CN216106703U - 用于从发酵液中分离乙醇的装置 - Google Patents
用于从发酵液中分离乙醇的装置 Download PDFInfo
- Publication number
- CN216106703U CN216106703U CN202120506690.3U CN202120506690U CN216106703U CN 216106703 U CN216106703 U CN 216106703U CN 202120506690 U CN202120506690 U CN 202120506690U CN 216106703 U CN216106703 U CN 216106703U
- Authority
- CN
- China
- Prior art keywords
- ethanol
- fluid communication
- clostridium
- ethyl acetate
- distillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn - After Issue
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 262
- 238000000855 fermentation Methods 0.000 title claims abstract description 60
- 230000004151 fermentation Effects 0.000 title claims abstract description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 165
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 105
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 238000004821 distillation Methods 0.000 claims abstract description 54
- 238000000926 separation method Methods 0.000 claims abstract description 44
- 239000002028 Biomass Substances 0.000 claims abstract description 43
- 230000000813 microbial effect Effects 0.000 claims abstract description 41
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 34
- 238000004891 communication Methods 0.000 claims abstract description 28
- 239000012530 fluid Substances 0.000 claims abstract description 28
- 150000003573 thiols Chemical class 0.000 claims abstract description 15
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 99
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 238000002309 gasification Methods 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 abstract 1
- 235000010633 broth Nutrition 0.000 description 44
- 239000000047 product Substances 0.000 description 41
- 241000193403 Clostridium Species 0.000 description 38
- 241000193171 Clostridium butyricum Species 0.000 description 24
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 20
- 239000003463 adsorbent Substances 0.000 description 17
- 239000006227 byproduct Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 244000005700 microbiome Species 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000895 extractive distillation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 241001656794 [Clostridium] saccharolyticum Species 0.000 description 4
- 239000001760 fusel oil Substances 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 3
- 241000589220 Acetobacter Species 0.000 description 3
- 241001656809 Clostridium autoethanogenum Species 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000011942 biocatalyst Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012978 lignocellulosic material Substances 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- 241000726119 Acidovorax Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 241000193163 Clostridioides difficile Species 0.000 description 2
