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    9 views22 pages

    US10179323B2

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    Akbar

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    © All Rights Reserved
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    USO1017 2, United States Patent Chinta et al. (54) METAL OXIDE CATALYST SYSTEMS FOR CONVERSION OF ETHANOL TO BUTADIENE (71) Applicant: FINA TECHNOLOGY, INC, Houston, TX (US) (72) Inventors: Siwadinarayana Chinta, Sugar Land, TX (US); Kaushik Gandhi, League City, TX US) (73) Assignee: FINA TECHNOLOGY, INC, Houston, TX (US) (4) Notice: Subjoct to any disclaimer, the term of this patent is extended or adjusted under 35 USC. 1846) by 0 days. 1) Appl. Now 19/175,727 (22) Filed: Jun, 7, 2016 Prior Publication Data US 201710349503 Al Dee. 7,2017 GI) Ime, cure 124 (2006.01) cure 120 (2006.01), BoLd 2306 (2005.01) BOLI 2436 (2006.01), BOL 2320 (2006.01) cure 45700 (2006.01), core 1207 (2006.01) BOL 2380 (2006.01) Bots 2916 (2005.01) Bod 38/10 (2006.01) Bors 23/92 (2005.01) BOLI 37/00 (2006.01), (2) USC. crc BOLT 23/06 (2013.01); BOLT 2320 (2013 01); Bory 2326 2013.01): BoLs 2380 (2013.01), BOLT 29/163 (2013.01), CO7C 1720 (2013.01): C07 12076 (2013.01), C07C 454002 (201301); BOJ 23/92 (2013.01); BOL 17932382 US 10,179,323 B2 Jan, 15, 2019 (10) Patent No.: (4s) Date of Patent: 37/0018 (2013.01); BOLY 38/10 (2013.01); BOLI 2329/86 (3013.01): BOL 2229/42 (2013.01); BOL 2523/00 (2013.01): Co7C 2521/06 2013.01): CO7C 2521/08 (2013.01) COPE 2521/10 (QO13.01}; CUTE 2523/06 (2013.01); CU7C 2523/20 2013.01}, CO7C 2523/36 (2013.01); CO7C 2523/72 (2013.01) COPE 2523/80 (201301): COTE 2529/16 (01301) (58) Fleld of Classification 8 cr COT 1/24; COTE 1/20 usec 585/608, 606, 609 ‘See application file for compete search history 66) References Cited u S. PATENT DOCUMENTS DABABL A * SIDA Spence Bo1s 208 (OTHER PUBLICATIONS “tnvstgnions ito the conversion of ethanol imo 1.3-btaione” Sones eal 2011, pp. 267-272. * cited by examiner Primary Esaminer — Thuan D Dang (14) Attorney, Agent, or Firm — Albert Stung, 6 A process includes reacting a feed stream containing ethanol ‘and optionally acetaldehyde in a dehydration reactor in the presence of @ dehydration catalyst system having a Group 4 ‘or Group 5 metal oxide ad a support The process includes ‘obtaining a prodict steam containing butadiene from the ‘hydration reactor, Another process includes reacting. a feed stream containing ethanol and optionally acetaldehyde in a dehydration reactor in the presence of a dehytration catalyst system containing a tungsten oxide supported of a zeolite of a tantalum oxide supported on a zeolite. The process inchides oblaining a product stream contsining ‘butadiene from the dehydration reactor, ABSTRACT 16 Claims, 8 Drawing Sheets Woe Pe kk. oJ | Ry = . 7 [f= U.S. Patent Jan. 15, 2019 Sheet 1 of 8 US 10,179,323 B2 FIG. 1A U.S. Patent Jan. 15,2019 Sheet 2 of 8 US 10,179,323 B2 FIG. 1B US 10,179,323 B2 Sheet 3 of 8 Jan. 15, 2019 U.S. Patent jouoaye Yaaro voneipmuan HO NA me euaypeang-e SA, oHOTHO Aan ‘ Hoe ssoneapayon een ephyeppeucIee sao 0 ronereay ww wy _— Re a yournghxospay-e voqusboipivep ep hyopmreay ee U.S. Patent FIG. 3 Jan. 15,2019 Sheet 4 of 8 How Py /OV US 10,179,323 B2 350. 