(2) 6a 03) 3) wo ay @ (86) wr ws) G0) on ) United States Patent Aasberg-Petersen et al. PROC SYNTHES! FOR THE PREPARATION OF BAS Inventors: Kim Aasberg-Petersen, Allen (DK), Poul Erik Hojlund Nielsen, Frederiksberg (DX); Peter Seier (Christensen, Virum (DK); Charlotte Stub Nielsen, Holte (DK); Burein Teel, Hellerup (DX) Assignee: Haldor Topsoe AVS, Lyngby (DK) Notice: Subject to any disclaimer, the team ofthis pateat is extended or adjusted under 35 USC. 154(b) by O days Appl.Nos 137701488 PCT Filed: May 13,2011 PCTNo: PC 1P201 02378 $371 (0M), (2),(4) Date: Now. 30, 2012 PCT Pub, Nos WO2OLI/IS1012 PCT Pub. Date: Dee. 8, 2011 Prior Publication Data 2013/0082211 AL Apr. 4, 2013, Foreign Application Priority Data Jun. 1,200 (DK) 201000874 Int. Cl. cor 48 (2006.01) us.cl. usp asua73 'US008765019B2 (10) Patent No. 4s) Date of Patent: US 8,765,019 B2 Jul. 1, 2014 Field of Classification Search None ‘See aplication file for complet search history 68) 66) References Cited US. PATENT DOCUMENTS 20070231221 AL* 102007 Aasherg Pesca al. 2o0g0237000 AL 102008 Much a. 20090188959 AL_ "72009. Steyner ta gnno0r32729 AL* 93009 Genkint a 23651 annorsisoo AL* 10200) Daviset al Se595 FOREIGN PATENT DOCUMENTS bp sos AL * 11 2007 Wo woouaets AL ‘62001 * cited by examiner Primary Examiner —Melvin © Mayes Douglas Call Agent, or Firm — Dickstein Shapiro LLP ABSTRACT Process forthe preparation of synthesis gas from an essen. tilly dry hydrocarbon feedstock (1) comprising, olefins, hydrogen and carbon monoxide, the proces comprising the steps: (a) selectively hyelrogenating the olefins in the hydro- carbon feedstock a a temperature between 6D t0 190° C. 2) ‘o obtain a hydrogenated hydrocarbon feedstock comprising hydrogen, carbon monoxide and ssturated hydrocarbons (3 () adding steam (4 to the hydrogenated hydrocarbon feed- stock; (¢) performing water gas shift rection in the presence ‘of steam on the hydrogenated hydrocarbon feedstock (6) t0 ‘obiaina shifted, hydrogenated hydrocarbon mixture; () con- vertng te shifted, hydrogenated hydrocarbon mixture (8) 10 obtain a synthesis gas Assistant Examiner (74) Attorney 9 Calms, 2 Drawing SheetsU.S. Patent Jul. 1, 2014 Sheet 1 of 2 US 8,765,019 B2 Fig. 1U.S. Patent Jul. 1, 2014 Sheet 2 of 2 US 8,765,019 B2 FIG. 2US 8,765,019 B2 1 PROCESS FOR THE PREPARATION OF ‘SYNTHESIS GAS, “The invention relates to 8 process for preparation of syn= thesis gas from an essentially dry hydrocarbon feedstock ‘comprising olefins, hydrogen and carbon monowie. The pro= ‘cess for preparation of synthesis gas comprises the steps of hhydrogenating and shifing the hydrocarbon feedstock {0 ‘obtain a hydrogenated, shifted hydrocarbon feedstock. The hydrogenated, shifled hydrocarbon feedstock is subsequentiy ‘converted toa synthesis gas. In particulae the invention con: ‘eer a process whereby hydrogenation oF olefins presenti the hydrocarbon food is carried out at lw temperatutes. The synthesis gas produced issuable for use in the synthesis oF hydrocarbons by for example the Fischer-Tropsch process of the methanol-o-olfins (MTO) process. In the Fischer-Tropsch hydrocarbon synthesis stage, the synthesis gas is reacted using a Fischer-Lropsch catalyst to produce hydrocarbon products consisting of range of recov~ ‘ered compounds which ean comprise Irom one carbon atom to over 100 carbon atoms. Fischer-Tropsch processes are well-known in teat for applications using synthesis as that ‘ay be derived from a variety of earhon-cantaining feedstock sources, eg. coal, petroleum coke, biomass, natural gas and the like Por the optimum selectivity performance in the Fischer- Tropsch hydrocarbon synthesis stage isin most eases desir- able dat the hydrogen to carbon monoxide molar rato inthe fresh synthesis gas food is about 2.0. ‘Most ofthe hydrocarbons produced in the Fischer-Tropsch hydrocarbon synthesis stage ate olefins (unsaturated hydno- ‘earhons) and parafin (saturated hydrocarbons). Other less ‘desirable components that may be present in the effluent fom ‘Fischer-Tropsch reactor are carbon dioxide, wate, ad oxy entes. The oxygenates may include organic acids such as Jormic acd, acetic acid and higher acids, alcohols aldehydes, ketones and esters. Ther presence inthe product is undesir able ‘Typically about 70 to 90% of the hydrogen and carbon ‘monoxide in the synthesis gas feed tothe hydrocarbon syn- thesis stage react during said hydmearbon synthesis stage to produce products and the