- 241000193401 Clostridium acetobutylicum Species 0.000 description 2
- 241000193454 Clostridium beijerinckii Species 0.000 description 2
- 241000186566 Clostridium ljungdahlii Species 0.000 description 2
- 241000193469 Clostridium pasteurianum Species 0.000 description 2
- 241001611023 Clostridium ragsdalei Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000186398 Eubacterium limosum Species 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 240000006024 Lactobacillus plantarum Species 0.000 description 2
- 235000013965 Lactobacillus plantarum Nutrition 0.000 description 2
- 241000589308 Methylobacterium extorquens Species 0.000 description 2
- 241000186544 Moorella thermoautotrophica Species 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 241000589776 Pseudomonas putida Species 0.000 description 2
- 241000193448 Ruminiclostridium thermocellum Species 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 241000499912 Trichoderma reesei Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 241000193453 [Clostridium] cellulolyticum Species 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229940072205 lactobacillus plantarum Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical class C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 241000324499 Alkalibacillus Species 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001464894 Blautia producta Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241001171821 Clostridium coskatii Species 0.000 description 1
- 241000328950 Clostridium drakei Species 0.000 description 1
- 241000186570 Clostridium kluyveri Species 0.000 description 1
- 241001468167 Clostridium magnum Species 0.000 description 1
- 241000222511 Coprinus Species 0.000 description 1
- 241001528480 Cupriavidus Species 0.000 description 1
- 241001528539 Cupriavidus necator Species 0.000 description 1
- 241000228402 Histoplasma Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 241000186660 Lactobacillus Species 0.000 description 1
- 241000863391 Methylophilus Species 0.000 description 1
- 241000178985 Moorella Species 0.000 description 1
- 241000193459 Moorella thermoacetica Species 0.000 description 1
- 241000588771 Morganella <proteobacterium> Species 0.000 description 1
- 241000604373 Ovatus Species 0.000 description 1
- 241001509483 Oxobacter pfennigii Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000186339 Thermoanaerobacter Species 0.000 description 1
- 241001137870 Thermoanaerobacterium Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- ZMZINYUKVRMNTG-UHFFFAOYSA-N acetic acid;formic acid Chemical compound OC=O.CC(O)=O ZMZINYUKVRMNTG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940039696 lactobacillus Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
