2) United States Patent Koma 6a om a Osaka (P) Applicant: (72) Inventor: Satoshi Koma, Tokyo (JP) ow ISUL C Osaka GP) Assignee: MICAL CO.,LTD. Notice: Subject to any disclaimer, the tem ofthis pateat is extended or adjusted under 35 USC. 184(b) by 0 days. ay Appl. Now 15527,033 (22) PCT Filed: Jan, 13, 2016 (86) PCT No, § 371 (XI), @) Date: PCTNP2016S0844 May 16, 2017 (87) PCT Pub, Nos WO2016/114306 PCT Pub, Date: 21, 2016 co) Prior Publication Data US 201710327435 Al Nov. 16, 2017 G0) Foreign Application Priority Data Jan. 13, 2015 GP) 2015-00460 Gly Int. core 120 BOL 2320 (2006.01) (2006.01) (Continued) €07C 1/20 (2013.01); BOLI 29720 (2013.01): BOLy 29446 (2013.01); BOLT 23/464 (201301) (Continued) USO10189754B2 US 10,189,754 B2 Jan. 29, 2019 (10) Patent No.: (4s) Date of Patent: (58) Fleld of Classification Search CPC , BOLI 25/20, BOL! 23/464; BOLI 21/08; BOL) 28/58; BOLJ 23/6562; BOLI 24/80: Continved) 66) References Cited US. PATENT DOCUMENTS. 20140058146 AL 22014 Bricker ta FOREIGN PATENT DOCUMENTS rast 2006 (Continsed) (OTHER PUBLICATIONS International Search Report dats Mat 1, 2016 in lntermtionsl (PCT) Application No, PCTAP2O1G DSO8A4, (Continved) Primary Esaminer — Sharon Pregler (74) Autores, Agent, or Firm — Weaderot, Lind & Ponack, LLP. ABSTRACT A butadiene production system and a butadiene production ‘method aze frovided in Which butadiene can be prodiced with a high yield. The butadiene production system (1) includes: a gas preparation device (10) that heats raw materials to prepare 8 mixed gas incliding hydrogen and fearon monoxide an ethanol production device (12) that is provided downstream of the gs preparation device (10) and brings the mixed yas including hydrogen and earbon mon. oid into contact with a first calalyst to obtain ethanol; butadiene produetion device (16) that is provided down. seam of the etbanol production device (12) and brings the ethanol into contact with a second eatalyst to obtain bua diene; and return means (18) for returning hydrogen, whieh is produced as a by-product in the butadiene production vice (16), to the ethanol produetion device (12). In add (Continved)US 10,189,754 B2 Page 2 tion, in the butadiene production method, the butadiene production system (1) is used. 10 Claims, 2 Drawing Sheets (1) nec. BOLT 23/46 (2006.01) cor 3738 (2008.01), co7R 610 (2006.01) core 1167 (2006.01) C10K 370 (2006.01), corp 4734 (2008.01) core 29151 (2006.01) 10s 3982 (2006.01) 10K 306 (2006.01) (2) Us.cL crc COIR 4/34 (2013.01); COIB 338 (2013.01): CO7B 6i/m0 2013.01): C7 167 (201301): CO7C 29/1518 (2013.01), (C105 882 (2013.01); C1OK 3700 (2013.01; ‘C1OK 3/06 (2013.01); COIR 2203/0216 (2013.01); Co1B 2203/06 2013.01}; Clad 23000946 (2013.01), YO2P 20/52 (2015.11) (58) Fleld of Classification Search ce ‘BOL! 23/8926; BOLI 23/8093: BOI) 37102075, COI 2203/0216; COLB 220806; CO1B 34: COIC 1/20; COTC 29/1518: COIC 3108; C1OG 11/18; C1OG 2300/1011; C106 23007708; C10G 9136 ‘See application file for complete sear history. 66) References Cited PORPIGN PATENT DOCUMENTS w mons? gia ® aoootat = 12013 3 doers 112012 @ dous-21099 ‘62013, » Jobo 102013, Wo oomtr7s90 to 2007 wo oo2s19 "82010 wo oss 42012 wo ‘osesok $201 Wo 201208719 2012 WO 20130KI77 «6013 Wo downs £2013 WO du1aoIss 414 (OTHER PUBLICATIONS "Exendod European Search Report dated Jun. 1, 2018 in European Patent Application No, 167573778U.S. Patent Jan, 29, 2019 Sheet 1 of 2 US 10,189,754 B2 FIG. 1 2 2 10-—- a 20—-U.S. Patent Jan. 29, 2019 Sheet 2 of 2 US 10,189,754 B2 FIG. 2 3 32 i i 42 im | BH \ -~ 45 1 [ 14a = 22A— L rl ~2ha 10A—~- | 16 a | | 26 20a, | ) 47 LJ | 44 46] | a | 30 EdUS 10,189,754 B2 1 BUTADIENE PRODUCTION SYSTEM AND. BUTADIENE PRODUCTION METHOD ‘TECHNICAL FIELD ‘The present invention relates to @ butadiene production system and a butadiene production method. Priority is claimed on Japanese Patent Application No. 2015-4460, filed on Jan. 13, 2015, the content of which is Jncomporated herein by reference BACKGROUND ART Btadiene such af 1.3-butadiene is wed asa raw material ‘of styrene-butadiene rubber (SBR) or the like. In general butadiene is purified from a C4 fraction which is produced as a by-product when ethylene is synthesized from petro- eum, However, recently, bioethanol synthesized from a. bio mastderived raw material has attracted attention as an temative raw material to petroleum. For example, PTL 1 discloses. method of proxivcing butadiene from ethanol using a catalyst. However, in the method of obtaining butadiene from ‘ethanol using the catalyst as in PTL 1, the yield is aot industrially sullciently