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2) United States Patent 6a 03) 3) wo ay @ (86) on) (2) Klanner et al METHOD FOR PRODUCING BUT FROM N-BUTANE DIENE, Inveators: Catharina Klanner, Mannheim (DE) Gétr-Peter Schindler, Mannbeim (DE) Sven Crone, Limburgerhof (DE) Frieder Borgmeier, Mannheim (DE) Mark Duda, Liwigshafen (DE); Fall ‘Simon, Beasheim (DE) Assignee: BASF SE, Ludwigshafen (DE) Notice: Subject to any disclaimer, the team ofthis pateat is extended or adjusted under 35 USC. 154(b) by 1204 days. Appl.Nos — L1813,935 PCT Filed: Jan, 16, 2006 PCT Nos PCT/EP2006/080217 $371 (0M), (2),(4)Date: Jul. 13, 2007 PCT Pub, Nos WO2006/075025 PCT Puls Date: Jul. 20, 2006 Prior Publication Data US 200810183028 A1 Jul. 31, 2008 10 200 002 127, Int.Cl. core $33 (2006.01) S.C ‘585/325; 585/616; S8S1621; 585/628 ‘US008088962B2 (10) Patent No. 4s) Date of Patent: US 8,088,962 B2 Jan. 3, 2012 (58) Fleld of Classification Search 5851325, S85i616, 621, 628 ‘See application file for complete search history 60) References Cited US. PATENT DOCUMENTS 2OOSIOL7I311 AI $2005 Schindler ea PORPIGN PATENT DOCUMENTS be Issis2 7969 Gs tors 1968 Wo 2mosouros = L004 Primary Examiner —Towan Dinh Dang (74) Attornes, Agem, or Firm — Connally Bove Lodge & Fut: LEP on ABSTRACT A process for preparing butadiene, comprising A) providing ‘stream (a) comprising n-butane: B) feng steam (a) com: prising into atleast one first dehydrogenation zone and non- Dxiatively catalytically dehydrogenating n-butane to obtain ‘stream (b) comprising n-butane, I-butene, 2-butene, bu ‘dene, hydrogen and low-boiling vecondary constituents; C) feeding stream (b) and an oxyBenous ga info a lest one sevond deiydrogenation one and oxidatively dehydrogenat- ing n-butane, I-butene and 2-butene to obin a seam (c) comprising n-butane, 2-buten, butadiene, os-boling see- ondary constituents, carbon Oxides and steam, wherein stream (6) has & higher content of butadiene than siream (): 1D) removing the low-boiling secondary constituents and steam to obtain a stream (a) substantially consisting of n-bu ‘ane, 2-butene and butadiene; F) separating stream () ito a stream (e1) consisting substantially of n-butane and 2-bute and a steam (¢2) consisting substantially of butadiene by extractive distillation; F) recycling stream (el) into the frst Seydropenation zone: 7 Claims, 1 Drawing Sheet U.S. Patent Jan. 3, 2012 US 8,088,962 B2 US 8,088,962 B2 1 METHOD FOR PRODUCING BUTADIENE ROM N-BUTANE. RELATED APPLICATIONS, ‘This application is a national stage application (under 35, USC. §371) of PCTIEP2006/050217 filed Jan. 16, 2006, which claims benefit of German application 10 2005 003 127.1 filed Jan. 17,2005, ‘Butadiene is an important basic chemical and is used, for ‘example, to produce synthetic eubbers (butadiene homopoly~ mers, siprene-buladiene rubber or ntsile rubber) or for pre- paring thermoplastic terpolymers (aerylonitele-butadiene- styrene copolymers). Butadiene is also converted. t0 silfolne, chiloroprene and 1,4-hexamethylenodiamine (via 1 4-dichlorobutene and adiponitle) Dimerization of butad ‘ene also allows vinyleyelohexene to be obtained, which ean, be dehydrogenated to styrene. ‘Butadiene may be prepared by thermal cracking (steam- cracking) of saturated hytdrocarbons, ia which ease the raw Sarsing material used istypically naphtha, [nthe steamerack- ing of naphtha, a hydrocarbon mixture of methane, ethane cthene, acetylene, propane, propene, propyne, allen butenes, butadiene, butynes, methylallene, C, and higher hydrocarbons is obtained. ‘A isdvantage of obtaining butadiene inthe eracking pro ‘ess is that relatively large amounts of undesired coproduets are inevitably obiained I is an object of the invention to provide a process for preparing butadiene fom n-butane, in which copreducls are ‘obtained to minimal extent. The objects achieved by aprocess for preparing butadiene fiom n-botane, comprising the steps of A) providing feed yas stream a compeising n-butane; 1B) fewding the food gas stream » comprising n-butane into at Teast one frst dehydrogenation zone and nonoxidatively catalytically dehydrogenating n-butane to obtain a product gs stream b comprising n-butane, I-butene, 2-butene, butadiene, hydrogen and low-boiling secondary const ats, with oF without carbon oxides and with oF without (©) feoding the product gas stream b of the nonoxidative catalyie dehydrogenation and an oxygenous pas into at least one second dehydrogenation zone and oxidatively dehydrogenating n-butane, I-butene and. 2-butene 10 obiain a product gas stream e comprising. n-butane, 2-butene, butadiene, ow-boiling secondary constituents carbon oxides and steam, said produet gas stream c having ‘higher eootent of busdiene than proder gas stab D) removing the low-boiling secondary constituents and steam to obtain a C, product gas stream d substantially consisting of n-butane, 2-butene and butadiene; ) separating the C, product gas stream d ino a stream el ‘consisting substantially of n-butane and 2-butene and a productorvalue stream 2 consisting substantially of butadione by extractive distillation; ) reveling stream el into the fst dehydrogenation zone. The process according to the invention features particu larly effective ntilization ofthe raw materials, Thus, losses of the n-butane ra material are minimized by reeling uncon verted n-butane into the dehydrogenation. As a result ofthe ‘coupling of nonoxidative catalyie dehydrogenation and oxi ‘dative dehydrogenation, a high butadiene yield is achieved, Tn fist process part, A, a feed gas stream a comprising s-butane is provided. Typically, the starting aw materials are cbutane-ich gas mixtures sich as liquetied petroleum gas (LPG). LPG comprises substantially strated C,-C, hydro- 2 also comprises methane and trees of The composition of LPG may vary aeatly. Advantageously, the LPG used comprises at leat 10% by weight of butanes. 5 _Altematively, a refined C, stream from crackers or refiner- jes may be used The n-butane-containing dehydrogenation feed gas stream is generally cride butane. It wll preferably be enide butane ‘which fulfils the specifications listed below (analogously 10 DE 102 45 585, data in parts by volume): content of n-butane 290% by volume, usually volume, geaeally 95% by volume: content of isobutane 1% by volume, usually volume, generally 0.3% by volume: content of I-butene 21% by volume, usually 0.5% by volume, generally 50.3% by volume: content of eis-butene 19% by volume, usually 0.5% by volume, generally 0.3% by volume! content otrans-butene =1% by volume, usual volume, geaerally 0.3% by volume: content of isobutone =1% by volume, usually volume, generally 0.3% by volume: ‘Total content of C, hydrocarbons other than butanes and 293% by 50.5% by 5% by 59% by butenes = 1% by volume, usually 0.5% by volume, gener- 2s ally 20.3% by volume: content of methane 10 ppm, usually SS ppm, generally from 010 1 ppm: content of propane $100 ppm, usually =90 ppm, generally from 50 to $0 ppm; {otal content of C, hydrocarbons 5% by volume: total content af C, hydrocarbons =5% by volume: {otal content of C;-C. hydrocarbons =20 ppm; total content of oxygen-containing organic compounds