remaining about 10 t0 30% end up ‘na tail gas including unreacted hydrogen and carbon moa ‘oxide, methane, carbon dioxide, inert gases such as nitrogen. ‘and argon, and some residual C,, hydrvearbons. The Co, ‘includes paraffins and olefins, The wil gas is essentially cy, ‘and may therefore contain only traces of water ‘By the term “essentially dry” in relationto the hydrocarbon. ‘eestock water content is meant a water concentration i the hydrocarbon feedstock which is lower than 2 wt %, prefer= ably ower than 1 wt % most preferably lower than 0S wt %. ‘The tll gas fom te Fischer-Tropsch hydrocarbon synthe~ sis stage contains generally residual unreacted hydrogen and ‘carbon monoxide ina typical rato of about 0.5 t0 2.0 (HH ‘CO-molar ratio), Some methane is produced by the Fischer. ‘Tropsch hydrocarbon synthesis process, and some of the ‘methane the tal gas may be derived from methane fom the sythesis gas preparation step. The al gas cathe recycled othe synthesis fed stream for the Fischer-Tropsch resetor in order to improve the liquid product yield "Another option disclosed in WO 0381035590 is to use the tal gas for power generation. Here the tal ws is fist com busted, and power is generated by expanding the combusted ts in'a gas thine, andlor the combusted gs is used for “generation of steam which is expanded thrwigh a steam tur bine 2 ‘Wo patent application no, 03/0830113 discloses a Fischer. Tropseh synthesis process whereby tail gas is pretreated to remove olefins contained in the tail gas by hydrogenation or ‘anbati pr-reforming, followed by stripping off excess H mixing with recycled CO, and steam, subjecting the gas t0 steam reforming, and, after removing excess CO, and water, directing the gas back tothe Fischer-Tropsch reactor. ‘WO patent application no. 0142175 discloses process for conversion of natural gas and other fossil fuels to higher hydrocarbons, whereby a portion of or all tail gas is steam reformed in a separate steam reformer, and this steam reformed gasis introduved wo the main ga stream before tis directed (0 the Fischer-Tropsch reactor. Optionally, the tail gas is hydrogenated in orler to saturate any unsaturated hydrocarbon before being sent to the separate steam reformer, The operating temperatire of the hydrogenator is typically 220 to 250" C. The hydrogenation is not necessaily pre- fered, However, itis stated tht the unsaturated hydrocarbon hhave a greater tendency towards coking than the saturated hydrocarbons during the subsequent high temperature tret- TEP patent application no, 1860063 and WO 2006/056594 disclose © process for preparing a paraffin product from a solid carbonaceous feedstock and a process of treating tail as, respectively. Tail gas is used for preparing a hydrogen comprising gas. The hydrogen comprising gas is used to ‘optimise the hydrogen-to-CO-rato in the feed gas for the Fischer-Tropsch synthesis and/or further upgrade the prod ‘et fom the Fischer-Tropsch synthesisby one or more hydeo- processing steps, The hydrogen comprising gas is preferably prepared by reforming the tail gas. Some orall ofthe olefins in the tail pas are hydrogenated adiabatically at reactor inlet temperatures of about 200" Cand reactor out temperatures ‘fabout 100°C. or morehigher than the inlet temperature and Jn the presence of steam proto the process for preparing the hydrogen comprising yas. This is tated to be preferred since olefins are known t cats coking ofthe estalyss wed in the hydrogen manufacturing unit, Carbon monoxide in the tail gs is removed by high temperature shift or converted cither| prior fo, simultaneously with or after the olefin hydrogens tion, This is to avoid coking of the catalysts used in the hhydrogen manufacturing according to the Boudouard reae- sion (1): 20004€0, o Preferably’ a catalyst is used which combines olefin hydeo= gation activity and water gas shift (WGS) activity. The WGS reaction is shovin in reaetion (2) cont o=n1nco, @ The catalysts preferably adapted not to promote methanol formation from CO. When the til yas contains highsamount ‘of COitisespecially important thatthe catalyst used does not promote formation of methane or methanol sinee these reae- ‘ions are highly exothermic which may result in a high tem- perature which in tum may damage the catalyst. Hiydrogena- ‘ion may beachieved ina first reactor. Steam maybe added to the ist reactor to suppress Boudouard carbon formation. The {temperature ofthe first