high. CITATION LIST tent Literature [PTL 1} PCT Intemational Publication No. WO2013/ 125389 SUMMARY OF INVENTION Technical Problem An object of the present invention isto provide a buta- «diene production system and a butadiene production method in whieh butadiene ean be produced with a high yiek Solution to Problem A butadiene production system (apparatus) acconling 10 ‘an embodiment of the present invention includes: a. gas preparation device that heats raw materials 0 prepare @ mixed gas including hydrogen and carbon monoxide; an ‘ethanol production device that is provided downstream of the gas preparation device and brings the mixed gas inchud- ing hydrogen and carhon monoxide into contact with first ‘catalyst to obtain ethanol: butadiene produetion device that provided downstream of the ethanol production device tnd brings the ethanol into contact with a second eatalyst 0 ‘obtain butodiene; and return means for returning hydrogen, shih is produced as a by-product in the butadiene prodac- tion device, to the ethanol production devie. ‘A butadiene production system (apparatus) acconding to ‘another embodiment of the preset invention includes: 2 gas preparation device that heats raw materials to. prepare @ mixed was including hydrogen and carbon dioxide; an etha- nol production device that is provided downstream of the gs preparation device and brings the mixed gas ineluding hydrogen and carbon dioxide into contact with a third ‘catalyst to obtain ethanol; butadiene produetion device that js provided downstream of the ethanol production device ‘and brings the ethanol into eontact witha Second catalyst to 0 o 2 ‘oblain butadiene; and return means for returning hydrogen, \whiel is produced as a by-product in the butadiene produe- tion device, to the ethanol production deviee. It is preferable that the retum means include a pipe ‘rough which the butadiene production device and the thao! production device are connected. ‘A butadiene production method according to an embodi- ‘meat of the present invention includes: 2 gas preparation step of heating raw materials fo prepare a mixed as inci ing hydrogen and carbon monoxide; an ethanol production step of bringing the mixed gas into contaet with a first catalyst 10 obtain ethanol: a butadiene production step of bringing the ethanol into contact with a second catalyst t0 oblain butadiene: and a retum step of returning hydrogen ‘which is prodiced as by-product inthe butadiene produc- sion step, 1 the ethanol prodvetion step. ‘A butadiene production method! according t another ‘embodiment of the peseat invention includes: a gas prepa- ration sep of heating raw materials to prepare a mixed gas including hydrogen and carbon dioxide; an ethanol produe- tion step of bringing the mixed gas into contact witha third catalyst to obtain ethanol: a butadiene production step of bringing the elhinol into contact with a second catalyst to jobiain butadiene; and a rotum step of returning hydrogen, ‘which is produced as by-product in the butadiene prodnc- sion step, 1 the ethanol produetion stp. Advantageous Etfeets of Invention In the butadiene production system according © the present invention, butadiene can be produced with a high yield In the butadiene production method according 0 the present invention, butadiene can be produced with a high yield BRIBE DESCRIPTION OF DRAWINGS FIG. 1 is a schematic diagram showing an example of a ‘butadiene production system aeconding tothe present inven- TFIG. 2 isa schematic diagram shoving another example ‘of the butadiene prodnetion system aeconling to The present DESCRIPTION OF EMBODIMENTS ‘The definitions ofthe following terms are applied to this specification and claims The meaning of “returning hydrogen to the ethanol pro- duction devies” includes a configuration of returning hydro gen to a portion, which is provided upstream ofthe ethanol production deviee, where hydrogen retumed due to an ‘equilibrium reaction represented by CO,+11,€ COMO is ‘ot consumed. For example, a configuration is ineludd in ‘whieh, inthe pipe through which the gas preparation device and the ethanol proivction deviee are connected, hydrogen js retumed to portion where the temperate of the mixed ip temperature (for example, 200° C, 0 800° C.) which Js lower than a temperature (for example, 1000° C. to 1200° CC.) at which the equilibrium reaction i shifted to the earbon monoxide side, "The meaning of “returning hydrogen tothe ethanol pro- {duction step” inches a step of returning hydrogen to a step before the ethanol production step where the temperature oF