pm content ofionogenic C150.1 mg/kg: 30 ‘otal content of Cl-eontaning compounds and expressed as 120.1 meg; ‘otal content of F-contaning compounds and expressed as F50.1 mak: {otal content of S-contaning compounds and expressed as S=0.1 mg: wake hele, Gast jes, Ge=2 jks, Hest ji Inst eh, rel ake, KES ugikg, Lis wake, Mg= I nek Hike Moe np Niseko npg NSS (Oupkg, Pa= ugikg, PES! woke, RHE yw, otk, SmI jigrky. Sr pkg, Toss pglkg, Tis pkg, TT ghkg, VE ygike, 2020.1 mag, Zr=1 wake none variant ofthe process according othe invention, the provision ofthe dehydogenation feed gas stream comprising ‘butane comprises the steps of (AD providing a liquefied petroleum gas (LPG) stream, (A2) removing propane and any methane, ethane and C,* hhydrocarbons (mainly pentanes, additionally hexanes, Dheptanes, benzene, toluene) from the LPG stream to obtain stream comprising butanes (n-butane and isobutane), (A3) removing isobutane from the steam comprising butanes tw obtain the feed gas stream comprising n-butane, and, if appropriate isomerizig the isobutane removed to ive an ‘mbutaneisobmtane mixture and reeycling the n-butane! ‘sohutane mixture ito the isobutane removal, Propane and any methane, ethane and C;" hydrocarbons are removed, for example, in one or more customary rect cation columns. For example, ina fist column, los boilers (methane, ethane, propane) may be removed overeadan o US 8,088,962 B2 3 ‘second colt, high boilers (C,* hydrocarbons) may be Temoved atte bottom ofthe colon. streams competing batanes (bua and isobutane) i obtained, from which isobutane is removed, for example in cstomary rectifis- tion coma. The remaining steam comprising nebtane is teed asthe fed gas sea forthe downstream butane dehy dogenaton The isobutane seam removed is preferably subjected to isomerization. To thisend, the steam conyesing Bobulaeis {elino an ioserzation reactor, The isomerization of scbo- tane to n-butane may be eared ow as desetibed in GB-A 2 18815. Ana-butanenobutane mixture iscblained ands fed ino the n-butanelsbane separating cofumn. “Theisohtane stm emeved my alo Be sent to farther use, Tor example for preparing methacrylic acid, poly ‘sobutene or mei ter-buly ether 1 one precess pat, B, the feed gas stream comprising s-buteneis fed ino a dehydrogenation zone and subjected to anonoxidative catalytic dehydrogenation. In this dehydroge- ‘tin, n-butane spar debydrogente in a Jchydrogease thn reacorovera dehydogeating exalt to give I-buene ‘and 2butene, and butadiene fs ako formed. In addition, tydrogen and small amounts of methane, ethane, ethene propane and propenearcbained. Depending on the method Df the dehydrogenation carbon oxide (CO, CO.) water and nitrgen may alo be presen inthe product gas nntre of the honoxilave catalytic naulane deiyrogenation. Uncone verted nsbutane js adtonally present inthe product gs “The nonoxidative catalytic n-butane dehydrogenation may te cared out with or wilout oxygens gas a cof One feature of the nonoxidave method compared 10 an ‘oxidative method is the presence of hydrogen inthe fun! tus. Inthe oxidative delvrogeaton, fee hydrogen is aot Formed in sobstanal amounts. “The uonoxidative catalytic n-butane dehydrogenation may in principle be caried oa in any reactor pes and methods isclosed hy the pir art A comparatively compehensive ‘description of deydogenation processes sulale in accor ‘dance with the invention is also contained in "Catalytica Studie Division, Oxidative Dehydrogenation and Altemns- tive Dehydrogenation Processes” (Staly Number 492 OD, 10993, 430 Ferguson Drive, Mouttain View, Cali, 4083 5272, USA), ‘Aauabl reactor fom xed bed tubular or tube bundle reactor. In these rectors the catalyst (dehydrogenation eat Iystand, when working with oxygen as the cofed, a special ized oxidation catalyst if appropriate) is disposed a a fixed tee in eatin tube o in a bundle of reaction tes, The reaction tubes are customarily heated indetly by the come bastion of pa, for examples iydrocarbon sucha ethane, inte space sunounding the reaction tubes. I's Evora ppl his indies foro heating only to about heist 20t0 $Me the length ofthe fixed be and o heat the remaining ie Fength othe required ation temperature by thei heat released inthe couse of indirect heating. Customary Feaction tube internal dimetrs are from about 1010 15 ex ‘typical dehydrogenation tube bundle reactor comprises From about 300 t 1000 reaction bes, The ineralenpers- ture in the wction tubes typically varies inthe range fom 300 to TOY C. preferably i the range fom 40040700" C “The working pressures customarily fom 0 to 8 bat, fre «quently from 1 to 2 bar, when a smal steam dain is wsed the Linde process for propane dey drogenation), for else fom 3 108 Bar when ising a high stam dilition (Gmilar to the steam active reforming process (STAR pro ‘ess for delydrogeting propane oF butane of Philips 0 o 4 Petroleum Co,, see U.S. Pat, No. 4,902,849, U.S, Pat, No. 4.996.387 and US. Pat. No, 5.389.342). Typical catalyst hhouely space velocities (GHSV) are from $00 to 2000 I ‘based on the hydrocarbon used. The catalyst geometry may, or example, be spherical or eylindreal (hollow or sold) (On the industri! scsle, a plurality of (for exemple tee) such tbe bundle reactors may be operated parallel in the I” Sehydrogenation zone. Iti possible in accordance with the invention, ifappropriate, for one (or two) ofthese reactors 10 bein dehydrozenating operation, while the catalyst charge is being regenerated in a second (thnd) reactor, without the ‘operation in the 2” dehydrogenation zone having to be shut down, Such a procedure is appropriate, for example, in the [BASF-Linde propane dehydrogenation process described in the literature Sueha procedure ca hatiskaownas thesteam active reforming (STAR) process” which has been developed by Phillips Petroleum Co. (ct, for example, US. at No 4,902,849, US, Pat. No. 4,996,387 and US, Pat. No. 5,380,342), The dehydrogenation catalyst used in the STAR process is preferably platinum, comprising promoters, on ine -amagnesium) spinel asa support (efor example, US. Pat. No. $073,662). In contrast tothe BASF-L inde propane ‘dehydrogenation process the propane to be dehy drogenated js diluted with steam in the STAR process. A typical molar ratio of steam fo propane is inthe range from 4 to 6. The starting reator pressure i frequently from 3 to 8 bar and the reaction temperature is appropriately from 480 10 620° C. ‘Typical catalyst hourly space velocities of propane are from 200 to 4000 hr (GHSV), ‘The heterogencously catalyzed, nonoxidative n-butane {dehydrogenation in the process according to the invention ‘may also be carried out in a moving bed. For example, the noving catalyst bed may be accommodated in a radial How eactor. In this reactor, the catalyst moves slowly from top 10 bottom, while che reaction was mixture Hows radially, This procedure is employed, for example, in what is known as the ‘UOP.Olelex dehydrogenation process, Since the reactors in this process ae operated quasi-adiabaticlly. ts appropriate {0 operate a plurality of reactors connected in series as a battery (rypically up to four). Within the battery, a reeyele stream comprising n-butane