400) | 450: 60027550) = (6001 (650) =| 7001) 750) TIK 300 U.S. Patent Jan. 15,2019 Sheet 5 of 8 US 10,179,323 B2 FIG. 4 U.S. Patent Jan. 15, 2019 Sheet 6 of 8 US 10,179,323 B2 1%/1%/1% 21/tn/Cu ABUTADIENE SELECTMITY mol% ISETHANOL CONVERSION mol% | RE 3%/0.5% Zr/tn E oe : | get By | | | | | PPL. | 7 | ss 8 8R 8B 8 2 (ow) AUALOSTaS 3N3IQVLNG “(xiow) NOISYIANOD TONVHI US 10,179,323 B2 Sheet 8 of 8 Jan. 15, 2019 U.S. Patent uu SO = ASHT so= ! Z ‘Old (aa Hsaui/TI0A034) OU XMABY on Isa Wu ger'0 = ASHT o= Bees8 888 ‘IW NOISU3ANOD TONVHGS BiOW AUALOTISS INSIOVING a AUNLOTTES NO OLlWY XM1I3Y 40 JONININI %IOW AUALOTTAS 3NSIQVING ‘%IOW NOISA3ANOD TONVHII US 10,179,323 B2 1 METAL OXIDE CATALYST SYSTEMS FOR CONVERSION OF ETHANOL TO BUTADIENE CROSS-REFERENCE TO RELATED [APPLICATIONS Not applicable FIELD Embodiments of the present disclosure generally relate to ‘conversion of ethanol to butadiene. More particularly. ‘embodiments of the present disclosure relate tothe use of supported metal oxide catalyst systems for conversion of ‘ethanol to butadiene. BACKGROUND butadiene i manufactured primarily as ‘8 co-product of sieam erucking to produce ethylene in the United States, Westem Europe, and Japan, In certain parts of the world where biomass lor fermentation is plentiful, 1 3-butadiene is produced from ethanol. Butadiene has also.» been produced by the dehydrogenation of n-butane and coxydelydrogenation of n Bioethanol is a renewable alters asoline. For the purposes ofthis disclosure, bioethanol is defined ae ethanol manufactured from plant materials. Vari ‘ous feedstocks may be used in the production of bioethanol, inchiding sugars, starches and cellulosic biomass (eg. straw, wood, ete). Bioethanol may be converted to butadi SUMMARY, The present disclosure provides fora process that includes reacting a feed stream conisining ethanol in a dehydration reactor in the presence of a dehsration estalyst system ‘containing « Group 4 or Group 5 metal oxide and a support “The process includes obiining a prodet stream contsiing butadiene from the dehydration reactor, The disclosure provides for another process that includes reacting a feed stream containing ethanol and optionally ‘acetaldelyde in a dehydration reactor in the presence of a ‘dehydration catalyst system containing a tungsten oxide supported on a zeolite or a tantalum oxide supported oa @ zeolite. The process includes obtaining @ product stream ‘containing butadiene from the dehydration reetor BRIEF DESCRIPTION OF DRAWINGS ‘The present disclosure may be wnderstood from the fol= lowing detailed desripton when read with the accompsiny- ing figures, TIG. LA depicts a reaction fw diagram in aecondance ‘with certain embodiments ofthe present disclosure FIG, 1B depicts a reaction flow diagram in accordance with certain embodiments of the present disclosure. FIG. 2 depiets a reaction mechanism for the Formation of butadiene from ethanol in accordance with certain embodi- ments of the present disclosure TFIG. 3 isa line graph depicting free energy change forthe ormation of butadiene from ethanol as calculated by the HISC7 software package in accondance with certain embod mens of the present disclosure 0 2 FIG. 4 depicts the process seheme used in the ex provided hervia, FIG, 5 js a bar graph comparison of ethanol conversion and butadiene selectivity on various SiQ, supported dehy- ration catalyst systems, FIG. 6 isa bar graph depiting the influence of support acidity on butadiene and ethylene selectivity. PIG. 7 isa bar graph depicting the influence of a recycle eflaent and reflux ratio on butadiene selectivity DETAILED DESCRIPTION A dotted description will now be provided. The fallow- ing disclosure includes specific embodiments, versions and ‘examples, but the disclosure isnot limited to these embodi- ‘meals, versions or examples, which are included to enable a person having ordinary skill the art to make and use the isclosure when th information in this