the mixed gas is lower than a temperature at which theUS 10,189,754 B2 3 ‘equilibrium reaction is sifted to the carbon monoxide side or example, a step where the temperature ofthe mixed gas js 200° C. 0 800" C) “Raw materials” are organie materials fom which the mixed gas including hydrogen and carbon monoxide is ‘obtained by heating, and include both of solid raw materials suel as biomass or organie waste and raw material gases such a natural gas or waste gs. “The ratio H1,(CO between hydrogen and carbon monox= fide supplied to the ethanol prod refers toa ratio between hydrogen and carbon monoxide ina state where the mixed gas supplied from the gas preparation step to the ‘ethanol production step is brought into contact with hydo- fen retumed to the eltanol production step by the rekira step. The same shall be applied to “the rato FCO, between hydrogen and carbon monoxide supplied to the ethanol production step” “CO conversion ratio” refers to a percentage of the umber of moles of earbon monoxide consumed by 2 reaction tothe number of moles of earfon monoxide in the mixed as, “Selection ratio” refers tw percentage ofthe number of moles of carbon monoxide converted iato a specie eom- pound to the number of moles of carbon monoxide cone fumed in the mixed gas, First Embodiment (Butadiene Production System) ‘Ina butadiene production system according to the present ‘invention, rave materials are heated to prepare a mixed gas including’ hydrogen and carbon monoxide, ethanol is ‘obtained from the mixed gas, and butadiene is produced from the ethanol, Hereinafter, an example of the butadiene production system according tothe present invention will be Aeseribed, ‘As shown in PIG. 1, a butadiene production system 1 ‘acconting t0 the embodiment inehudes: a ans preparation device I; an ethanol production device 12 that's provided ‘downstream of the gas preparation deviee 10; a purfiation device 14 that is provided downstream of the ethanol produetion device 12: a butadiene production device 16 that 's provided downstream of the purification device 14; and return means 18 for rturning hydrogen from the butadiene production device 16 to the ehanol production device 12 ‘The gas preparation device 10 inehudes a gasification fir: race 20 and a reforming fmace 22 that is provided down- stream of the gasification furnace 20, The butadiene pro- duction device 16 includes a reaction pipe 24 and a pase liquid separator 26 that is provided downstream of the reaction pipe 24 ‘The gasification furnace 20 and the reforming furnace 22, ‘are connected to each other through a pipe 41, The reforming fumace 22 and the ethanol production device 12 are con- rected t0 each other through a pipe 42. The ethanol produc. tion device 12 and the purification deviee 14 are connected to eveh other through a pipe 43. An exhaust pipe 4 is ‘connected t0 the purification device 14. The purification ‘device 14 and the reaction pipe 24 ofthe butadiene produ: tion device 16 are connected to each other through a pipe 4. ‘The reaction pipe 24 and the gas-liquid separator 26 are ‘connected to each other through a pipe 46. A pipe 47 is ‘connected to the gas-liquid separator 26 TInthis example, the ethanol production device 12 and the as-iquid separator 26 of the butadiene production device {are connected to each other through pipe inched in the return means 18, 0 o 4 The gas preparation device 10 heats raw materials 10 prepare a mixel gas including hydrogen and carbon non- oxide at an arbitrary ratio, and includes the gasification furnace 20 and the reforming furnace 22 ‘The gasification furnace 20 thermally decomposes solid ‘aw materials such as biomass, organie waste (for example, waste plastic, waste paper, or waste cloth), or coal 10 Produce a mixed gas ineluding hydmgen and carbon mon- ‘oxide. As the gasification furnace 20, for example, a furnace that can produce the mixed gas by ring a portion of biomass fr organic waste in the presence of oxygen s0 as t0 be thermally oxidized can be adopted. AS the gasification {umace, a fluidized bed type gasification furnace is prefer able. The Muidized bed type gasification furnace is prefer able from the viewpoint that tis nt likely to be affected by the forms of the raw materials and the viewpoint that the ‘amount of auxiliary fel used is smal The reforming furnace 22 hydrocarbon in the mixed gas reacts with water 50-98 be reformed into hydrogen and carbon monoxide. In the reforming furnace 22, the concen- {ration of carbon monoxide inthe mixed gas priced from the gasification fumoce 20 is increased such that @ ratio between hyilmgen and carbon monoxide is adjusted to 8 desired value. For example, a ratio H./CO of hydrogen t0 carbon monoxide inthe reforming farce 22 is adjusted t0 120 iL ‘As the reforming furnace 22, for example, a cylindrical member which ean heat the mixed gas ia the presence of ‘water vapor ata temperature higher than a temperature for the thermal decomposition inthe gasification furnace 20 can be adopted. Iv is preferable that the pipe 41 be formed of a material Which is iner’ with the mixed gas and, for example, be Tormed ofa stainless steel pipe In the gas preparation device 10, the solid aw materials ‘are thermally decomposed inthe gasification Furaace 20 10 produce the mixed gas inchiding hydrogen and carbon ‘monoxide, and hyelrocarbon in the mixed gas reacts with water in the reforming furmoce 22 to he reformed into a mixed gas having a higher earbon monoxide eonceatration. ‘Asin the case of the pipe 4, its preferable thatthe pipe 442 be formed ofa material which i inert with the mixed gas and, for example, be formed ofa stainless steel pipe. is preferable that a was purifier be provided inthe pipe 42. By providing the gas purifier in the pipe 42, impurities in the mixed gas such as tar, sulfur, nitrogen, chlorine, or Water ean be removed As the gas purifier, for example, various well-known gas puriflers ofthe related art using a wet method, a dry method. fr the lke can be adopted. Examples of the wet method include a sodium hydroxide method, an ammonia absorption ‘method, a lime-plaster method, and a magnesium hydroxide smethod. Examples ofthe dry method include an absorption ‘method gach as pressure swing absonption (PSA) and an clectron beam meted Inthe pipe 42, cooler for reducing the temperature the mixed gs may be provided. By providing the cooler in the pipe 42, it i easy to suficietly' reduce the temperature of ‘the mixed gas supplied t the ethanol production deviee 12 In addition, by rapidly cooling the mixed gas using the cooler the shift of equilibrium may be prevented, and the ‘concentration of carbon monoxide can be maintained at @ high level “The ethanol production device 12 is fillad with a first catalyst to form a reactor bed 12a tis preferable tht the ethanol production device 12 be ormed of s material which is inet with the mixed gas andUS 10,189,754 B2 5 ‘ethanol. In addition, tis preferable thatthe ethanol produe~ tion device 12 have a shape that can endure heating at about 100° C. to 500° C. or pressing at about 10 MPa. As the ‘ethanol production device 12, for example, a substantially ‘ireular Stainless stool member is used ‘The reactor bed 12a may be any one of a fixed bed, 2 ‘moving bed, fluidized bed, and the like. The mixed gas is supplied to the ethanol production device 12 without any change from the gas state The first catalyst is a eatalyst for synthesizing ethanol from hydrogen and carbon monoxide, As the first catalyst, @ well-known catalyst ean be adopted, and a metal catalyst is preferable, Fxamples of a catalyst metal used in the metal ‘catalyst include a hydrogenation-active metal and an aggre pate of a hydrogenation-aetive metal and an auxiliary active metal described belo. In. case where ethanol is synthesized from a mixed gas ‘of hydrogen and carbon monoxide using the metal catalyst typically, a primary product inchuding acetaldehyde or acetic reactions (1) t0 (8) 2H 20=C#,C0081 oy Le2C0-=€1,C1101,0 o 21CH,COOH-=€,1,0168,0 ° As the hydrogenation-active metal, a well-known metal of the related art in which ethanol ean be synthesized from the mixed gas can he adopted. Examples ofthe bydrogenation- ‘etive metal inelnde alkali metals such as fithium and ‘ol; elements belonging to Group 7 inthe periodic table, such as manganese and rhenium; elements belonging ‘Group 8 in the periodic table, such as ruthenium: elements belonging to Group 9 in the periodic table, such as cobalt ‘and rhodium; and elements belonging to Group 10 in the Perio table, soch as nickel and palladium. ‘Among these, hydrogenation-active metas, one kind may be used alone, and two or more kinds may’ be used in ‘combination. As the hydrogenation-aetive metal, from the viewpoints of further improving the CO conversion ratio and improving the selection rato of ethanol, a combination of rhodium, manganese, and lithium, a combination of rathe- nium, chau, and sodium, ora combination of rhodium or ruthenium, an alkali meta, and another hydeogenation- ‘etive metal is preferable Examples of the auxiliary active metal inchide titanium, ‘magnesium, and vanadium. By not only the hydrogenation- fctive