from the 2 dehydrogenation ‘anc my be fed in. This allows excessively great temperate lrences of the reaction gas mixture atthe reaetor inlet and fat the reactor outlet toe prevented and good overall yields ‘nevertheless t he achieve. ‘When the catalyst hed as left the moving bed reactor, its sent fo regeneration and subsequently reused. The dehydro- zenaton catalyst used for this process may, for example, bea spherical dehydrogenation catalyst which consists substan- tally of platinum on spherical alumina support. Inthe UOP variant, ydrogen is added to the propane o be dehydroge- ‘ated inorder fo prevent premature catalyst aging, The wo ‘ng pressure is typically fom 2 40 § bar. The molar hydrogen to propane ratio is typically ffom 0.10 1. The eaetion tem- pefatures are preferably fom $50 t0 650° C andthe residence time ofthe eatalyst in one reactor is from about 210 10 In the fixed bed process deseribod, the catalyst geometry may likewise be spherical, but also eylindsieal (bollow or solid) or be configured geometrically in a diferent way. “The nonoxidative etalytien-butane deliydeogenation may also be eared out under heterogeneous catalysis in a ide ined bed, as desribed in Chem. Eng, Sci 1992 6,47 (9-11) 2313. Appropriately, two fluidized beds are operated in par allel of which one is generally inthe state of regeneration. ‘The working pressure is typically from I to 2 bar. the deby~ drogenation temperature generally fom $50 to 600° C, The US 8,088,962 B2 5 hat required for the dehydrogenation is introduced into the reaction system by preheating the dehydrogenation catalyst ‘o the rection temperature, The admixing ofa cofeed com- prising oxygen allows the prcheaterto be dispensed with, and the heat required to he generated direely in the reactor system by combustion af hydrogen and/or hydrocarbons inthe pres- ‘enceof oxygen. appropriate, a cofeed comprising hydrogen, ‘may adalitionally be admixed, The heterogeneously catalyzed n-butane dehydrogenation jn a Muidized bed may also be caried out as described for propane in proceedings De Witt, Petrochem Review, Hous- ton, Tex, 1992 a, NI. Altematively to the above-described procedures, the heterogeneously estalyzed n-butane hydro: fenaton may also be realised analogously to the process ‘developed by ABB Lummis Crest (ef proceedings De Witt, Petrochem. Review, Houston, Tex, 1992, PL, The nonoxidative catalytic n-butane dehydrogenation may be caried out in a tray reactor with or without oxygenous as as # cofeed. This reactor comprises one or more successive ‘catalyst beds. The numberof catalyst beds may be from 110 20, advantageously from L106, preferably from 1 0 4 and in particular rom 1103. Thecatalyst beds are preferably owed through radially or axially by the reaction gas, In general, sucha tay actor is operated with fixed catalyst bed. Inthe simplest case, the fxed catalyst beds ina sha irace reactor ‘are arranged axially or in the annular gaps of concentric ‘vlindrial grids. One shaft famace reactor corresponds (0 ‘one tay. The performance of the dehydeogeoation ita single shaft famace reaetor corresponds toa prefered embodiment, in which i is possible ro work with oxygenous cofeed. In.3 furor prefered embodiment, the dehydrogenation scarred ‘out in a tray reactor having 3 catalyst Beds. In 4 method. ‘without oxygenous gas as coleed,the reaction gas mixture is subjected to intermediate eating inthe tray reactor on ts way from one catalyst bed to thenex catalyst bed, forexample by passingitoverliat exchanger plates heated by hot gases orby passing it though tubes heated by hot combustion gases. Ina preferred embodiment ofthe process according to the invention, the nonoxidative catalytic n-butane dehydrogena- tion is earied out autothermally. To this end, the reaction gas mixture of the n-butane dehydrogenation is additionally admixed with oxygen in at least one resetion zone and the hydrogen andor hydrocarbon present in the reaction gas mix- ture sat least parially combusted, which generates directly jin the reaction gas mixture at least @ portion of the beat required for dehydrogenation in theat least one reaction zone. In general, the amount of oxygenous gas axed to the reaction gas mixture is selected in such way that the amonnt ‘of heat required forthe dehydrogenation of n-butane i pen- ‘erated by the combustion of the hydrogen present in the reaction gas mixture and of ay hydrocarbons present in the reaction gas mixture andor of carbon present in the form of ‘coke. Ia general, the loll amount of oxygen supplied, based ‘onthe total amount of Butane is from 0.001 t0 05 mol/mol preferably fram 008 to 0.2 molol, more preferably Irom 10,05 t9 0.2 mol/mol. Oxygen may be used either in the form ‘of puie oxygen or in the form of a oxygenous gas in a rmixtuee with inet pases, for example in the form of at: The prefered oxygenots gis air or oxygen-enriched air having an oxygen content of up to 50% by volume. The inert gases ‘and the resulting combustion gases generally have an add tional diluting action and thus promote the heterogeneously catalyzed delydrogenation. “The hydrogen combusted to generate heat isthe hydrogen ormed in the catalytic n-butane dehydrogenation and also any hydrogen adlitionally aed tothe reaction gas mixture ‘as hydrogenous gas, The amount of hydrogen present should 0 o 6 preferably be such thatthe molar H./O, ratio inthe reaction ‘as mixture immediately afte the oxygen has been fed in is irom 1 to 10 mol/mol, preferably from 2 to 5 molimol. la ‘multistage reactors, this applies to every intermediate feed of ‘oxygenous and any hy drogenous ga, “The hydrogen is combssted catalytically. The dehydroge- nation catalyst used generally also catalyzes the combustion ofthe hydrearhons and of hydrogen with oxygen, sa that in principle no specialized oxidation catalysts required apart {rom it, One embodiment works in the presence of one oF ‘more oxidation catalysts which selectively catalyze the com: bustion of hydrogen to oxygen inthe presence of hydrvcar- bons. The combustion ofthese hydrocarbons with oxygen to ive CO, CO, and water therfore proceeds only’ to a minor extent The dehydogenation catalyst and the oxidation cata- Ist are preferably present in different reaction zones. ‘When the reaction iscaried out ia more than one stage, the ‘oxidation catalyst may be present only in one or in sore than ‘one ezetion zone oF in all reation zones. Preference is given to disposing the catalyst which selec- sively catalyzes theoxidation of hydrogen at the points where there are higher partial oxyzen pressures than af other points inthe reactor, in pancular near the feed point forthe oxyg- {enous gas. The oxygenous gas andr hydrogenous gas may be fed in at one or more points in the reactor. n one embexliment ofthe process according to the inven sion, thor is intermediate feeding of exygenous g26 and of hhydrogenous gas upstream of every tay ofa tay reactor. laa funherembodimentof the process according tothe invention, ‘oxy genous gas and, ifappeopriate, hydrogenbus gare fein ‘upstream of every iy except the fist tay. In one embodi- meat, layer of a specialized oxidation catalyst is present downstream