reactors preferably 15010250? C. at the inlet and 200 o $00” Cat the outlet. Further CO removal ‘can optionally be achieved in separate reactor by use of & high temperatereshif catalyst. The temperature inthe second actor is preferably in the range 300 to 500° C. In conven tional processes the molecular H.JCO ratio ofthe hydrogen comprising mixture is 4:1 10 9:1 “According othe present invention the olefins contained in an esentially dry hydrocarbon feedstock, preferably tal zs,US 8,765,019 B2 3 are hydrogenated in first reactor ad subsequently waters ‘ded and CO is converted by the Water gas shift rection ia second reactor. The gas i then converted to synthesis gas. The conversion of an essentially dry hydrocarbon feed sock comprising olefins, hydrogen and carton monoxide into a synthesis gas presents a number of challenges. In onder to convert the hydrocarbon feedstock into syn- thesis was, the feedstock gas must be eated to become reac- tivein hecatalytic andor non-catalytic conversion steps. The ‘olefins in the hydrocarbon Feedstock may cause carbon for. ‘mation when the gas is heated, which results in earbon lay- ‘down ia heater or other process equipment. The olefins may also form carbon on catalysts and thereby damage or destroy the catalyst. “The carbo monoxide in the hydrocarbon feedstock may ‘case metal dusting when the gs is heated and hereby dam= age or destroy the tubes in heaters and transfer line andor reactors, Metal dusting is initiated by carbon formation by the Boudouard reaction (1) andor the reduction of earbon mo ‘oxide by reaction (3) coset) Carbon monoxide may also result in carbon formation on catalysts, tis therefore necessary to remove or lower the contents of ‘olefins and the earhon monoxide in the hydrocarbon feed stock to. level whore these reactions na longer consitte 8 problem. The olefins in the pas ean be removed, partially or filly by hydrogeuation with iydrogen into the corresponding parafin secording to reaction (4) Hydrogen forthe hydrogenation tal gas. ‘The CO content ean be reduced by the water gas shift reaction (2). Tris necessary to add steam tothe tal gas in order o convert the CO. “According to the prior art it is possible to earry out the ‘olefin hydrogenation and the shill reaction combined in a single step using one catalyst “This has, however, several drawbacks: the presence ofolefinsin thehydrocarhon feedstock owers the Water gas shift eaction rate, the presence of water necessary forthe shift reaction may Tower the reaction ite ofthe hydrogenstion, ‘lower limit fore ike temperature i set by the require ‘meal of voiding condensation 9 as to prevent liquid water Irom damaging the eatalys, itis necessary to ruse the inlet temperature of the water- ‘gs shift (WGS) reactor to an increased temperature 0 ensure a sufficiently high reaetion rate forthe Water gas shift reaction, compared to the novessary inlet tempera- ture ofa reactor performing dry hydrogenation of olefins alone, the exit temperature of the reactor must be kept below ‘erin evel inorder to reduce the CO content toa given level defined by the equilibrium ofthe water gas shift the temperature inrease over the reactor is increased due to the cubated effect of the exothennic hydrogenation ‘and water ga shifl reactions, This may’ result ia a rather Complicated reactor layout andlor more inefficient enerey use, s already present in the 0 o 4 There is the risk of formation of ethanol or other higher alcobols eg. propanel, butanol, pentanol, hexane, accorting 0 reaetion (5); © ‘Tis revetion is exothermic and may further inerease the reactor temperate ‘Any ethanol formes ean be debated to ethene and water downstream the combined hydrogenation shift reactor ‘a shown in reversible reaction (6): HoHPe.H0 6 ‘This causes the problems described above with regards to carbon laydown and eatalyst damage from ethylene or other olefins These drawbacks ean be avoided by frst hydrogenating the olefins inthe essentially dry til gas ina frst reactor, and by subsequently adding Water and converting the CO by the ‘water gas shift reaction ina sovond reactor ‘The hydrogenation of the olefins inthe fst reactor is most advantageously done at a low femperatire, i. at or below 190° C. Operating the reator ata high temperatire, ie. above 190° C., has several drawbacks: pethanol can be formed fom the reactants reactions (7) and (8). These reactions are ‘andthe eeaetion rates inerease With het