- B01D15/361—Ion-exchange
- B01D15/362—Cation-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/001—Processes specially adapted for distillation or rectification of fermented solutions
- B01D3/002—Processes specially adapted for distillation or rectification of fermented solutions by continuous methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/007—Energy recuperation; Heat pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/10—Vacuum distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/145—One step being separation by permeation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/065—Ethanol, i.e. non-beverage with microorganisms other than yeasts
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Analytical Chemistry (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
本公开内容涉及一种用于从发酵液中分离乙醇的装置,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述装置包括a.第一分离单元,其与生物反应器流体连通;b.第二分离单元,其与所述第一分离单元流体连通,与碱化合物导管流体连通;c.第三分离单元,其与所述第二分离单元流体连通,与含硫化合物导管流体连通;和d.蒸馏系统,其与所述第三分离单元流体连通。
Description
相关申请的交叉引用
本申请要求2020年3月11日提交的美国临时专利申请第62/988,176 号的权益,其全部内容通过引用的方式纳入本文。
技术领域
本发明涉及用于从发酵液中分离乙醇的装置。具体来说,该用于从发酵液中分离乙醇的装置可以用于从发酵液中回收和纯化产物(如乙醇),其中所述发酵液含有微生物生物质、乙醇和异丙醇。
背景技术
二氧化碳(CO2)占由人类活动引起的全球温室气体排放量的约76%,剩下的是甲烷(16%)、一氧化二氮(6%)和氟化气体(2%) (美国环境保护局)。尽管工业和林业实践也向大气排放CO2,但大部分CO2来自用于产生能量的化石燃料燃烧。减少温室气体排放,特别是 CO2排放,对于停止全球变暖进程以及随之而来的气候和天气变化至关重要。
人们早已认识到,催化方法(如费托法(Fischer-Tropsch process)) 可用于将含有二氧化碳(CO2)、一氧化碳(CO)和/或氢气(H2)的气体,如工业废气或合成气,转化成各种燃料和化学品。然而,最近,气体发酵已脱颖而出,成为用于这类气体的生物固定的替代平台。具体来说,已证明C1-固定性微生物将含有CO2、CO和/或H2的气体转化成诸如乙醇和异丙醇的产物。
通常,通过常规蒸馏分离通过费托法和/或气体发酵生产的产物。蒸馏方法基于待分离组分的挥发性差异,即沸点差异。产生并因此存在的副产物也必须与产物分离。然而,对于一些最终用途,已经证明仅仅简单的常规蒸馏无法以足够高的纯度水平将所需产物从溶液中有效地分离出来。
例如,在使用C1-固定性微生物的气体发酵中,当乙醇是所需产物时,副产物可为甲醇、乙缩醛(acetal)、乙醛、乙酸乙酯,以及可能的某些含硫化合物。根据乙醇的最终用途,可能需要将这些副产物中的一种或多种去除到指定水平以下。为了获得高纯度产物乙醇,可能需要多个分离步骤。
因此,仍然需要一个系统,其可有效地从气体发酵产物(例如乙醇) 中分离副产物化合物,以获得高纯度乙醇产物。
发明内容
本公开内容涉及一种用于从发酵液中分离乙醇的装置,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述装置包括:
a.第一分离单元,其与生物反应器流体连通,并被配置为从所述发酵液中至少分离微生物生物质并产生工艺流,其包含乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物;
b.第二分离单元,其与所述第一分离单元流体连通,与碱化合物导管流体连通,并被配置为通过将乙酸乙酯与碱化合物反应,然后蒸馏,从所述工艺流中去除乙酸乙酯;
c.第三分离单元,其与所述第二分离单元流体连通,与含硫化合物导管流体连通,并被配置为通过吸附或反应成二硫化物来去除至少一种硫醇;和
d.蒸馏系统,其与所述第三分离单元流体连通,并被配置为分离甲醇、具有3个或更多个碳原子的化合物和乙醇,其中所述蒸馏系统包含单个塔或者两个或更多个塔,并与甲醇导管、C3+(具有3个或更多个碳原子的化合物)导管和乙醇导管流体连通。
在本实用新型一个优选实施方案中,所述用于从发酵液中分离乙醇的装置还包括与所述乙醇导管流体连通的脱水单元。
在本实用新型一个优选实施方案中,所述用于从发酵液中分离乙醇的装置还包括至少一种与所述蒸馏系统流体连通的侧取馏出物。
在本实用新型一个优选实施方案中,所述生物反应器与底物导管流体连通,所述底物导管与工业过程或气化过程流体连通。
本实用新型装置可用于从发酵液中回收乙醇的方法,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述方法包括:从发酵液中至少分离微生物生物质以产生工艺流(process stream);以任何顺序从工艺流中去除:乙酸乙酯,通过将乙酸乙酯与碱化合物反应,然后蒸馏;至少一种硫醇,通过吸附或反应成二硫化物;甲醇,通过蒸馏;具有3个或更多个碳原子的化合物,通过蒸馏;和通过蒸馏回收乙醇;其中蒸馏可在单个塔(column)或者两个或更多个塔中进行。