of every feed point, followed by a layer of the ‘dehydrogenation catalyst. In a further embodiment, no spe- cialized oxidation catalyst is present. The dehydrogenation ‘emperatureis generally from 400 to 1100" Che pressure in the lost catalyst ed othe tray reactor is generally from 0.2t0 ‘Shar, peferably’from I 10° br. The GHSV is generally from $500 to 2000 5 ad in high-load operation, even upto 100 (000, preferably from 4000 10 16 000 i ‘A prefered catalyst which selectively catalyzes the com- bustion of hydrogen comprises oxides andor phosphates selected fom the group consisting of the oxides ance pos phates of germanium, Gn, lead, arsenic, autimoay’ ad bi ‘uth, A further preferred catalyst which catalyzes the com- bustion of hydrogen comprises a noble metal of transition cup VIII andlor [ofthe periodic table. ‘Typically, the heterogeneously catalyzed partial detydro- genation of n-butane requires comparatively high reaction femperatures. The achievable conversion is limited by the thermodynamic equilibrium. Typical reaetion temperatures are from 300 to 800° C. or front 400 to 700° C. High tem- peratures and removal ofthe H, reaction product shift the ‘uilbrium position in the direction ofthe target product Since the heterogeneously catalyzed dehydrogenation reaction proceeds with increasing volume, the conversion may be increased by lowering the partial pressure of the products. This ean be achieved in a simple manner, for ‘example by dehydrogenating under reduced pressure andlor by admixing substantially inert diluent gases, for example steam which normally constitutes an inert gas or the dehy- ‘drogenation reaction. As a further advantage, dilution with steam generally eauses reduced carbonization of the catalyst ‘sed, since the steam reats with earbon formed by the prin- ciple of coal gasification. Purther diluents suitable foe the heterogeneously catalyzed butane dehydrogenation are, for example, CO, methane, elbane, COs, ittogen and noble US 8,088,962 B2 1 pases suchas He, Ne and Ar The dents mentioned are tener ls suitable as dentin the dehydrogenation tis favorableto carry othe nonoxidative n-butane dehy ‘adiabatic passthrough the catalyst bed, the reaction gas mix- ‘ure wll then coo}, depending onthe conversion and dilution, by from about 30 to 200° C, |As the first dehydrogenation zone, a single shaft furnace reactor may’ bo sufficient asthe fixed bed reactor which is flowed through axially andlor radially by the reaction gas mixture, nthe simplest cas, it isa single closed reaction volume, or example a vessel, whose interal diameter is from 0.1 10 10m, possibly also fom 0.5 to $m, and in which the fixed ‘catalyst bed is applied to a support device (or example a aid), The reaction volume which is charged with eaalyst and ‘ssubstantallyhea-insnlatedin adiabatic operation sawed through axially by the hot n-itane-contsiing reaction gas. The catalyst geometry may either be spherical orelse annulae ‘orstrand-shaped. The n-hitane-contsining resi gas stem= ming from the 2" dehydrogenation zone may be injected via ‘ee lines introduced into the catalyst bed. Since the reaction volume can be realized in this ease by a very inexpensive apparatus, preference iso be given wo all eatalyst geometries ‘which have a particularly low pressure drop. These are in particular catalysts which lead to a particulaey lage cavity volume or are structured, for example as monoliths or hon- ‘eycombs, To realize a rail New ofthe n-hutane-containing reaction gs, the reactor may, for example, consist of Wo ‘concentric cylindrical grids disposed in a shell and the cata Jystbed may be arranged in their annular gap. Inthe adiabatic ‘ease, the shell would aguin be thermally insulated if appro- priate Afteraprolonged operating time, the aforementioned eat Jysts ean Be regenerated ina simple manner, for example, by initially passing air (preferably) cuted with nitrogen andor steam in first regeneration states over the eaalyst bed at an fnlet temperate of from 300 to 600°C. frequently from 400 ‘tw $50? C. The catalyst hourly space velocity of regeneration as Jar example ar) may be, for example, from 50 0 10000 heandthe oxygen content of theregeneration gas from 0.10 21% by volume, In subsequent furer regeneration stages, the regeneration gas used under otherwise ientcal regener tion conditions may be air Suitable regeneration gases are alsa fue gases which have a residual oxygen content of from 1 to 6% by volume and are formed in the combustion, and sill ‘comprise nitrogen, team, carbon oxides and residual hydro- carbon. Its recommended to flush the eatalyst befor i is regenerated with inert yas (Tor example N,), Ils generally 10 be recommended 0 subsequently regenerate with pure hydrogen or with hydrogen diluted by inert gs (preferably steam) (the hydrogen cantent should he = 1% by volume) The heterogeneously catalyzed, nonoxidative n-butane hydrogenation may he operated with comparatively low ‘butane conversion (15 mo %: in tis ease, the high selec- tivity and catalyst lietime are advantageous. The n-butane \elyydrogenation should preferably be operated at conver- sions of =15 mol %, aioe preferably >30 mol %, The hourly space velocity of reaction ges may, for example, be from 100 10.000 or 400000 h?,for example from 300 to 7000 h- or from about 500 40 4000 h-* a the simplest case, the fixed catalyst beds in a shat fumsce reactor are arranged axially or inthe annular gaps of concentric cylindrical grids. However, it is also possible to anrange the annular gaps in seaments one on top of another ‘and conduct dhe gas afer it as passed radially through one segment into the next segment above i or bel it Appropriately, the reaction gas mixture is subjected 10 intemsite heating in the tray reactor on its path fom one catalyst bed tothe next catalyst bed fr example by passing it ‘over heat exchanger surfaces (e ribs) heated by hot gases or by passing it through pipes beated by hot combustion gases. When the tray reactor isotherwise operated adiabatically it is sullcient for butane conversions of 30 mol %, in partie Jar when using the catalysts doseribod in DE-A 199 37 107, especialy those of the exemplary embodiments, to conduct the reaction gas mixture into the dehydrogenation reactor preheated io a temperature of from 450 to 550°C. and keep i within thie temperature range inside the tray reactor. For igher butane conversions, the reaction gas mixture is appro prilely conducted into the dehydrogenation reactor pre Deated to higher temperatures (dhese may be up to 700" C.) and kept within this elevated temperature range inside the tray reactor. Tt is even more elegant to cary out the above-outlined intermediate heatinginadirect way (atothermal method). To this end, limited amount of molecularoxygenis added tothe reaction gas mixture either before it flows through the frst catalyst bed (in that case the starting reaction gas mixture should comprise add! molecular hydrogen) andor between the downstream catalyst beds. Its thus possible (generally catalyzed by the dehydrogenation catalysts themselves) t0 bring about a Fimited combustion of molecular hydrogen whieh is present in the reaction gas mixture, has been formed inthecourseoftheheterogencously catalyzed n-butane dey- sdrogenation andlor has heen added tothe reaction gas mix- ture. Itmay be appropriate provide catalyst beds in the tray reactor which are charged with a catalyst which selectively catalyzes the combustion of hydrogen, Fxamples of usefil catalysts include those ofthe documents U.S. Pat. No. 4,788, 371, US. Pat. No. 4.886.928, US. Pu. No. $430,209, US. at. No.