conn, e101 coyssty sca 0HH.0 o ethanol or other higher alcohols ean be formed from the ‘reactans inthe pas by action (9), Formation of ethanol is not wanted. The reation rate increases with inereas- ing temperature. The rection is exothermicandin worst ‘case tis may accelerate the reaction casing a thermal runaway ofthe reactor 20044 C,,01888,0 nickel and/or iron compounds may be present in the gs, for example inform of NCO), and/or Fe(CO), which may deposit Fe andioe Ni panicles on the eaalyst in the reaetor. The Ni andor Fe compounds may also be ‘resent inthe gas inthe form of particles, Fe catalyses a Fisher-Tropseh (PT) reaction (10) in the reaetor if the {emiperature is suficiently high for example above 190° . of above 200° C. The long-chained hydrocarbons formed by these reactions may deposit in the catalyst and block the pore system, which results in oss oF ativ- ity or hydrogenation of the catalyst. conti —cit, 18.0 oo [Nickel may catalyse earbon formation andior the FT syne thes at elevated temperature Tis thos an object ofthe present invention to provide a process for converting a hydrocarbon feedstock comprising olefins, hylrogen and carbon monoxide into a synthesis gas, in which the above mentioned drawbacks ofthe known tech. niques have been overcome The invention concerns, as defined inc the preparation of synthesis hydrocarbon feedstock comprising olefins, hydrogen and car ‘bon monoxide, the process comprising the following steps (@) selectively hydrogenating the olefins in the hydrocarbon feedstock at a temperature between 60 and 190° C. 10 ‘oblain a hydrogenated hydrocarbon feedstock comprising bydmgen, carbon monoxide and saturated hydrocarbons, (b)adking steam othe hydrogenated hydrocarbon feedstock, Aa process for as from an essentially dryUS 8,765,019 B2 5 (6) performing a water gas silt reaction in the presence of steam on the hydrogenated hydrocarbon feedstock t0 ‘obiaina shifted, hydrogenated hydrocarbon mixture, (4) converting the sifted, hydrogenated hydrocarbon mix- ture to obtain synthesis gas ‘Accordingly. the hydogenating step (a) is purposively ‘conducted without inttoduetion of steam or Water “As used herein the term essentially dry hydrocarbon feed stock"means a water concentration inthe hydrocarbon feed- sock which is lower than 2 wt %, eq lower than 1 of lower than 0.5 90%, ‘When preparing synthesis gas according to the inventive process, converting the shifted, hydmgenated hydrocarbon mixture to obtain a synthesis gas can be done by partial ‘oxidation (catalytic or non-eaalytie) and/or reforming ‘Reforming can be selected from any conventional reform= ing process such a adiabatic reforming, fired tubular steam reforming, two-step elorming, heat exchange reforming. oF autothermal reforming and combinations theroof. Ifautother- ‘mal reforming is chosen then its preferred tha ts carried ‘ut ina reactor by partial oxidation using substoichiometic “amounts of oxygen ina fame reaction, followed by a catalytic stam reforming step ina fixed bed in the reactor downstream the partial oxidation step. The resulting synthesis gas is suitable for use inthe syn= > thesis ofhydrocarbons by catalytic processes and can be used slone or it ean be mixed with a gaseous feedstock derived Troma carbonaceous eedstock converting the combined syn- thesis gas and the gaseous feedstock to obtain a product ‘comprising one or more hydrocarbons. Specifically, such Cetalytic processes comprise the Fischer-Tropsch reaction using conventional catalysts comprising Fe or Co, but the ‘invention slso applies to other pmcestes for production of hydrocarbons in Which undesired hydrocarbons may’ be con- verted into synthesis as, e.8 other processes for the produe- tion of synthetic luels or processes for the production of hydrocarbon-containing chemicals. Examples of such processes are processes fo the produe= tion of synthetic gasoline, comprising the MTG (Methanol- To-Gasoline [S. Yurchak, Stud. Surf Sei, Catal, 36 (1988) 251) and TIGAS (Topsoe Integrated Gasoline Synthesis) Topp-longensen, Stud. Surf. Se. Catal. 36 (1988) 293) pro= ‘ceses. Both theve processes roquire a syathess gas fod (for MIG process to produce the methanol feedstock) and eo- produce oneormore sieaas contsising hydrogen and carbon ‘monoxide and undesired or less desired hydrocaebons such as (C.