application is com- bined with available information and technology. ‘Varions terms a¢ used herein are shown below: To the ‘extent ler used i claim is not defined below, it should be given the broadest definition persons in the pertinent art ‘have given that term as reflected in printed publications and issued patents, Further, unless etherwise specie, all co pounds described herein may be substituted or unsubstituted And the isting of compounds includes derivatives thereof, Punter, variows ranges andor numerical limitations may be expressly stated below. It should be recognized that unless sated othiervise, itis intended that endpoints ae to be interchangeable. Where numerical ranges of limitations fre expressly stated, such express ranges or limitations should be understood to include itorative ranges orl tions of like magnitude falling within the expressly slated ranges or limitations (et from about 1 to about 10 includes, 2,3,4, ete; preater than 0.10 includes 0.11, 0.12, 0.13, ete). Cerisin embodiments of the present disclosure relate 1 3 process for producing butadiene from ethanol. Conversion ‘of ethanol, such as bioethanol, to butadiene may be per Tormed by'a one-step process (ie. the Lebedev process) or a two-stop process (ic. the Ostromislensky process). The {wo-Hep Ostrmislensky process proceeds generally accord- ‘ng tothe following reaction schemes Ia and Ib ily, Oidtogetion C1l,—€11, ONC, CHO seine aupareC cH CCH, © Reaction scheme la exhibits a heat of reaction AH=+16 51 Keal/mole, and reaction scheme Tb exhibits a heat of reaction ALI-47.11 keal’mole. As shown by reaction scheme Ia. below. the dehydrogenation step (Ia) may be carried 0: aulothermally in the presence of air or oxygen (eg. the ‘eba-Chemie process), with the concomitant combustion of the hydrogen fommed supplying the necessary heat of dehy cdrogenation, Reaction scheme Ia, exhibits a heat of raetion AH=-43, Keal/mole (catalytic) ‘The one-step Lebedev process generally proceeds accor ‘ng tthe following reaction scheme Il; 2€1)-CH, OH CH =CH-CH=CH 210 o Reaction scheme I exhibits a heat of reaetion AH=+23.63, kcal/mole. The combination of the two-step Ostromislensky process using the autothermal dehydrogenation mute (19) nay have a lower set heat of reaction than the one-step ii, 01030, +cH,cH0,0 a) US 10,179,323 B2 3 Lebedev process. Without being bound by theory, it is believed that butadiene produced by the one-ep Lebedev process is typically less than 80% pure as compared with & ‘ppieal 98% or better purity of butadiene produced by the two-step Ostromislensky process, The two-step Ostromis- leasky process may exhibit a lower deactivation mic of ‘catalyst. The first step of the tso-step Ostromisleasky’pro= ‘ess (la or In) may exhibit a 30-50% conversion of enol to acetaldehyde at 90-95% selectivity FIG, 1Ajs a low diagram of two-step conversion process 5 for conversion of ethanol to butadiene using the (o-sep (Ostromisleasky process, and FIG. 1B is a low diagram of ‘one-step conversion process 15 for conversion of ethanol 10 butadiene using the one-step Lehedev process ‘With reference to two-step conversion process 5 in FIG. A, ethanol feed stream 10 may be fed t0 dehydrogenatir reactor 14. In certain embodiments, suchas that depicted in FIG. 1A, exygea may be fed to deiydrogenation reactor M4 through oxygen feod stream 12. Oxygen feed steam 12 may include sir Although showa as separate sireams, elhanol 2 food stream 10 and oxygen food stream 12 may be combined prior 1o dehydrogenation reactor 14. Fthanol feed stream 10 ‘may contain ethanol, including, but not limited to, bioctha- nol. Dehydrogenation