$,530,171, US. Pat. No. 5,527,979 nd US. Pat.No. 5,563,314; for example, these and the dehydrogenation cat Jyst may be arranged in the tray reactor in alternating catalyst beds In genera, the oxygen feeding as described above is under ‘ake in sue a way thatthe oxygen content ofthe reaction gas mixture, based on the amount of molecular hydrogen con- ‘ained therein, is from 0.5 t0 50% by volume, preferably from 10 to 25% by volume, Useful oxygen sources include both ‘pure molecular oxygen and oxygen diluted with inert pas, for example CO,CO,,N; andor noble gases, but especialy also airand oxygen-enriched st, The resulting combustion gases US 8,088,962 B2 9 renerally have an additional diluting eect and thus promote heterogeneously catalyzed n-butane deliydrogenation. ‘The isothermivty ofthe heterogeneously eatalyzed n-ba- tane dehydrogenation canbe further improved by incorper Jing closed intemal i the spaces between the catalyst beds ia the tay reactor. These intemals comprise suitable solids oF liquids which evaporate or melt above a certain temperature, ‘consuming heats they doo, and, when the temperature falls below this value, condense again and thereby release heat, ‘Another means of heating the gas mixture fed to the first ‘deiydeogenation zone to the reaction temperature required orthe heterogencously catalyzed butane dehydrogenation in the fist dehydrogenation zone isto add molecular hydrogen to it and combust it by means of molecular oxygen over suitable specific combustion catalysts, and bringing about the heating 10 the desired reaction temperature by means of the heat of combustion thus releasod. The resulting combustion products suchas CO, 1,0, and the N; whichisinsome cases present in the molecular oxygen required forthe combustion are advantageous inert diluent gases Tone embadiment of the invention, oxygeneous gsi ed, appropriate, inteinedistely upstream of each ray ofthe tray reactor. na further embodiment ofthe process acconding to the invention, oxygeneovs gs is fed upstream of each 2 ‘except forthe ist ia Ina further embodimentof the process according othe invention, shed o specific oxidation catalyst Suitable for the H, oxidation is present dowasteeam of each ‘oxygen feed point, followed by a bed of dehydrogenation ceaialyst. If requited, external molecular hydrogen (in ure orm or diluted with inert gs) may, if appropriate, adition- ally be fed upstream of each tay. In a less preferred embod ‘ment, the catalyst beds may also comprise mixtures of dehy- “drogenation and I, oxidation catalysts, The dehydrogenation temperature in the tray reactor is zenerally from 400 0 800” C,, the pressure generally rom 0.2 1p 10 bar, prefarably from 0'5 to 4 bar and more preferably from I to Shar. The overall gas hourly space velocity (GHSV) js generally from 500 to 10 000 bin highload operstion ‘even upto 80 000 regularly from 30 0001 0 40000 In principe, useful dehydrogenation catalysts forthe het- ‘erogeneously catalyzed n-butane dehydrogenation ae ll, “dehydrogenation catalystsknown in the priorart. They can be divided roughly into to groups: into those which are of ‘oxide nature (forexample chromium oxide andr aluminum, ‘oxide) and into those which comprise at Teast one noble metal ‘deposited ona generally oxidie support. Ansong. others 38 tis possible to use all dehydrogenation catalysts which are be prepared from the powder form of the active composition ‘ris uncaleined or parially ealeined precursor composition by compacting and shaping (for example by tableting oF extruding) if appropriate with the addition of assistants, for ‘example graphite or stearie acid as lubricats andor shaping assistants and reinforcing agents suchas microfibers of glass, asbestos, silicon earbide or potessium titanate. Examples of stable unsupported catalyst geometries include solid eylin- ers or hollow eylinders having an extemal diameter and a length of trom 2 © 10mm. Inthe ease of the hollow eylinder, ‘Wall thickness of from 1 103 mais appropriate. The uasup ported catalyst ean also have spherical geometry, in which case the spherical diameter ean be from 2to 10 mn, ‘A particularly favorable hollow eylinder geometry has the dimensions $ mv mnvx2 mm (external diameterstengthx {intemal diameter), especially inthe ease of unsupported cata- lyst “The plveralent active composition or is pulverilent pre= ‘cursor composition whichis yet tobe caleinedand/orhas only US 8,088,962 B2 15, been partly caleined may also be shaped by applying to pre- shaped inert catalyst supports. The coating of the support bodies to produce coated eatalyssis generally performed ina suitable otatable vessel, as disclosed, for example, by DF-A 20 09 671, EP-A 293 859 or EP-A 714 700, To coat the ‘support bodies, the posider composition to be applied is appropriately moistened and dried again ater application, for ‘example by means of hot air. The coating thickness of the powsder composition applied tothe support body is appronei- ‘ately selected within the range from 10 to 1000 jm, prefer- ‘bly within th range from 50 to 500 jum and more peelerably within the range from 150 0 250 um, Usefil support materials are the customary porous or non Porous aluminum oxides, silicon dioxide, thorium dioxide, Zirconium dioxide, silicon carbide or silicates such as mag” nesium silicate or alurtinum silicate. They behave substan- ‘ally inely. The support bodies can havea regular or irrezu- Jar shape, although preference is given to regularly shaped support bodies having. distinet surface roughness, for ‘example spheres or hollow eylinder. I is suitable to use substantially nonporous, surface-roughened spherical seatite supports whose diameter is from 1 to 10 mayor from Ito 8 ‘mu, preferably from 410 5 mm, However, itis also suitable use cylinders as support bodies, whose length is from 210 10 sim and whose extemal diameter i from 4 «9 10 mm. Inthe se of rings suitable in accordance withthe invention as support bodies, the wall thickness i also typically fom to 44m. Annular support bodies to be used with preference havea length of from 2o 6 mm, an external diameter of from 4410 8 mum and e wal thickness of from 1 to 2 mm. Support bodies suitable ia accordance with the invention are in par- ticular also rings oF geometry 7 mn mam mm (external ‘diameterslengtxinternal diameter). The fineness of the eat Iytically ctive oxide compositions to be applied to the st face of the suppon body is adapted to the desied coating thickness ef. also EP-A 714 700. ‘Maltimetal oxide ative compositions to be used for the ‘oxydehydrogenation of n-butenes to butadiene are also com- Positions of the general fomula V POM NOL in which the variables are cach defined as follows ‘Y"only bismuth obsmuth and atleast one