-C, hydrocarbons that may advantageously be converted ino Synthesis gas in accordance with the invention. An ‘example of a process for the synthesis of hydrocarbon-con- taining chemicals js the MTO (aethanol-to-olefins) process in which non-olefinic hydrocarbons may serve as a adic tional source for synthesis zs to provide the methanol feed- sock. Catalysts suitable for selectively hydrogenating the olefins to saturated lydrocarhons are based on copper, for instance a ‘Cu/Z0 catalyst, or acombination of copper and noble metal {or instance platinum or palladium, "A copper based catalyst, such as a Cu/ZnO catalyst, is particularly setive inthe selective hydrogenation of olefins to paralins with a reduced formation or without the formation ‘of methanol oF higher aleohols having two oF more carbon, stom in their structure Suitable shift catalysts comprise copper, zine, aluminium for instance in their oxide form as the entalytically active material. Fxamples are LK-811 (based on Cu, Zn and Cr) LK-821-2 (based on Cu, Za and Al) and LK-823 (based on Cu, Za, Aland Cs), all available from Haldor Topsoe AVS, o 6 The synthesis was prepared by the invention has a molecu Jar bydrogen-to-carbon monexide-moler rato lower than oF equal 10 26 (H1JCO-molar ratio). Preferred ratios are between 15 and 2.6, most preferably between 1.8 and 2.3. ‘A gatoline synthesishydrogen-o-curbon monoxide-molar nto of the prepared synthesis gas is preferably lower than 2.6, more prelerably 101.5, and most preferably appeoxi- mately 1 ‘When the synthesis zs prepared by the invention is mixed with a gaseous Feedstock derived fom a earbonacenus feed- stock, and the synthesis gas mixed with sad gaseous feed- stocks converted in ane or more catalytic conversion steps t0 jobiain one or more hydrocarbon products, the gaseous feed- stock derive from a earhonaceous feedstock has preferably a hhydrogen-to-carhon monoxide-molar ratio below 2.3, and ‘more preferably between 1.7 and 23. After gasification ofthe earbonaccous feedstock into gas- cons feedsioek, an initial molecular hydrogen-to-earbon ponoxidesmolar ratio (H,/CO-molar ratio) of 03 to 0.6 is, ‘obtained in some eases, which is thea further adjusted to a ‘molecular hydrogen-to-carkon monoxidesmola ratio of 1.7 023, In other eases the H,/CO-molae ratio may directly afer aasiication be inthe range of 0.6 0 2.0. ‘Spevifially, the embodiments disclosed ia the following ‘ean be combined with one or more embodiments disclosed before or afte either embodiment ‘In the general embodiment ofthe invention we provide a process forthe preparation of synthesis gas from an essen- tially dry hydrocarbon feedstock comprising olefins, hyde zen and carbon monoxide, the process comprsing the follo dng steps (@) selectively hydrogenating the olefins inthe hydrocarbon feedstock at a tempemiture between 60 and 190° C. 10 ‘oblaia hydrogensted hydrocarbon feedstock comprising hydrogen, carbon monoxide and saturated hydrocarbons, (b)ading steam tothe hydrogenated hydrocarbon feedstock, (6) performing a water gas shift reaction inthe presence of steam on the Iydrogenated hydrocarbon feedstock 10 ‘oblaina shifted, hydrogenated hydrocarbon mixture, and (4) converting the sifted, hydrogenated hydrocarbon mix- ture to obtain a synthesis gas. As mentioned above “essentially dry hydrocarbon feel stock” means a water concenlration in the hydrocarbon feed- stock whichis lawer than 2 w1 %, e.g lower than 1 oF lower than 0.5 wt %, Tn-an embodiment ofthe iaventon, the conversion othe shied, hydrogenated hydracarbon mixture to obtain a syn- ‘thesis zs (step (€) comprises partial oxidation. ‘In an embodiment ofthe invention, the conversion ofthe shifted, hydrogenated hydrocarbon mixture to obtain a syn- ‘hes gas comprises « non-catalyic partial oxidation step, Tn an embodiment ofthe invention, the conversion ofthe shifted, Kydrogenated hydrocarbon mixture to obiin a syn- thesis gns comprises a catalytic partial oxidation stp. Ttisto Be understood that partial oxidation isa generie term ‘whieh comprises non-eatalytic partial oxidation and catalytic partial oxidation, ‘In an embodiment of the invention, the conversion ofthe shiffed, hydrogenated hydraearboa mixture to obtain a syn- thesis gs is done by eaalyte reaction, ‘Tn an embodiment of the iavenion, the conversion ofthe shifted, hydrogenated hydrocarbon mixture to obtain a syn- thesis gas i done by reforming. Tn the embodiments of the invention, the reforming is selected fom the group consisting oF autothermal reforming,US 8,765,019 B2 1 ‘adiabatic steam