Oman from Reformate 2008 Jiantao Chemical Co. Ltd. Benzene/Toluene/Xylenes 45,000 Uhde Hebei, China from Coke Oven Light Oil 2008 Yunnan Kungang IT Co. Ltd. Benzene/Toluene/Xylenes 44,000 Uhde Kunming, China from Coke Oven Light Oil 2007 Shanxi Sanwei Group Co. Ltd. Benzene/Toluene/Xylenes 178,000 Uhde Zhahocheng, China from Coke Oven Light Oil 2007 Sasol Benzene 100,000 Uhde Secunda, South Africa from Pyrolysis Gasoline 2007 Hood Oil Benzene 110,000 Uhde Sanaa, Yemen from Reformate 2007 Japan Energy Co. Benzene/Toluene 310,000 Uhde Kashima, Japan from Reformate 35

Completion Customer Process Feed Capacity Licensor or Plant Site Plant t/year Know-how Reformate Hydrogenation 2002 Shell Nederland Chemie B.V. Selective Hydrogenation 850,000 Axens Moerdijk, Netherlands 2000 Tonen Corporation Selective Hydrogenation 320,000 BASF Kawasaki, Japan 2000 Saudi Chevron Petrochemical Selective Hydrogenation 860,000 BASF Al Jubail, Saudi Arabia Pyrolysis Gasoline Hydrogenation 2010 Shell Eastern Petroleum Ltd. First and Second Stage Hydrogenation 733,000 Axens Singapore 2005 CNOOC / Shell Petrochemicals Co. Ltd. Hydrogenation 800,000 Axens Huizhou, China 2005 BASF / Yangzi Petrochemical Co. Hydrogenation 600,000 BASF Nanjing, China of Pyrolysis Gasoline 2004 Bouali Sina Petrochemical Co. First Stage Hydrogenation 139,000 Axens Bandar Imam, Iran Second Stage Hydrogenation 106,000 2001 BASF/FINA First Stage Hydrogenation 795,000 BASF Port Arthur, Texas, USA Second Stage Hydrogenation 563,000 Coke Oven Light Oil Hydrorefining 2010 Xingtai Risun Coal&Chemical Company Hydrorefining 100,000 Uhde/BASF Xingtai, China 2010 Baosteel Chemical Co. Hydrorefining 100,000 Uhde/BASF Baoshan, China 2010 Tangshan Risun Chemical Co. Hydrorefining 200,000 Uhde/BASF Tangshan, China 2009 Yunnan Dawei Group Co. Ltd. Hydrorefining 100,000 Uhde/BASF Yunwei, China 2009 Wuhan Iron and Steel Co. Ltd. Hydrorefining 100,000 Uhde/BASF Wuhan, China 2009 Xingtai Risun Coal & Chemical Co. Hydrorefining 100,000 Uhde/BASF Xingtai, China 2009 GCW Anshan I&S Group Co. Hydrorefining 150,000 Uhde/BASF Anshan, China 2008 Jiantao Chemical Co. Ltd. Hydrorefining 50,000 Uhde/BASF Hebei, China 2008 Yunnan Kungang IT Co. Ltd. Hydrorefining 50,000 Uhde/BASF Kunming, China 2007 Shanxi Sanwei Group co. Ltd. Hydrorefining 200,000 Uhde/BASF Zhahocheng, China Divided Wall Column Distillation and Single-Column Morphylane® 2000 Saudi Chevron Petrochemical Divided Wall Column Distillation 140,000 BASF/Uhde Al Jubail, Saudi Arabia 1999 VEBA OEL AG Divided Wall Column Distillation 170,000 BASF/Uhde Münchsmünster, Germany 2004 Aral Aromatics GmbH Single-Column Morphylane® 28,000 Uhde Gelsenkirchen, Germany Toluene from Coke Oven Light Oil Isomerisation, Transalkylation, Adsorption 2004 Bouali Sina Petrochemical Co. p-Xylene Adsorption 428,000 Axens Bandar Imam, Iran 2004 Bouali Sina Petrochemical Co. Xylenes Isomerisation 1 970,000 Axens Bandar Imam, Iran 2004 Bouali Sina Petrochemical Co. Transalkylation 883,000 Sinopec Bandar Imam, Iran ThyssenKrupp Industrial Solutions AG Business Unit Process Technologies Friedrich-Uhde-Str. 15 · 44141 Dortmund Phone +49 231 5 47-0 · Fax +49 231 5 47-30 32 www.thyssenkrupp-industrial-solutions.com PT 012/0/e/1000/201505/PM/Printed in Germany