发酵液还可包含乙醛,并且所述方法还可包括在去除微生物生物质以产生工艺流之后去除乙醛,通过使用金属将乙醛还原成乙酸酯,然后蒸馏。
发酵液还可包含至少一种醛,并且所述方法还可包括在去除微生物生物质以产生工艺流之后,通过还原成醇来去除醛。可使用活性金属、汞奇(amalgam)或包含活性金属的化合物来进行还原。活性金属、汞奇或化合物可包含锌或铝。可通过用肼的处理来进行还原。可将醛还原成醇,作为通过将乙酸乙酯与碱化合物反应,然后蒸馏来去除乙酸乙酯的步骤的一部分,参见下文。
可回收产物乙醇,作为其中去除甲醇或者其中去除具有3个或更多个碳原子的化合物的蒸馏步骤的一部分。
可进行所述方法,其中进行通过将乙酸乙酯与碱化合物反应,然后蒸馏来去除乙酸乙酯,和通过吸附或反应成二氧化硫来去除至少一种硫醇的步骤,然后进行通过蒸馏去除甲醇和通过蒸馏去除具有3个或更多个碳原子的化合物的步骤。
可进行所述方法,其中在惰性气氛中进行至少一次蒸馏,或者其中在惰性气氛中进行所有蒸馏。可进行所述方法,其中在空气中或在惰性气氛下去除至少一种硫醇。
可进行所述方法,其中吸附采用强酸性阳离子交换树脂。强酸性阳离子交换树脂可为在具有强酸性磺基(sulfonic group)的大孔网状聚苯乙烯基离子交换树脂(macroreticular polystyrene based ion exchange resin)上的Ag。
发酵液还可包含额外的杂质,并且所述方法还可包括用吸附剂处理工艺流以去除额外的杂质。吸附剂可为活性碳(activated carbon)、活性炭(activated charcoal)或强酸性阳离子交换树脂。强酸性阳离子交换树脂可为在具有强酸性磺基的大孔网状聚苯乙烯基离子交换树脂上的 Ag。
本公开内容的另一个实施方案涉及用于从发酵液中分离乙醇的方法,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述方法包括:从发酵液中至少分离微生物生物质,以产生微生物生物质耗尽(depleted) 的工艺流;通过将乙酸乙酯与碱化合物反应,然后蒸馏,从工艺流中去除乙酸乙酯,以产生乙酸乙酯耗尽的流;通过吸附或反应成二硫化物,从乙酸乙酯耗尽的流中去除至少一种硫醇,以产生硫醇耗尽的流;和通过蒸馏从硫醇耗尽的流中分离甲醇、乙醇和具有3个或更多个碳原子的化合物,所述蒸馏可在单个塔或者两个或更多个塔中进行。
本公开内容的另一个实施方案涉及用于从发酵液中分离乙醇的方法,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述方法包括从发酵液中至少分离微生物生物质,以产生微生物生物质耗尽的工艺流;通过吸附或反应成二硫化物来从工艺流中去除至少一种硫醇,以产生硫醇耗尽的流;通过将乙酸乙酯与碱化合物反应,然后蒸馏,从硫醇耗尽的流中去除乙酸乙酯,以产生乙酸乙酯耗尽的流;和通过蒸馏从乙酸乙酯耗尽的流中分离甲醇、乙醇和具有3个或更多个碳原子的化合物,所述蒸馏可在单个塔或者两个或更多个塔中进行。
本公开内容的另一个实施方案为用于从发酵液中分离乙醇的装置,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述装置包含:第一分离单元,其从发酵液中分离微生物生物质以产生工艺流,所述工艺流包含乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物;第二分离单元,其通过将乙酸乙酯与碱化合物反应,然后蒸馏,从工艺流中去除乙酸乙酯;第三分离单元,其通过吸附或反应成二硫化物来去除至少一种硫醇;和蒸馏系统,其用于分离甲醇、具有3个或更多个碳原子的化合物和乙醇,其中蒸馏系统包含单个塔或者两个或更多个塔。
附图说明
图1示出了根据本公开内容的一个实施方案的一系列简化的分离步骤,并特别示出了分离步骤的有用顺序。
图2为示出本公开内容的一个实施方案的示意性工艺流程图。
图3为一个示意性工艺流程图,其示出了一个实施方案的一部分,其涉及产生发酵液以及分离和去除微生物生物质以产生微生物生物质耗尽的工艺流。
具体实施方式
本发明提供了用于从发酵液中回收产物的方法,所述发酵液包含微生物生物质、产物、副产物和杂质。所述方法允许纯化产物,用于需要高纯度产物的用途。为了便于理解,在本文中将产物描述为乙醇。乙醇是使用生物催化剂在气体发酵系统中生产,并作为发酵液的一部分离开一个或多个生物反应器。发酵液包含微生物生物质、乙醇和副产物,如甲醇、乙酸乙酯、至少一种硫醇、至少一种具有3个或更多个碳原子的化合物,以及可能的杂质。发酵液还可包含乙醛。发酵液还可包含至少一种醛。发酵液还可包含杂质。
气体发酵过程的底物和/或C1-碳源可为作为工业过程的副产物获得的或来自另一来源,如汽车废气、沼气、填埋气或来自电解的气体。底物和/或C1-碳源可为热解、烘干(torrefaction)或气化产生的合成气。换句话说,可通过热解、烘烤或气化来再循环废料,以产生合成气,所述合成气用作底物和/或C1-碳源。
在某些实施方案中,工业过程选自黑色金属产品制造,如钢厂制造、有色金属产品制造、石油炼制、电力生产、炭黑生产、造纸和纸浆制造、氨生产、甲醇生产、焦炭制造,或其任何组合。在这些实施方案中,可使用任何已知的方法在底物和/或C1-碳源被排放到大气中之前将其从工业过程中捕获。
底物和/或C1-碳源可为合成气,如通过以下方法获得的合成气:煤气化、精炼厂残渣气化、生物质气化、木质纤维素材料气化、黑液气化、城市固体废物气化、工业固体废物气化、污水气化、来自废水处理的污泥气化、天然气重整、沼气重整、填埋气重整,或其任何组合。
城市固体废物的实例包括轮胎、塑料,以及和鞋、服装、纺织品中的纤维。城市固体废物可分类或不分类。生物质的实例可包括木质纤维素材料,且还可包括微生物生物质。木质纤维素材料可包括农业废物和森林废物。