metal but also the auxiliary setive metal being sup- Ported on the metal catalyst, the CO conversion ratio and the selection ratio of ethanol and acetaldehyde ean be further improved. As the metal catalyst, rhodium catalyst having a ome position represented by the Following Foanvla (il) is preferable, eR MacNab ane In Formula (aml), Me' represents an alkali metal, Me? represents an auxiliary active metal, and a, b, c, and d represent molar frations in which asbsced-1 ‘From the viewpoint of easily increasing the CO conver: sion rato, ain Formula (ml) preferably represents 0.083 10 (0.98, more preferably 0.24 to 08, and sill more preferably 03210 087 id is obtained in addition to elbanol due wo the following. > o 6 From the viewpoint of easily inwas sion ratio, bin Formula (ml) preferably represents 0.0006 t0 (0.67, more preferably 0.033 Wo 0.37, and sill mote prefer ably 0.089 to 0.44 From the viewpoint of easily increasing the CO conver. sion ratio, ¢ in Formula (mil) preferably represents 0.00056 to O51, more preferably 0.026 to 0.42, and still more preferably 0075 t0 033, «d may’ be 0 (that i, the auxiliary active meta is not included) and may be more than O (ht is, the wuxiliary ‘active metal is included), Ina case where the auxiliary active ‘metal is included, from the viewpoint of inereasing the CO conversion ratio, d preferably represents 0,0026 to 0.94, mone preferably 0.02 00.48, and still more preferably 0.039 10 025. AS the metal catalyst, a shodium eatalyst may be used combination with another metal catalyst other than. a rho- dium catalyst. Examples of the other metal catalyst include 4 catalyst in which copper alone or copper and another ‘nunsition metal other than copper are supported on w support (herwinater, also referrod to. as “eopper catalyst") It is preferable that the copper catalyst be represented by the following Forasala (en2) scope! =) In Formula (m2), Me? represents a transition metal other tan copper, and ead f represent molar fractions in which orl ‘As Me* in Formula (m2), zine or chromium is preferable. As Me’, one transition metal may be used alone, of two oF ‘ore transition metals may be used in combination, ‘From the viewpoint of increasing the yield of ethanol, & preferably represents 0.5 to 0.9 and more preferably 05 to 07, From the viewpoint of inereasing the yield of ethanol, £ preferably represents 0.1 (0 05 and more preferably 03 4 05, Tn a case where a rhxtium catalyst and a copper catalyst fare used in combination asthe metal catalyst, itis preferable that the rhodium catalyst do not include copper and the copper eatalyst do not inchide shod, AAs the meal catalyst, a so-called supported catalyst in whieh a catalyst metal i supported on a porous support is preferable. In the case of the supported catalyst, @ ratio between ethanol and acetaldehyde ina product can be easily controled ‘A auaterial of the porous support is not particularly Timited, and examples thereof include sliea, zirconia, itr nia, and magnesia. Among thes, slia is preferable because various products thereof having differ specific surface areas and dillerent pore diameters are commercially avi able "The size ofthe porous support is not particulary limited. Por example, in the case of a silica porous support, the particle size thereo? is preferably 0.5 to $000 jum. The particle size of the porots support i adjusted by sieving. Purher, itis preferable tha the particle size distribution of the porous support be as narrow as possible. The sum of pore volumes (total pore volume) in the porous support not particularly limited and is preferably 001 c 1.0 ml/g and more preferably 0.1 008 mL‘. In a case where the total pore volume isthe lower limit value or higher, the specific surfice area of the porous suppor is stiicently large, the suppor amotnt ofthe metal eatalyst is silicent, and thus 2 decrease in the CO conversion ratio is ‘asily prevented. Incase where the total pore volume isthe valle of lower, the diffsion rate ofthe mixed gasUS 10,189,754 B2 1 js not excessively fast, and the contact time between the ‘catalyst and the mixed gas is sullicient. Therefore, decrease inthe selection ratio of ethanol is easily prevented. ‘The total pore volume is a value measured using a water tivation method. Tn the water tiation method, water mol- ‘cules are adsorbed on a surface ofthe porous support, and 1 pore distribution is measured based on agaregation of the molecules The average pore diameter of the porous support is not particularly limited and is preferably 0.1 to 8 nm and more preferably 3 10 6 nm. In 2 