reforming, heat exchange reforming, fred reforming for example tubular reforming, and combinations thereof In an embodiment ofthe invention the reforming step is ‘conducted by antothermal reforming, and the shifted, hydeo- _zenated hydrocarbon mixture of stop (c) is passed to a fred heater prior to conducting said autothermal reforming Tn an embodiment of the invention, the reforming i done by a combination of heat exchange reforming and autother- mal reforming, and in which the heat exchange reformer receives a Teast part of the required energy fom the efluent ‘reum from the autothemal reformer. Compared to situa- tion where no such arrangement comprising heat exchange reformerisused, but where the stream from step (¢)is simply heated in a fiod heater before conducting step (A) in an autothermal reforming step, an increase of 6 to 8% in plant production (liquid hydrocarbons via FT synthesis down- stream) can be achieved ‘Hence in tis particular embodiment the use of low tem= perature in the hydrogenation step (a, low temperature inthe Shift stop (c) and use of heat exchange reforming and ato- thermal reforming where heat for hea exchange reforming is supplied by the eflient steam from the autothennal reformer, results in particular advantages in tems of plant production as deseribed above. An adiabatic pre-efoeming Sep is preferably also provided prior to the heat exchange reforming, eater step (©) Inn embodiment of the inveation, the reforming is done by two-step reforming, for example « tubular reformer in series witha secondary reformer. Tn an embodiment of the invention, the reforming is done by two-step relorming as mentioned above, ie. a tubular reformer (ire reformer) in series witha secondary reformer, ‘and after the hydrogenation step (a) a froetion ofthe hydo= nated hydrocarbon leedstock bypasses sep (c) and option- ally steam step (b) and is added downstream the tubular reformer and upstream the secondary reformer. The fraction ‘of the hydrogenated hydrocarbon feedstock is thus added t0 thecfflient from the tubular reformerercating the net stream Jno the secondary reformer, The tubulae reformer is located sirectly upstream the secondary reformer, In an embodiment of the invention, the water-gas-shif reaction in the presence of steam of the hydrogenated hydro- carbon feedstock in WGS.step (c) is done in a reactor pro- ded with meuns for cooling thebydrocarbon feedstock d= ing reaction. “In an embodiment of the invention, the water gas shift reaction is earied out a temperature below 350° C, prefer ably below 300° C., and more preferably between 230 and. 350° C, such as between 230 and 300° C., most preferably between 185 and 275°C. This enables thatthe exit gas Irom the hydrogenating step ean be passed to @ medium or low temperature shift without requiring addition of much heat. By Jor temperature shift, i. below 300°C. itis possbleto bring ‘down the CO content in the as toa level which is not possible ‘with high temperature shift (temperatures above 300° C.). A Jow CO content in the gas limits the extent of the Boudouard reaction (1) In an embodiment of the invention, watersgassbi reac: tion in te presence of steam ofthe hydrogenated hydroear- bon feedstock in WGS-step (¢) is done in two or more alae butt reactors with adjustment of temperature in-between 880 ‘oF more reactors, Ina farther embodiment of the invention, an adiabatic reformers arranged in series with and directly downstream a WS reactor The adiabatic reformer ean for instance he & pre-eformer, such as an adiabatic pre-reformer, for conert- 0 o 8 og higher hydrocarbons into a mixture of methane and car- bon oxides, hydrogen and steam, Tn an embodiment of the invention, the obtained synthesis 25 has @ molecular hydrogen-to-carbon monoxidesmolar raiio lower than or equal 0 26 Inanembodimentor te invention, the hydrogenation reac ‘ion is catalysed hy a catalyst comprising either copper or @ combination of copper and noble metals. Ta an embodiment of the invention, the water-gat-shift reaction is catalysed by a catalyst comprising metalic or ‘oxide form of metals selected from the group eoasisting of copper, zinc, aluminium, chromium, cesium and combina- ‘ions threo Ta an embodiment of the invention, the essentially dry hydrocarbon feedstock comprising olefins, hydrogen and car- ‘bon monoxide is obtained from hydrocarbon synthesis, for instance from tail gas from Fischer-Tropsch synthesis or a reeycle