使用生物催化剂的底物和/或C1-碳源的气体发酵过程提供了同时含有产物和微生物生物质的发酵液。从发酵液中分离微生物生物质,以产生微生物生物质耗尽的工艺流。一般来说,工艺流将包含产物和某一浓度的副产物和可能的杂质。例如,工艺流可包含产物乙醇以及副产物,如甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物。工艺流还可包含乙醛,和/或至少一种醛,和/或其他杂质。发酵液的其余部分包含微生物生物质,其可以被再循环到生物反应器中。发酵液通常为水溶液。微生物生物质包含至少一种合适的微生物,其用作发酵过程的生物催化剂。例如,微生物可选自大肠杆菌(Escherichia coli)、酿酒酵母(Saccharomyces cerevisiae)、丙酮丁醇梭菌(Clostridium acetobutylicum)、拜氏梭菌(Clostridium beijerinckii)、糖丁酸梭菌(Clostridium saccharbutyricum)、糖产丁醇丙酮梭菌(Clostridiumsaccharoperbutylacetonicum)、丁酸梭菌(Clostridium butyricum)、二醇梭菌(Clostridium diolis)、克氏梭菌(Clostridium kluyveri)、巴斯德梭菌(Clostridiumpasterianium)、诺维氏梭菌(Clostridium novyi)、艰难梭菌(Clostridium difficile)、热纤梭菌(Clostridium thermocellum)、解纤维梭菌(Clostridium cellulolyticum)、噬纤维梭菌(Clostridium cellulovorans)、植酵梭菌(Clostridium phytofermentans)、乳酸乳球菌 (Lactococcus lactis)、枯草芽孢杆菌(Bacillus subtilis)、地衣芽孢杆菌(Bacillus licheniformis)、运动发酵单胞菌(Zymomonas mobilis)、产酸克雷伯氏菌(Klebsiella oxytoca)、肺炎克雷伯氏菌(Klebsiella pneumonia)、谷氨酸棒状杆菌(Corynebacterium glutamicum)、里氏木霉(Trichoderma reesei)、杀虫贪铜菌(Cupriavidus necator)、恶臭假单胞菌(Pseudomonas putida)、植物乳杆菌(Lactobacillus plantarum) 和扭脱甲基杆菌(Methylobacterium extorquens)。在某些情况下,微生物可为选自以下的C1-固定性细菌:伍氏醋酸杆菌(Acetobacterium woodii)、巴氏嗜碱菌(Alkalibaculum bacchii)、长型布劳特氏菌(Blautia producta)、甲基营养丁酸杆菌(Butyribacterium methylotrophicum)、醋酸梭菌(Clostridium aceticum)、自产乙醇梭菌(Clostridium autoethanogenum)、嗜一氧化碳梭菌(Clostridiumcarboxidivorans)、科斯卡塔梭菌(Clostridium coskatii)、德氏梭菌(Clostridiumdrakei)、甲酸乙酸梭菌(Clostridium formicoaceticum)、扬氏梭菌(Clostridiumljungdahlii)、大梭菌(Clostridium magnum)、拉氏梭菌(Clostridium ragsdalei)、粪味梭菌(Clostridium scatologenes)、粘液真杆菌 (Eubacterium limosum)、热自养穆尔氏菌(Moorella thermautotrophica)、热醋穆尔氏菌(Moorella thermoacetica)、普氏产醋杆菌(Oxobacter pfennigii)、卵形鼠孢菌(Sporomusa ovata)、森林土壤醋酸鼠孢菌(Sporomusa silvacetica)、类球鼠孢菌(Sporomusa sphaeroides)和凯伍热厌氧杆菌(Thermoanaerobacter kiuvi)。在一个特定的实施方案中,微生物为梭菌(Clostridium)属的成员。在某些情况下,微生物为自产乙醇梭菌。
微生物可能够生产各种不同的产物。通过微生物生产的一种或多种产物可为低沸点发酵产物。在某些情况下,产物为乙醇、丙酮、异丙醇、丁醇、酮、甲基乙基酮、丙酮、2-丁醇、1-丙醇、乙酸甲酯、乙酸乙酯、丁酮、1,3-丁二烯、异戊二烯、异丁烯,或其任何组合。在某些实施方案中,所述方法是基于所生产的产物来进行优化。在一些实施方案中,在生物反应器中生产的产物为乙醇和异丙醇。对所述方法进行优化以使得可有效地从发酵液去除乙醇和异丙醇。在一些实施方案中,微生物生产至少一种副产物。在一个实施方案中,至少一种副产物为乙酸、乳酸、丙酮、3-羟基丁酸、异丁醇、正丙醇、正丁醇和2,3-丁二醇。
已知的用于分离微生物生物质以产生至少包含产物的工艺流的技术。例如,可将发酵液从生物反应器传递到真空蒸馏容器,在真空蒸馏容器中,发酵液被部分汽化以产生包含乙醇的产物富集流和包含微生物生物质的产物耗尽流。在例如US 2018/0264375中详细描述了真空蒸馏。
萃取蒸馏,单独使用或与真空蒸馏结合使用,为另一种已知的技术,其可用于从发酵液中分离微生物生物质耗尽的工艺流。萃取蒸馏剂通过与产物相互作用来起作用以增加所需产物与其他组分之间的相对挥发性。例如,萃取蒸馏剂对所需产物具有较高的亲和力,对副产物具有较低的亲和力。适当的萃取蒸馏剂不应与组分形成共沸物,并且其应能够通过后续分离技术(如蒸馏)与产物分离。例如,在US 2020/0255362 中列出了合适的潜在萃取蒸馏剂。
另一种技术涉及使用分离模块,所述分离模块被改造为适于从生物反应器接收发酵液,并使发酵液通过过滤器以产生保留液和渗透液。通常,渗透液至少包含产物,保留液至少包含发酵液的微生物生物质,可将所述微生物生物质再循环到生物反应器。过滤器可为膜,如横流膜 (cross-flow membrane)或中空纤维膜。
从发酵液分离的并耗尽微生物生物质的工艺流包含乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物。可发酵液的其余部分可被再循环到生物反应器,或者可被进一步处理,然后再循环到生物反应器。用于燃料应用的乙醇可能不需要高度的纯度,但乙醇的其他应用可能需要高度的纯度,以避免令人不愉快的气味或香味或对人类健康的影响。为了生产最高价值的乙醇,需要去除通常产生的并且与乙醇一起存在于工艺流中的副产物。蒸馏是分离所需乙醇的主要技术,但由于所需乙醇和不想要的副产物的相似的温度-蒸气压分布,仅蒸馏并不足以达到必要的纯度水平。此外,在一些情况下,可能形成共沸物,使得蒸馏困难。需要将多个分离步骤中的多种分离技术结合,以达到产物乙醇的所需的纯度水平。以特定的顺序进行特定的分离步骤以达到所需的结果是有利的。