ease where the average pore ‘Giameter i# the lower limit value or higher, the support amount ofthe metal catalysts sufficient, and thus decrease jn the CO conversion ratio is easily prevented. In a case ‘where the average pore diameter isthe upper limit value oF lower, the diffusion rate ofthe mixed gas not excessively fast, and the contact time between the catalyst and the mixed as is sullcient. Therefore, a decrease in the selection ratio ‘of ethanol is easily prevented. ‘The average pore diameter isa value measured using the following method. Inacase where the averse pore diameter #8 0.1 sm or more and less than 10 nm, the average pore ameter is calculated fase onthe total pore volume ad 3 [BET specie surface area n'a eae wher he average poe ameter i 10 nm of move, the average pore diameter is ‘measured sing porosimeter according to 4 merry pres in method Here, the total pore volume i a value measured wsing @ ‘water tration method and the BET specie surfs arc x vale calculated based on the adsorbed amount measired by using nitrogen as an adsorption gas and the presi ia the measurement Inthe mercury prestin method, mercury is presse inthe pores ofthe porous support and the average pore diameter 4 calculated based on the presse at this ime and the ‘amount of mercury peessed in. “The specific surlice ara of the porous suppor. is not particularly Timed and is preferably 1 to 1000 mg and ‘nore preferably 10 to 8000, Ina case where the specific surface aren is the lower limit valve oF more the sipport fmovnt of the catalyst metal i sulci, and the CO ‘conversion rato i further inereased. Ina case where the specific surfe ara i the upper iit value or lower, the slifsion rat of the mixed gas is more appropriate, andthe Selection ratio of ethanol i fare increased “The specific surface area is @ BET specific surface area measured sing @ BET gas adsorption meth ia which nitrogen is used a an adsorption a8 “The prod of the total pore volume and the specie surface area in the porous sdppon is preferably 110 1000 tania” and more prefers 100 to S00 ml-mnla. In a ‘ease where the predtt i the lower limit value or more, the Suppor amount ofthe catalyst metal is sien andthe CO ‘conversion ratio i further inreased. In a ease where the produc isthe upper init value or lower, the difusion rate Df he mixed gas Is more appropriate and the selection ratio ‘of ethanol is further increased The state where the hydrogenstion-active metal or the saxiiay ative metal is supported onthe metal catalyst is not paricuary limited and, for example, may be a stte where de met in the form of a powder i supported onthe Porous seppor, or may bea sate where the metal inthe form ‘of @ metal clemeat is supported on the porous, support, Among thes, the state where the metal inthe form of 3 tell element is supported on the porous spp i prefer tbe. In the stite where the mal inthe frm of 9 mctl ‘ements supported on the porous suppor the contact area 0 o 8 between the metal catalyst and the mixed was is inereased, and the CO conversion ratio and the selection ratio of ethanol age further increased ‘The support amount of the eatalyst metal on the porous support is determined in consideration of the kind and composition of the eatalyst meta the material of the porots suppor, and the ike and is preferably 0005 w 30 pars by ‘mags and more preferably 110 10 parts by mass with respect to 100 parts by mass ofthe porous support. Ina case where the support amount is the lower limit value oF more, the support amount of the metal is sufficient, and the CO ‘conversion rato and the seletion rato oF ethanol are easily improved. In a case where the support amount isthe upper Timit value or lower, the amouat of the ailiary ative nical {snot excessively lage, hydrogenation-setive metal is likely {o be uniformly and highly dispersed, and thus the CO conversion rato and the selection rato of ethanol are easily increased. ‘The supported catalyst can be produced using a well- known method of producing @ supported catalyst of the related art. Pxarmples ofthe method include an impregnation ‘method and an ion exchange method. Among these, an ‘impregnation method is preferable. In case where the metal catalyst is produced using an impregnation method, a metal js more uniformly dispersed, and the contact ficiency between the metal catalyst and the mixed gas is further improved. Therefore, the CO conversion ration the selee- ‘ion ratio of ethanol can be further insproved. Inthe embodiment, the pipe 4 includes a pressure contol portion 28, The pressure contol portion 28 isnot