reactor 14 may contain any dekydro- nation eatalyst system known to one skilled inthe at. Ia certain embodiments, the dehydrogenation catalyst may ‘contain silver. Within dehydrogenation reactor M4, atleast ome ethanol from ethanol feed stream 10 may’ reat in the presence of the dshydrogenation catalyst systom and, in ‘certain embodiments, oxygen, to form acetaldehyde, The temperitre in dehydnogenation reactor may range, in cor twin embodiments, from 260 to 310° C. Products from dehiydmgenstion reactor 14 are discharged through dehy “dnogenstion product stream 16a, Dehydrogenation reaetor product stream 160 may contain acetaldehyde and unreacted ‘ethanol. Reaction of ethanol feed stream 10 in deby/droge= nation reactor 14 may also form fist side procact stream 18 ‘containing water Dehydrogenation reactor 14 may be located upstram of ‘dehydration reactor 22a. In certain embodiments, dehyra- tion reactor 22a may be a fixed bed continuous flow reactor, for example. Dehydrogenation reactor product stream 16. may be fed to dehydration reactor 22a. In some embodi- ments, dehydrogenation bypass steeam 10a, whieh is & portion of ethanol feed stream 10, may be Fe to dehydration Feactor 22a, For example and without limitation, a portion af ‘ream ethanol feed stream 10 may be diverted us dehydra- tion bypass steam 10¢ and combined with dehydrogenation Feactor product steam 16a upstream of dehydration reactor 2a or fed 10 dehydration reactor 22a separately from Ldeiydrmgenation reactor product stream 16a. Within dehydration reactor 22a, ethanol and acetaldehyde rom dehydrogenation reactor product stream 16a may react in the presence of a dehydration catalyst system inckading & ‘Group 4 metal oxide, Group 5 metal oxide, or tungsten oxide and a suppor to fonm dehydration product stream 24a. Dehydration product steam 24a may contsin | 3-butadiene Dehydration product steam 24a may be obtained from “deiydrtion eetor 2. In some embodiment, dehydration product stream 24a isin the gas phase. In some embodiments, two-step conversion process 5 inchides reeyeling dehydration reeyele stream 30a from \dehydration reactor 22a, Dehydration reeyele steam 30a ‘may contain tnrescted ethanol from dehytration reactor 22a. Dehydration recycle stream 30a may contain ethanol acetaldehyde, butadiene, diethyl ether, other oxygenates, of nations thereof. Two-step conversion process S may 0 o 4 include feeding dehydration reeyele stream 300 into dehy ration reactor 224, For extmple and without imitation, Gehydration recyele steam 30a may be combined with «dehydrogenation bypass stream 1a, dehydrogenation reac- for product stream 16a, or both. In some embodiments, Sehydration roeycle stream 4a may be fed to dehydration reactor 22a separately from dehydrogenation bypass stream 10a and dehydrogenation reactor product stream 164. In some embodiments, a reilx ratio ranges from 0.5 10 1.0. Reflux ratio” as sed herein refers to the ratio the amownt ‘of dehydration reeyele stream 304 to the amount of dehy ‘Grogenation reactor product stream 16a and optionally dehy drogenation bypass stream 104 fed to dehydration reactor 22a, as determined by volume, ‘Reacting dehydrogenation reactor product steam 16a in dehydration reactor 22a in the presence ofthe dehytration catalyst system may form second side product steam 264 ‘containing H, and third side prodct steam 28a containing ‘water: In some embodiments, hid side product stream 28 is in the liquid phase, While ond side product steam 26a fand dehydration product stream 2a are shown as exiting

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