乙酸乙酯可作为副产物存在于工艺流中,并且需要从工艺流中去除乙酸乙酯以产生高纯度乙醇产物。乙酸乙酯难以与乙醇分离。例如,由于乙酸乙酯与乙醇的沸点接近,因此不能通过蒸馏或精馏将其由于乙酸乙酯与乙醇分离。然而,本公开内容采用酯的碱性水解,或更具体地,用碱(如氢氧化钠)水解乙酸乙酯以形成乙醇和乙酸的技术,所述乙酸被中和为乙酸盐,如乙酸钠。在接近工艺流向分离步骤的进料的位置处添加碱。可将碱添加到工艺流进料到塔中的位置的上方,例如在塔的顶部或顶部附近。可将碱添加到再沸器进料中,特别是在分批操作中。所得乙酸盐与乙醇不反应,然后可通过蒸馏容易地将乙酸盐与乙醇分离。其他碱适合用于该分离步骤,并包括碱,例如氢氧化钾、氢氧化钙、氢氧化锂、氢氧化铷、氢氧化铯、氢氧化钡、氢氧化铵、氢氧化镁,及其组合。在该分离步骤中,将乙酸乙酯从工艺流中去除,从而从产物乙醇中去除。
然后可以用吸附材料处理现在耗尽乙酸乙酯的工艺流,以去除含硫化合物,例如硫醇。已知含硫化合物会产生令人不愉快的气味,使乙醇不适合一些高纯度的应用。低水平的硫化合物即可导致令人不愉快的气味,例如在十亿分之一份范围内的浓度。将包含至少一种硫醇的工艺流与吸附剂(能够吸附并由此从工艺流中去除硫醇)接触,由此也将从流中去除令人不愉快的气味。合适的吸附剂包括例如强酸性阳离子交换树脂。一个实例为银处理或浸渍的中和的强酸性离子交换树脂催化吸附剂。树脂可为磺化的苯乙烯-二乙烯基苯树脂。这种合成树脂以名称Rohm& Haas的Amberlyst 15和Bayer AG的LEWATIT SPC 118销售。合适的吸附剂以名称Rohm&Haas的Ag/Amberlyst-15销售。在US 4,760,204 中详细描述了合适的吸附剂。可以连续方式、分批方式、摇摆床方式或任何其他合适的操作方式来操作对工艺流的处理。吸附剂可以布置在固定床、移动床、流化床、模拟移动床中或为任何其他合适的布置。
在另一个实施方案中,可以使用碳将存在的任何硫醇氧化以形成二硫化物,以便将有气味的硫醇以化学方法转化为无臭的二硫化物。
可以在空气中进行或可以在惰性气氛中进行去除硫化合物的处理。惰性气氛的非限制实例包括氮气气氛和氦气气氛。使用惰性气氛的一个优势是避免产生不想要的乙醛。可以用惰性气体(例如氮气)吹扫吸附剂容器,并且可以用氮气连续吹扫。
蒸馏现在同时耗尽乙酸乙酯和硫醇的工艺流以分离乙醇、甲醇和至少一种具有3个或更多个碳原子的化合物。可以在一个、两个或多个蒸馏塔中完成蒸馏。例如,可使用单个蒸馏塔从甲醇塔顶馏出物流和高纯度乙醇侧馏份流(side cut stream)中分离至少一种具有3个或更多个碳原子的化合物作为塔底流(bottoms stream)。在另一个实施方案中,第一塔可以(作为塔顶馏出物和塔底馏出物塔)将甲醇与乙醇和至少一种具有3个或更多个碳原子的化合物分离。在第二塔中,将高纯度乙醇与至少一种具有三个或更多个碳原子的化合物分离。
可在惰性气氛中进行一次或多次蒸馏。一个或多个蒸馏塔可为萃取蒸馏塔,并使用萃取蒸馏剂。
发酵过程可产生杂醇油作为副产物。因此,耗尽微生物生物质的发酵液和工艺流还可包含杂醇油。在蒸馏步骤中,可从工艺流中去除杂醇油。在一个实施方案中,将杂醇油作为侧取馏出物(side-draw)从至少一个蒸馏塔中去除。也可以将硫物质与杂醇油一起去除,作为来自至少一个蒸馏塔的相同侧取馏出物的一部分。可在此处去除在此过程中较早时未去除的含硫化合物。
发酵液和工艺流还可包含乙醛。乙醛是工艺流中不想要的组分,并且可以将其去除以免污染产物乙醇和降低产物乙醇的纯度。该分离步骤是任选的,并且可取决于工艺流中存在的乙醛的量。通过以下方式从工艺流中去除乙醛:使用金属将乙醛还原为乙酸酯,然后蒸馏以去除乙酸酯。所形成的乙酸酯可为乙酸乙酯。因此,可在与去除乙酸乙酯的步骤相同的步骤中去除乙醛。
发酵液和工艺流还可包含醛。醛是工艺流中不想要的组分,并且应被去除以免污染产物乙醇和降低产物乙醇的纯度。可以将醛还原成醇,然后从工艺流中去除。可以使用活性金属、汞奇或包含活性金属的化合物完成对醛的还原。适当的金属、汞奇和化合物可包含锌或铝。可使用不同金属、汞奇和化合物的混合物。在另一个实施方案中,可用肼处理工艺流以与醛反应并形成烷烃(alkane)。可在蒸馏步骤中去除所产生的醇或所产生的烷烃,使得可以回收高纯度的乙醇。
发酵液和工艺流还可包含不想要的杂质。可使用吸附剂处理工艺流以去除杂质。合适的吸附剂包括活性碳、活性炭和银处理或浸渍的中和的强酸性离子交换树脂催化吸附剂,如以名称Ag/Amberlyst-15销售的吸附剂。可在该过程中的任何点处理工艺流以去除杂质。在一个实施方案中,在其他分离步骤之前,处理工艺流以去除杂质。在另一个实施方案中,在与去除至少一种硫醇的步骤相同的步骤中,处理工艺流以去除杂质。
可以任何顺序进行分离步骤,但是按一定顺序进行所述步骤具有优势。从工艺流中去除乙酸乙酯和硫醇,然后去除甲醇和具有3个或更多个碳原子的化合物是有利的。在一个实施方案中,首先从工艺流中去除乙酸乙酯。
任选地,可将纯化的乙醇流干燥或脱水。因为乙醇与水形成共沸物,简单的蒸馏可以使乙醇脱水至追高达约90重量%,但去除剩余的水需要另一种技术。这种技术是已知的,合适的技术包括使用膜脱水和吸附剂脱水。膜技术的实例包括膜蒸气渗透或渗透蒸发模式。多种不同的膜是可商购的,以用于乙醇脱水。吸附和变压吸附(PSA)是已知的生产无水乙醇的技术。许多沸石吸附剂是可商购的,以用于PSA系统。
图1示出了一种工艺流程图,其中在步骤104中从发酵液102中去除微生物生物质以形成耗尽微生物生物质的工艺流。将工艺流传递到分离步骤112的序列108或序列110。在分离步骤112的序列108中,首先在109中通过将乙酸乙酯与碱化合物反应,然后蒸馏,除去乙酸乙酯,然后在111中通过吸附或反应成二硫化物分离至少一种硫醇。在分离步骤112的序列110中,首先在113中通过吸附或反应成二硫化物分离至少一种硫醇,然后在114中通过将乙酸乙酯与碱化合物反应,然后蒸馏,去除乙酸乙酯。在分离步骤112之后,工艺流耗尽乙酸乙酯和硫醇,并被传递到分离步骤120的序列116或序列118。在分离步骤120的序列 116中,首先在117中通过蒸馏分离甲醇,然后在119中通过蒸馏分离至少一种具有3个或更多个碳原子的化合物。在分离步骤120的序列118 中,首先在121中通过蒸馏分离具有3个或更多个碳原子的化合物,然后在122中通过蒸馏分离甲醇。然后在步骤122中回收乙醇。