gas from gasoline synthesis, Thus, in a particular embodiment said essentially dry hydrocarbon feedstock is tail as fiom Fischer-Tropsch synthesis. Thereeycle gas com prises light products such as light paraffins and light olefins and unconverted synthesis pas Tn an embodiment of the invention, selectively hydroge- ating the olefins inthe hydrocarbon feedstock in hydroge- ‘ation step (a) is conducted in an isothermal reactor, prefer ahly at temperature in the singe of 100 ta 150° C. This ‘enables high conversion of olefins such as C,H, while atthe same time avoiding significant formation of methanol or higher alcohols and other by-prodnets ‘In an embodiment ofthe invention, selectively hydroge- ‘ating the olefins inthe hydrocarbon feedstock in hydroge- sation step (a) is conducted in an adiabatic eactr in which the inet temperature i preferably in the range of 70 to 120° CC, more preferably 800 100° C., and the outlet temperature 58140 t0 190° C,, more preferably 150 0 185°C. In an embodiment of the inveation, the pressure in the hydrogenation step () is in the range of 20 0 70 bar, prefer ably 20 to 50 ba, more preferably 20 1040 bar In yet another embodiment, the invention also encom- passes the use of the synthesis gas prepared according t0 Anyone of the process embodiments in the preparation of gasoline said embodiment comprising the steps of combin- ing the synthesis gas with a gaseous feedstock derived from a ‘carbonaceous feedstock ad covering the syithesis 2s With the gasonus feedstock in at least two catalytic coaversion steps to obtain a product comprising one or more Cy-C, hydrocarbons. BRIEF DESCRIPTION OP THE DRAWINGS. ‘The following Figures disclose two embodiments of the FIG. 1 shows the proces steps for preparation of synthesis ‘as according wo an embodiment ofthe invention, and FIG. 2 shows the process steps for preparation of gasoline ‘sing the synthesis gas obtained by the inventive process. The essentially dry hydcarbon feedstock 1 comprising olefins, methane, hydrogen, carbon monoxide and light hydrocarbons, is transferred to hydrogenation reactor 2 for selective catalytic hydrogenation ofthe olefins. The operation ‘emperature of the seletive hydrogenation reaction is 60 10 190" C. and hydrogenated hydrocarbon feedstock 3 is ‘obiained from the hydrogenation reactor 2, Essentially no fleohols are formed. ‘The hydrogenated hydrocarbon feedstock 3s mixed with steam 4 and the mixture § is subjected to a water gas shift ft reactor 6.A shifted hydrogenated hydrocar-US 8,765,019 B2 9 bon mixture 7is obtained from shift reactor 6 and this mixture 7s reformed in reforming reator 8 to obtain synthesis was 9. Synthesis gas 9 can optionally be subjected 10 further processing 10, for instance at a Fischer Tropsch plant for ‘conversion to liquid hydrocarbons. Turning t0 FIG. 2, the obtained synthesis gas 9 is as described in connection with FIG. 1. Synthesis yas 9 is com- bined with # gnseous feedstock 11 derived from a carbon- aceon feedstock 11. Thecombined gas iscoavertedinat least ‘80 catalytic conversion steps inside unit 10 t0 a product ‘comprising one or more CC, hydrocarbons 12, EXAMPLES Example 1 A nb test on dry hydrogenation was done using the feed ‘gas showin in Table 1. The catalyst wsed was a Cu-based ‘catalyst, specifically A Cu/Za0 catalyst “The gas was pasted hmougha bed ofthe catalystin reactor ‘operated at isothermal conditions, and the efiluent gas com- Position was measured. The space velocity was 2000 NUKwh. The pressure was 20 bar ‘The conversion of propylene to propane, and of butyleneto butane is shown in Table 2 TABLE 1 Compooen Moe Teco (ar Ns Ci) a7 ©, la TABLE 2 Tenpestue —Cillgcomenion —C.H,comeron 0 10 TARL Tren ans Cy a cost, a 1, a ote an ‘The effluent gas was analysed for methanol and higher hydrocarbons. Measurements were done at reactor temper- tures of 62, $0, 100, and 150° C. No methanol or higher aleolols were detectable at temperatures of 62, 80, and 100° C. Ata temperature of 150° C,, the methanol concestration was measured t0 be 0.16 mole %. No higher aleobots were ona. ‘These tests show that when the hydrogenation is done at Jow temperature, the formation of methanol and other by products are very low. Example 3 Simulations of hydrogenation ofthe model gases shown in ‘Table 4 have heen done. The simulations have heen done assuming adiabatic conditions. As can be seen from Table 5, itis possible tooperat below 200° C. particularly