ofthe elements _eluiu, antimony in and copper, ‘¥--molybdenim or molybdenum and tungsten, Yea alka etl thai aoe sama ‘Yan alkaline earth metal, nicks, cobalt, eoppee, manga- ese, ne, tn cadmium andlor mercury. ‘¥ironorironandat least oneot theelementschromiumand "phosphors anseni, boron andor antimony, 7-3 rte cart metal, lai, zonium, niobium, ant Jum, renium, rhenium, rhodium, siket, gol, lumi ‘num, gallium, indium, silicon, germanium, lea, thorium andor uranium, sifrom 001 08, g'-numbers Which are determined by the valeney and fre- ‘quency of the elements in V other than oxygen and aq-numbers whose pq ratio is from 0.1 1 10, 0 o 16 ising threeimensional regions of the chemical composition YY", which are delimited from thie local ‘environment osving to their different composition, and whose ‘maximum diameter (longest direct line passing through the ‘eater ofthe region snd connecting (points on the surface terface) ofthe region) is from T am to 100 um, frequently rom 10 nm t $00 nm or from I jm w $0 oF 25 jum. Particularly advantageous inventive multimetal oxide ‘compositions V are those ia which Y* is only bismuth Among these, preference is given in tum to those ofthe genera formula VI PLO Lt ofa LP Dp le wo ‘in which the variables are each defined as follows molybdenum or molybslenum and tungsten, Z'-nieke! andor cobalt, Z*-thalium, an alkali metal andlor an alkaline earth metal, phosphorus, arsenic, boron, antimony, tin, cerium andor lead, 2-silicon, aluminum. titanium andr zirconium, Z’-copper, silver andor gol, from 001 0 5, preferably from 0.1 10 3, Pfrom O10 5, "trom 01010, from Oto 1, xty"-numbers which are determined by the vatency and in VL other than oxygen, ratio is from 0.1 10 5, preferably P fom 0.5 2, and very panicular preference is given to those compositions ‘Vin which Z2,—Cangsten), and 2", -(molybdenm), Itisalso advantageous when atleast 25 mol % (preferably at feast 80 mol % and more preferably’ at least 100 mo) of the total proportion of [Y!,7, Og] (Biyw23,.O,,0) ofthe snultimetat oxide composiions Vor of the moltimetal oxide compositions V1 sin the form of threedimensianal regions ofthe chemical composition Y!,.Y",.0,1Bi,-2°,-O,-| which ‘ve delimited from their local environment owing to their Giferen chemical composition, and whose maximum diam eters in the range from 1 nmto 100 um. "The preparation of mulimetal oxide active compositions V is deserbed, for example, in EP-A 575 897 and also in DE-A 19855913, The inet support materials recommended above are also etl, inter alia, as inet materials forthe dilution andior limitation ofthe appropiate fixes catalyst beds fom one nother or as a preliminary bed which protees them andlor heats the gas mixture ‘The oxydelydrogenation s generally carried outa a em peratre of from 230 to 490° C. and preferably from 250 t0 450°C. A reatorinlet pressure is selected which sufficient to overcome the flow resistances inthe plant an! the subse- quent workup. This reactor inlet pressure is penerally fe 0.005 10 1 MPa gauge, preferably from 0.01 t0 05 MPs gauge. By it nature, the gas pressure applied in the ialet region of the reactor falls off substantially over the entire catalyst bed. “The oxydehydrogenation of n-buteneso butadiene may be carried out withthe catalysts described, for example, in a fne-7one multiple catalyst tuhe fixed bed rector as described BA 4431 957, US 8,088,962 B2 17 The oxidizing agent used is generally oxygen. When N, is scocted a the inet diet gs. its found to be particularly ‘advantageous to use air or oxygen-enriched at asthe oxygen, Frequently, an n-butenessoxygensinert gases (including steam) volume (I (STP)) ratio of 1:(1.0 10 3.0)(5 to 25), preferably 1:(.7 2.3}: (10 to 15) is employed. The reaction pressures typically inthe range from 1 o 3 bar ad the total hourly space velocity’ preferably fom 1500 4000.0r 600 (STP) or more. The loading based on n-buteaes i typi- ‘ally from 90 to 200 (STP orto 300 (STP or more, “The low ofthecharge gas mixture tothe one-one multiple ‘catalyst tube fixed bed reactor i preferably from above. The heat exchange medium used i appropriately a salt melt, pref- ‘erably consisting of 609% by weight of potassium nitrate (KNO, and 40% by weight of sodium nitete (NaNO.) or of 53% by weight of potassium nitrate (KNO,), 40% by weight (of sodium nitrite (NaNO) and 7% by weight of sodium nitrate (NaNO. ‘Viewed over the reactor, salt mek and reaction gas mixture may be eandhicted either in eoctrrent or in countercurrent. The salt melt itself's preferably conducted in a meandering smanner around the catalyst tubes. ‘When the flow tothe catalyst tubes is from top to bottom, itis appropriate to charge the catalyst tubes from bottom t© {op with catalyst as follows (for low from bottom to top, the ‘change sequence should appropriately be reversed) fist, (a length of from 40 to $0 oF (0 60% ofthe catalyst tube lenth, ether only catalyst ora mixture of eatalyst And inert material, the later, based on the mixture, mak ing up a proportion by weight of upto 20% by weight (section C); {allowing this, to length of from 20 050 oro 40% the {otal tube Length, ether only catalyst or a mixture of catalyst and inert material, the later, based on the mix- ture, making up a proportion by weight of up to 402% by ‘weight (section B) and finaly, to a length of from 10 t0 20% of the total ube length, a bed of inert material (section A) whichis pref cerbly selected seh that it eauses a minimum pressure drop. Section C is preferably undid. The aforementioned charge variant is expecially appropei= ‘ate when he catalysts used are those accoing to example 3, ‘of WO-A 04107408, example 1 of DE-A 100 46 957 oF ‘aeconting to example 3 of DE-A 100 46 957 and the inert ‘material used issteatte rings having the peometry 7 mm»7 ‘mmsed mm (external. diametersheightxinternal diameter). ‘With regard tothe salt bath temperature, the statements made in DE-A 44 31 957 apply. However, the oxydehydrogenation of n-butenes to butadi- ‘ene may also be earied out withthe catalysts described in 3 ‘wo-zone multiple catalyst tube fixed bed reactors deseribed in DE-A 199 10506. In both ofthe above-ceseribed eases, the ‘conversion of s-butenes achieved in single pass is nommally 85 mol %, or 290 mol % ar =95 mol %. “The salt bath emperaturcof multiple catalyst tube reators forthe oxydetydrogenation of n-butenes to butadiene is gen- ‘erally from 300 to 400° C. In addition, the heat exchange medi (preferably salt melts) sre normally conducted through the multiple catalyst tube fixed bed resetors in such amounts that the difference between their inlet and their outlet tem- perature is generally =5°C Tt should also be mentioned thatthe oxydehydrogenation| may be carried out in sueh a way tata resetion gas mixture ‘hich does not comprise any oxygen is initially possed over the catalyst bed. In this ease, the oxygen required for the 0 o 18 ‘oxy'dchydrogensaton is provided in the fom of lattice oxy fn, ln a subsequent regeneration step with an oxygen-con- ‘aining gas (for example ar, oxygen-eiriched ie or oxygen- depleted ar), the catalyst bed is regenerated inorder in tum to ‘rawide an oxygen-free reaction gas mixture