图2示出了本公开内容的一个实施方案,其中分离步骤以特定顺序排列。在管线204(line 204)中传导(conduct)一种工艺流,其已从发酵液中分离出来,并包含乙酸乙酯、至少一种硫醇、甲醇、至少一种具有3个或更多个碳原子的化合物和乙醇,并将其引入容器206,在容器 206中去除乙酸乙酯。在管线208中,将碱(如氢氧化钠)引入容器206。碱与乙酸乙酯反应形成乙酸钠,其在管线210中被去除。将乙酸乙酯耗尽的工艺流通过管线212从容器206传递到容器214。容器214容纳能够吸附至少一种硫醇的吸附剂。将乙酸乙酯和硫醇耗尽的工艺流在管线 218中从容器214传递到容器220。在该过程的某一点,在解吸步骤中解吸被吸附剂吸附的硫醇,并通过管线216将其去除。容器220是蒸馏塔,其中在管线224中将甲醇作为塔顶馏出物去除,并在管线222中将包含乙醇和至少一种具有3个或更多个碳原子的化合物的塔底馏出物传递到容器226。还示出了任选的侧取馏出物232,其中可以取出杂醇油和/或含硫化合物。容器226是蒸馏塔,其中去除塔底流228中至少一种具有 3个或更多个碳原子的化合物。还示出了任选的侧取馏出物234,其中可以取出杂醇油和/或含硫化合物。在塔顶馏出物管线230中去除纯化的乙醇。任选地,可在乙醇脱水单元238中干燥管线230中纯化的乙醇,以在管线236中提供纯化的脱水乙醇。乙醇脱水单元238可为膜系统或PSA。
图3示出了产生发酵液以及分离和去除微生物生物质以产生微生物生物质耗尽的工艺流的实施方案的部分。工业过程或气化单元310在导管304中提供底物,该底物被传递到生物反应器300中,在该反应器中使用微生物对底物进行发酵以产生目标产物如乙醇。从生物反应器300 中去除发酵液312并将其传递到分离器314,所述发酵液312包含微生物生物质、乙酸乙酯、至少一种硫醇、甲醇、至少一种具有3个或更多个碳原子的化合物和乙醇,在分离器314中将微生物生物质分离到管线 316并再循环到生物反应器300中。耗尽微生物生物质的工艺流204准备如图2所述进行纯化,所述工艺流包含乙酸乙酯、至少一种硫醇、甲醇、至少一种具有3个或更多个碳原子的化合物和乙醇。
Claims (4)
1.一种用于从发酵液中分离乙醇的装置,所述发酵液包含微生物生物质、乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物,所述装置包括:
a.第一分离单元,其与生物反应器流体连通,并被配置为从所述发酵液中至少分离微生物生物质并产生工艺流,其包含乙醇、甲醇、乙酸乙酯、至少一种硫醇和至少一种具有3个或更多个碳原子的化合物;
b.第二分离单元,其与所述第一分离单元流体连通,与碱化合物导管流体连通,并被配置为通过将乙酸乙酯与碱化合物反应,然后蒸馏,从所述工艺流中去除乙酸乙酯;
c.第三分离单元,其与所述第二分离单元流体连通,与含硫化合物导管流体连通,并被配置为通过吸附或反应成二硫化物来去除至少一种硫醇;和
d.蒸馏系统,其与所述第三分离单元流体连通,并被配置为分离甲醇、具有3个或更多个碳原子的化合物和乙醇,其中所述蒸馏系统包含单个塔或者两个或更多个塔,并与甲醇导管、C3+导管和乙醇导管流体连通。
2.根据权利要求1所述的装置,还包括与所述乙醇导管流体连通的脱水单元。
3.根据权利要求1所述的装置,还包括至少一种与所述蒸馏系统流体连通的侧取馏出物。
4.根据权利要求1所述的装置,其中所述生物反应器与底物导管流体连通,所述底物导管与工业过程或气化过程流体连通。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US202062988176P | 2020-03-11 | 2020-03-11 | |
US62/988,176 | 2020-03-11 | ||
US17/183,204 US11731926B2 (en) | 2020-03-11 | 2021-02-23 | Process for purification of products |
US17/183,204 | 2021-02-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN216106703U true CN216106703U (zh) | 2022-03-22 |
Family
ID=77617421
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202120506690.3U Withdrawn - After Issue CN216106703U (zh) | 2020-03-11 | 2021-03-10 | 用于从发酵液中分离乙醇的装置 |
CN202110260178.XA Active CN113387773B (zh) | 2020-03-11 | 2021-03-10 | 用于纯化产物的方法 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110260178.XA Active CN113387773B (zh) | 2020-03-11 | 2021-03-10 | 用于纯化产物的方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US20230357112A1 (zh) |
EP (1) | EP4065722A4 (zh) |
JP (1) | JP7440643B2 (zh) |
KR (1) | KR102508039B1 (zh) |
CN (2) | CN216106703U (zh) |
AU (1) | AU2021234241B2 (zh) |
BR (1) | BR112022013249B1 (zh) |
CA (1) | CA3163619C (zh) |
MY (1) | MY193502A (zh) |
TW (1) | TWI760140B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113387773A (zh) * | 2020-03-11 | 2021-09-14 | 朗泽科技有限公司 | 用于纯化产物的方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3143734A1 (de) | 1981-11-04 | 1983-05-11 | Hoechst Ag, 6230 Frankfurt | Verfahren zur kontinuierlichen rektifikation eines alkohole enthaltenden fluessigkeitsgemisches" |