partien- larly limited as long a it can adjust the intemal pressure of the ethanol production deviee 12 to an arbitrary valve. For ‘ample, a well-known pressure valve is used The purification device 14 removes materials (for ccxample, acetic acid, ethyl acetate, unreacted mixed gas, a culture medium, oa catalyst) other than ethanol and acet- fldeiyde from the primary product "Examples of the purifieation device 14 inchide a device ‘including a separation membrane, Examples ofthe separ- ‘ion membrane inelude an acidic gas-eontaning gas treat ‘ment separation membrane deseribed in PCT Intemational Publication No. W02014i080570 and. porous support- ~oolite membrane composite described in PCT International Publieation No, WO2013/125661, "The materials removed by the purification device 14 are exhausted through the exhaust pipe 44. Its preferable that the exhaust pipe 44 be formed of a material which is inert ‘with the materials removed by the purification device 14 and, for example, be formed of a stainless steel pipe. 1 is preferable that the pipe 45 be formed of a material whieh is inert with ethanol and acetaldehyde and, for ‘example, be formed of a stainless stl pipe. “The butadiene production device 16 brings ethanol into contact with a second eatalyst to obtain butadiene. The butadiene production device 16 includes: the rection pipe 24 in whieh ethanol is brought into contact with @ second catalyst to obtain butadiene; and the ens-liuid separstor 26 ‘that separates butadiene from a secondary product including butadiene obtained in the eesetion pipe 24, The butadiene production device 16 may further include a well-known Gevice, for example, « gas ow rate control portion that regulates the flo rate stich as mass flow rate of 6. “The reaction pipe 24 i filed with the scone catalyst 10 {form a reaetor bed 24a, It is preferable that the reaction pipe 24 he formed of a material Which s inert with ethanol. ia Addition, itis preferable that the reaction pipe 24 have a shape that can endure heating at about 100°C. 1 S00" C. orUS 10,189,754 B2 9 pressing at shout 10 MPa, As the reaction pipe 24, for ‘exumple, a substantially crvular stainless steel member is used, The reactor bed 24a may be any one of a fixed bed, 2 moving bed, Muidized bed, and the like. “The second eatlyst isnot particulary limited as long as butadiene ean be synthesized from ethanol using it As the second catalyst for example, catalyst including an oxide of ‘2 metal belonging to Group 4 to Group 13 in the periodic table and magnesium oxide, In the second catalyst, itis preferable thatthe metal belonging to Group 4 to Group 13 jin the periodic table he bonded to magnesium oxide through ‘one of more selected from magnesia and silica, Preferable examples of the second catalyst include a ‘catalyst in which tantalum oxide is honded throwgh magne~ sia and silica (Ta,0y/MgO/SiO, (mass ratiom2/89/15) refer 'e PCT International Publication No. WO2013/128388). The second catalyst is produced using a well-known method. Examples of a method of producing the second catalyst ‘include a method ineluding: dispersing a sol of a catalyst metal ina sol of one or more selected from magnesia and silica to obtain a catalyst sol and firing the catalyst sl. Its preferable that the pipe 46 and the pipe 47 be formed ‘of material which is inert with butadiene and, for example, be formed ofa stainless stool pipe Inthe embodiment, the pipe 46 includes a pressure contol portion 30, The pressure conta portion 30 is not paricu- Jory limited as long as it can adjust the internal pressure of the reaction pipe 24 tan arbitrary value. For example, 2 well-known pressure valve is used, "As the gas-liquid separator 26, a well-known gas-liquid separator formed ofa material which is inert with butadiene, hydrogen, and the like can be adopted. In te gas-liquid separator 26, butadiene is separated by Fiquefying butadiene in a state where hydrogen, which is produced as a by-produet, is gaseous, The separated and purified butadiene i collected in a storage tank or the like {oot shown) through the pipe 47 "The retum means 18 is meas for retuming hydrogen, ‘which is produced as a by-product in the butadiene produc tion device 16, o the ethanol production device 12. The return means 18 includes a pipe through which the gos- liguid separator 26 of the butadiene production device 16 ‘and the ethanol production deviee 12 are connected. Tis preferable thatthe pipe of the return means 18 be formed of material whieh is inee with hydrogen and, for ‘example, be formed of a stainless ste! pipe. Optionally, a