Instead of tbe bundle reactors, it s also possible to use plate heat exchanger reactors with salt coofing and/or evapo- ‘itive cooling, as described for example, in DE-A 19.929 487 and DE-A 19 952 964, or fuidized bed reactors. Tnprinciple, the frst and the second dehydrogenation zone inthe process aeconting to the invention may also be config- lured as deseribed in WO-A 04007408, DE-A.19 837 517, DE-A 19 9108 05, DE-A 19 910 S08 and DE-A 19837 519. ‘Typically. the external heating in the two dehydrogenation ‘zones, if appropriate in multizone reactor systems, sadist ina manner known pe seo the specific reaetion gas mixtare composition and catalyst charge. Tn this cate, an excess of molecular oxygen generally has ‘an advantageous effect on the kinetics of the dehydrogena- ‘ion, Since, in contrast 1o the conditions in the Hist debiydro- _genaton zone (nonoxidative dehydrogenation), the oxydehy- ‘drogenation of n-butenes to butadiene is subject to Kinet ‘contro, itis also possible in thesceond debydrogenation one (oxydehydrogenation) to work with a molar excess. of -butenes over molecular oxy'gen. In this ease, the excess tenes also assume the role ofa diluent gas ‘he source used for the molecular oxygen required inthe oxydehydrogenation, which is, for example, admixed 10 product gas mixture b before itis charged to the second ehydrogenation may either be pure molecular oxygen or ‘molecular oxygen diluted with inert gas such as CO,, CO, noble gases, N, andlor saturated hydrocarbons. Appropri ately, the oxygen source used at leat to cover part of the ‘requirement for molecular oxygen will be ait, "Metering of cold air to hot product gas mixture b allows it ‘tobe cooled tothe temperature required forthe oxydeydeo- sgenation Tn the long-term operation of the two dehydrogenation ‘anes, a lowering of the catalyst quality (especially with ogand to activity andl seletivity) ofthe catalysts present in the reaction zones will normally occur. One way of counter acting this is to regenerate the particular catalyst bed from time to time (to this en, itis also possible inthe oxidation ‘one, for example, to conduct residual pas at elevated tem- perature over the catalyst bed oF the oxidation catalyst), as Geseribed, for example, in the documents DE-A 10351265 DE-A 10350812 and DE-A 10350822. Is also possible to increase the eaction temperature over the operating time in ‘onder fo compensate For a rxluced catalyst activity. However, it has surprisingly been found to be sdvantageous in both hydrogenation zones to increase the particular working pressure inthe gas phase, based on an dential hourly space velocity on the particular catalyst bed of reaction gas mixture in (STP), during the operating imeot the catalyst bed, in ‘der fo further counteract the deactivation of the eal beds as deserbed, for example, in the German patent ppl cation DE 102004025448 which wus yet tobe published st the priority date of the present application, For this purpose, itispossible to mountata suitable point a pressure eyulating device (in the simplest ease a throtle deviee, for example a throttle valve or else a vane regulator), for example also partially permeable perforated diaphragms whose holes may successively be partly or fully closed It sin principe su cient o introduce the pressure regulating dave at suitable point i the flow path ofthe reation gas mixture whence the pressure increase can propagate into the reaction zones as a result of backpressure. Typical pressure increases undertaken US 8,088,962 B2 19 (which may be undertaken continuously according to the deactivation, but also discontinuously) in the course of the ‘operating time may be up to 3000 mbar and more, ‘The coupling of the nonoxidative catalytic, preferably ‘autthermal, dchydeogenation wth the oxidative debydroge- ration of the a-itenes formed results in. very much bigher ‘yield of butadiene, basedon n-butane used, being obtained. In ition, the nonoxidative dehydrogenation may be operated ‘more gently. Comparable butadiene yields would be achiev- able with an exclusively nonoxidative dehydrogenation only ‘at the cost of distncly lower seletvities, In the ease of ‘exclusively oxidative dehydrogenation, only low butane ‘conversions are achieved. In addition to butadiene and unconverted n-butane, the product gas steam ¢ leaving the oxiative dehydrogenation ‘also comprises 2-butene and steam, As secondary consti ‘ents it generally comprises carbon monoxide, carbon diox= ide, oxygen, nitrogen, methane, ethane, ethene, propane and propene, with or without hydrogen nd oxygenous hydrocar- bons, kaown as oxy'genates, Ia general, it eomprises only small proportions of I-bitene. Oxygenous hydrocarbons (oxygenate) are, for example lower aldehydes, lower alkanccarboxylic acids (eg. acetic ‘acid, formic acid and propionic acd) and maleic anhydride, benzaldehyde, aromatic carboxylic acids and aromatic ear > boxylic anhydrides (eg. phthalic anhydride and benzoic id). In general, the product gas steam ¢ lewving the oxidative dehydrogenation comprises from 1 to 50% by volume of butadiene, from20%0 80% by volume of n-butane, from0.50 40% by volume of 2-butene, from 0 to 20% by volume of |-butene, from 0 w 70% by Volume of steam, fom 0 0 10% by volume of low-boiling hydmcarbons (methane, ethane, ‘ethene, propane and propene), from 0.1 (© 40% by volume of hydrogen. from 0 to.70% by volume of nitrogen, from 0 10 10% by volume of carbon oxides and from 0 tw 10% by volume of oxygenates. Oxygenates may, for example, be furan, acetic acid, maleie anhydride, Formie acid or butyral- dehyde Tone process par, D, the ls-boiling secondary consttu- ‘ents other than the C,, hydrocarbons (n-butane, isobutane, I-butene, eisvtrans-2-butene, isobutene, butadiene) are removed at least pally, but preferably substantially ally, from the product gas steam othe n-butane dehydrogenation tw obtsin a C, product gas stream d none embodiment ofthe process according 1 the inven- tion i process part D, water i iniially removed fom prod- ‘et gas stream e, Water may be removed, for example, by ‘condensing out, by cooling andior compressing prolct gas stream. and may becarried out inoneor more cooling andior ‘compression stages. The low-boiling secondary constituents may be removed from the product gas stream by customary separation pro- ‘cesses suchas dstilation, rectification, membrane processes, absomption or adsorption. "To remove the hydrogen present in prodt gas stream c, the product gas mixture, afer thas been cooled ifappropri= ate, for example in an indirect heat exchanger, may be passed through a membrane, enerally configured as. tube, which s permeable only to molecular hydrogen. The thus removed ‘molecular hydrogen may, if required, be used atleast partly in the dehydrogenation of sent to another wllization, for ‘example to the generation of electrical energy in fuel cells “The carbon dioxide present in prot gas stream e may be removed by CO, gas sonibbing. The carbon dioxide gas scrubbing may precede a special combustion stage in which ‘carbon monoxide is oxidized selectively to carbon dioxide o 20 na preferred embodiment ofthe process coring tothe invention the