at or blow 190° C. in the entire reactor (where high olefin conversion without methanol formation ie oblained) by selecting aa appropriate inet temperature, TABLE 4 Coayponest Maes Mots Taare ae Nac) ery = toca os i TABLES 2 er) " ES “The tests clearly demonstrate that the catalyst is ative in the desired temperature interval for use in the process of this invention, Example 2 A lab test on dry hydrogenation was done using the feed 2s shown in Table 3. The catalyst used was as deseribed in ample 1 ‘The gas was passed through bed of the catalyst ina reactor ‘operated at isothermal conditions, andthe eflluent gas com- Position was measured. Thespace velocity was 2000 NUkwh. The pressure was 20 bar o ‘Comparison Example 4 Lab test was done to study the influsnee of Fe contamina ‘ion of hydrogenation catalysts, A Cu-based catalyst was impregnated with 75 ppm Fe. The catalyst sed was as described in Example 1 ‘The catalyst performance was testedin separate tests using thegas compositions shown in Table. test was done under ‘isothermal conditions at 210°C. and at a pressure 65 bar. The space velocity was 6250 NUkg/h. The test duration was 14h. After the tests, the catalyst was analysed for earbon. The catalyst atthe ext ofthe reactor showed a carbon uptake of 696 wUS 8,765,019 B2 rn @ « a he is 00, “9 ts Another test was done with pas composition 2, at 230° C and pressure of 65 har, for $00 h. The space velocity was 12500 Nika, The catalyst atthe exit of the bed showed a ‘carbon uptake of ~13% wh. The carbon was in form of Wax, iv, long-ehained hydrocarbons. “The invention claimed is 1. Process forthe preparation of synthesis gas from an ‘essentially diy hydrocarbon feedstock comprising olefin, hydrogen and carbon monoxide, the process comprising the following steps: (@) selectively hydrogenating the olefins inthe hydrocar~ x ‘bon feedstock at a temperature between 60 and 190° C. to obtain a hydrogenated hydrocarbon feedstock com- prising hydrogen, carbon monoxide and saturated hydrocarbons, wherein selectively hydrogenating the olefins inthe hydrocarbon feedstock i conducted With- > ‘ut introduction of steam or water ineither anisothermal reactor, or in an adiabatic actor in which the inlet temperature is ina range of 7010 120°C. and he outlet temperature is ina range of 140 0 190° C (6) adding steam to the hydrogenated hydrocarbon feed stock: (© performing a water gas shift reaction inthe presence of steam on the hydrogenated hydrocarbon feedstock to cobiain a shifted, lydrogenated hydrocarbon mixture: and (@) performing partial oxidation or reforming of the shifed, hydrogenated hydrocarbon mixture, whe ‘the paral oxidation or reforming forms a synthesis pas 12 having a molecular hydrogen-to-carbon lar ratio lower than oF equal 1 26. 2. Process secordingto claim 1, wherein the reforming ep is selected from the group consisting of autothermalreform- ing, secondary reforming, adiabatic steam reforming, heat exchange refoming, fired reforming and combinations thereat 3. Process according to claim 1, wherein the reforming is carried out by 8 combination of heat exchange reforming and aulothermsl reforming, aad in which the heat exchange reformer receives at least part of the required energy by heat exchange with the efflant stream from the atothermal reformer, 4. Process according to claim 1, where the reforming is done by two-step reforming comprising tubular reforming followed directly by secondary reforming, and a fraction of the hydrogenated doearbon feedstock ota asses step (c) and optionally step (b) and Steam he tasting opal secondary reforming sp. 5, Process according to claim 1, wherein the water gas shift caction is carried out ata temperature below 350° C. 6. Process ccordingto claim 1, wherein the hydrogenation caction is etalysed bya catalyst comprising either copperar ‘8 combination of copper and noble metals 7. Process according ta claim 1, wherein the water gs shift reaction is catalysed by a catalyst comprising metalic or oxide form of metals selected from the group consisting of copper, zine, aluminium, chromium, eesium and combina tions thereof, 8. Process according to claim 1, wherein the essentially dry hydrocarbon feedstock comprising olefins, hydrogen and car- 'bon monoxide is obtained from hydrocarbon synthesis. 9. Process according to claim 8 wherein said essentially dry hnydrocarbon feedstock is tail gas from Fischer-Tropsch syn- thesis mnoxide-mo-