valve, # pump, a separation membrane, or the like is connected tothe pipe of the retum means 18, ‘A position of the ethanol praxluction device 12 10 which the pipe of the return means 18 is connected is not parieu- larly limited as long as the retumed hydrogen isin range where itis not suliiently consumed inthe reactor bed 12a. or example, the pipe of the retim means 18 may be ‘connected to a portion of the ethanol prodction deviee 12, ‘lose (0 4 gas supply port (close tothe reforming furnace 22), tothe center ofthe ethanol production device 12, or © ‘portion ofthe ethanol production device 12 close 10 a gas ‘exhaust poct (close tothe purification device 14). In the butadiene production system 1, the solid raw materials are thermally decomposed inthe gasification fur race 20 of the gas preparation device 10-to produce the mixed gas including hydrogen and carbon monoxide. The mixed gas is supplied to the reforming furnace 22 through the pipe 41, and hydrocarbon in the mixed gas reacts With 0 o 10 water in the reforming furnace 22 10 be reformed into a mixed gas having a higher carbon monoxide concentration “The reformed mixed gas is supplied from the reforming furnace 22 tothe ethanol production device 12 through the pipe 42 and brought into contaet with the fist catalyst to react with the first catalyst such that a gascous primary ‘product including ethanol and acetaldehyde i obtained. The Primary product is supplied to the purification device 14 throvgh the pipe 43 and is purified. The reformed primary pradct is supplied to the ection pipe 24 of the butadiene fraduction device 16 through the pipe 48. Ethanol in the gaseous primary product supplied to the reaction pipe 24 is brought info contact with the second catalyst react withthe second catalyst such tet gaseous secondary produet including butadiene and hydrogen is ‘oblained. The secondary product is supplied tthe pas-lignid separator 26 through the pipe 46, and the Iiguid butadiene fan the gaseous by-products including hydrogen are sepa- ‘ated from each other. Butadiene is collected through the pipe 47, Hydrogen, which is produced as a by-product, is retumed ‘o the ethanol production deviee 12 by the return means 18. (Butadiene Production Method) Hereinafter, a method of producing the butadiene produe~ sion system 1 will be described as an example ofa butadiene production method according tothe present invention. The butadiene production method according tothe embodiment includes ass preparation step, an ethanol production sep, 1 butadiene production step, and a rotum step described below. Gas preparation step: a step of heating raw materials to prepare a mixed gas including hydrogen and carbon mon- ide Ethanol produetion step: a step of bringing the into contact with a first catalyst to obtain ethanol Butadiene production step: a step of bringing the ethanol into contact with a second catalyst to obtain butadiene Return step step returning hydrogen, which is produced as 8 by-prodict in the butadiene production step to the gas preparation step Gas Preparation Step> The gas preparation step according to the embodiment includes @ gasification operation and a reforming operation in the gasification operation, solid raw materials are ther rally decomposed lo praduce the mixed gas including Ihydogen and carbon monoxide, and inthe reforming oper ‘ion, hydrocarbon inthe mixed gas is reformed ato hydro- agen and earbon monoxide by catsing it to reaet with water ‘In the gasification operation, inthe gasification furnace 20, of the gas preparation device 10, a portion of the crushed solid raw materials such as biomass, organic waste (lor ‘example, waste plastie, waste paper, or waste cloth, o eos is ied in the presence of oxygen. Asa resul, te solid aww ‘materials are thermally decomposed and gasified to produce the mixed gas including hydrogen and carhon monoxide, "A temperature forthe thermal decomposition ofthe solid ‘aw materials inthe gasification operation is not particularly Timited 28 ong as itis. a temperature at whieh the mixed gas including hydrogen and carbon monoxide is produced. The temperature for the thermal decomposition is preferably 200° C. to 1000° C, and more preferably S04” C. to 800" C. TIn-a case where the temperature forthe thermal decompo sition is lower than the Tower limit valu, substantially’ no solid raw materials are gasified, and the object cannot be achieved. Ina case where the temperature forthe thermal ‘Secomposition is higher than the upper limit value, the ‘proportion ofthe solid aw materials to be fired to increase ined yas