gas stream cis compressed in at lest one first ‘compression stage and subsequently cooled to condense out at least one condensate stisam comprising water and leave a gas stream e' comprising n-butane, n-butenes, butadien bydogen and steam, with or without carbon oxides and with ‘or without inert gases, The compression may be elfected in one or more stages ‘Overall, compression is effected from a pressure inthe range rom I.Ot040bar toa pressurein the range fo 3.50 20a Foch compression stge is followed by a cvoling stage in \whieh the gs stream is eooled to temperature i the range {rom 15 to 60° C. The aqueous condensate steam may thus ‘comprise several streams in the ease of multistage compres: The gas stream c? generally consists substantially of C, hnydrocarbons (essentially n-butane, 2-butene and butadiene), hhydrogen, carbon dioxide and steam. In addition, stream ¢ may also comprise low boilers, iner gases (aitrogen) and carbon oxides as une secondary components. Theaqueous ‘condensate seam consists generally to an extent of at least ‘50% by weight, preferably to an extent of at least 90% by ‘weight, of water, and additionally comprises, to a small extent, low boilers, C, hydrocarbons, oxygenate and earbon dioxide ‘Suitable compressors are, for example, turbocompressors and piston compressors inciting rotary piston compressors. ‘The compressors may’be driven, for example, by an electic ‘motor, at expander or gas or steam turbine. Typical com- pression ratios (outlet pressurinet pressure) per compres- sion stage are depending on the design, between 1S and 30, The compresses gsi cooled with heat exchangers which say be designed, fr example, as tube bundle, spiral or plate beat exchangers. The coolants used in the heat exchangers are cooling water or heat carrer ols. In addition, preference is sven fo using air cooTing withthe use of fans Tina preferred embodiment of the process according tothe ‘invention, the uncondensable oe ls -boling gas constituents sch as hydrogen, oxygen, carbon oxides, the low-boiling hydrocarbons (methane, ethane, ehene, propane, propene) and any nittogen are removed by means of a high-boiling sorbent in an absorpion/desorption eyele to obtain a C, product gas strcam d which consists substantially of the C, hydrocarbons. In general, the C, product gas steam d eon sss fo-an extent of at least 80% by volume, preferably to aa extent of at least 90Poby volume, more preferably toan extent ‘of at least 95% by volume, of the C,hyedroearhons. Stream d ‘consist substantially of n-butane, 2-butene and butadiene. "To this end, in an absonplon stage, product gas stam c after preceding water removal, is contacted with an inert absorbent andthe C, hydrocarbons are absorbed in the inet absorbent to obtain absorbent laden with C, hydrocarbons ‘and an ofa comprising the remaining gs constituents, laa desorption stage, the C, hydrocarbons are released agin trom the absorbent. Tne absorbents used in the absorption stage are generally high-boiling nonpolar solvents in whieh the C, hydrocarbon mixture tobe removed has a distnetly higher solubility than the remaining. gas constituents. The absorption maybe effected by simply passing the proxust gas stream e trough theabsorbent, However, itmay also be ellected in columns or in rotary absorbers. [tis possible to workin cocurrent,coun- {ercurrent or crosseurrent, Fxamples of suitable absorption columns inchide tray columns having bubble-cap, centrifugal andlor sieve trays, columas having sinetured packings, for cxample sheet meal packings having a specific surface area ‘of From 100 to 1000 nif such as Mellapak®® 250 Y, and US 8,088,962 B2 2 randomly packed columns. However, usefil absorption col- ‘umns aso inelude wiekle and spray towers, graphite block “absorbers, surface absorbers ses a ticki and thin-film absorbers and also rotary columns, plate serubbers, cross- spray’ serubbers and rotary scrubbers, ‘Snitable absorhents are comparatively nonpolar organic solvents, for example aliphatic C> t0 C, galkenes, or aro- matic hydrocarbons suc a the middle oll fractions from paraffin distillation naphtha orethershaving bulky groups, or mixtures of these solvents, to each of which a polar solvent such as dimethyl 1,2-phthalate may be added. Further suit- able absorhents include esters of henzoie acid and phthalic cid with straight-chain C,-C -alkanols, such as n-butyl ben- ‘uate, methyl benzoate, ethyl benzoate, dimethy] phthalate BOTENE fine e Sinn hos SoaUTEN ine Sino om WATER fuinea———e ‘use ‘eo hm L2BUTADIENE ‘mea ‘hao Simo Poa CARBON DIOXIDE ‘ine ‘io Simon om ypxoory fume ‘unm hom S ‘ine ate Tenperve [©] 1 00 29 Pree bar 30 ms th ‘What is claimed is 1. process for preparing butadiene from n-butane, com- rising ‘A) providing a fod gas stream (a) comprising n-butane: 1B) feeding said feed gns stream (a) into at least one first dehydrogenation zone and nonoxidatively catalytically dlhydrogenating n-butane t© obtain a product gas stream (b) comprising. n-butane, I-butene, 2-butene, butadiene, hydrogen, and Jow-boiling secondary con- stituents, and optionally comprising carbon oxides and © feeding said product gas steam (b) and an oxyzenous ‘2 into at least one second dehydrogenation zone and ‘oxidatively debydrogensting n-butane, I-botene and 2-butene to obtain a product was steam (e} comprising ‘butane, 2-butene, butadiene, low-boiling secondary ‘constituents, carbon oxides, and steam stream () having a higher content of butadiene than product gas seam (0); 'D) removing sai low-boiling scondary constituents and steam from said product gas stream (e) to obtain a C, product gs ane, 2-bitene and butadiene ) separating by extractive distillation sad C, product gas ‘ream (4) ito a stream (el) substantially comprising butane and 2-butene and a product-of-value stream (€2) substantially comprising butadiene; said product gas 4 rca (@) substantially comprising mbac 4S F) recycling suid stream (e1) imo said fist deliydrogena- wherein a lest a portion of the oxygen remaining in suid ‘rodict gas streams (¢) andor (@) after C) or D) is removed hy reating it catalytically with hydrogen. 2. The process according to claim I, wherei std oxidative dehydrogenation of C) is caried out autothermally while {eding in std oxygenous gas '3. The process according o claim 2, wherein said oxygens ous gas is it 4 The process acconling to claim 1, wherein suid feed stream (a) obtained from liquefied petroleum gas. 5. The process aeconding (0 clsim 1, wherein in D) said ston is moved by cooling and/or docompressing product sa stream (6) in one or more cooling andor evaporation Sages to oblain a low-sater product gas stream (), 6. The process aeconding (0 claim §, wherein in D) said low-water product gas steam (¢) is contacted with an inet absorbent (0 obain an inert absorbent len with C, hydro- ‘carbons und anoffgas comprising the remaining gus consti ents of said low-water prodet gas steam (@), wherein said Cy hydrocarbons are released from suid inert absorbent in a subsequent desorption stage. 7. The process according to claim 1, wherein sid extrac- ‘ive distillation in B)iseaeied out using an N-methylpyrr donelwater mixtire as an extractant,