US5800681A (en) | 1997-04-21 | 1998-09-01 | Berg; Lloyd | Separation of ethanol, isopropanol and water mixtures by extractive distillation |
US20070284310A1 (en) * | 2006-06-12 | 2007-12-13 | Van Leeuwen Johannes | Method and system for purifying ethanol |
MX2011003558A (es) | 2008-10-03 | 2011-05-02 | Metabolic Explorer Sa | Metodo para purificar un alcohol de un caldo de fermentacion usando un evaporador de pelicula descendente, un evaporador de pelicula enjuagada, un evaporador de pelicula delgada o un evaporador de trayectoria corta. |
US20100120104A1 (en) * | 2008-11-06 | 2010-05-13 | John Stuart Reed | Biological and chemical process utilizing chemoautotrophic microorganisms for the chemosythetic fixation of carbon dioxide and/or other inorganic carbon sources into organic compounds, and the generation of additional useful products |
CN103221547B (zh) * | 2010-11-09 | 2015-12-09 | 绿源乙醇公司 | 用于从木质纤维素性生物质生产乙醇的连续方法 |
CN102617281A (zh) | 2011-01-28 | 2012-08-01 | 株式会社大赛璐 | 从醇中除去硫化合物的方法 |
US8927784B2 (en) * | 2011-04-26 | 2015-01-06 | Celanese International Corporation | Process to recover alcohol from an ethyl acetate residue stream |
US8686200B2 (en) * | 2011-04-26 | 2014-04-01 | Celanese International Corporation | Process to recover alcohol from an acidic residue stream |
US8980596B2 (en) * | 2012-05-23 | 2015-03-17 | Lanzatech New Zealand Limited | Fermentation and simulated moving bed process |
NZ706072A (en) * | 2013-03-08 | 2018-12-21 | Xyleco Inc | Equipment protecting enclosures |
DK3411490T3 (da) * | 2016-02-04 | 2021-01-18 | Lanzatech New Zealand Ltd | Lavtryksseparator med en indvendig deler og anvendelser dertil |
CA3053053C (en) * | 2017-03-20 | 2020-04-14 | Lanzatech, Inc. | A process and system for product recovery and cell recycle |
CN110760548A (zh) * | 2019-08-26 | 2020-02-07 | 王松 | 一种甘蔗生产乙醇的系统及方法 |
MY193502A (en) * | 2020-03-11 | 2022-10-17 | Lanzatech Inc | Process for purification of products |
-
2021
- 2021-03-04 MY MYPI2022003639A patent/MY193502A/en unknown
- 2021-03-04 JP JP2022540828A patent/JP7440643B2/ja active Active
- 2021-03-04 CA CA3163619A patent/CA3163619C/en active Active
- 2021-03-04 AU AU2021234241A patent/AU2021234241B2/en active Active
- 2021-03-04 KR KR1020227022574A patent/KR102508039B1/ko active IP Right Grant
- 2021-03-04 EP EP21767035.5A patent/EP4065722A4/en active Pending
- 2021-03-04 BR BR112022013249-2A patent/BR112022013249B1/pt active IP Right Grant
- 2021-03-10 CN CN202120506690.3U patent/CN216106703U/zh not_active Withdrawn - After Issue
- 2021-03-10 CN CN202110260178.XA patent/CN113387773B/zh active Active
- 2021-03-11 TW TW110108634A patent/TWI760140B/zh active
-
2023
- 2023-07-14 US US18/352,623 patent/US20230357112A1/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113387773A (zh) * | 2020-03-11 | 2021-09-14 | 朗泽科技有限公司 | 用于纯化产物的方法 |
CN113387773B (zh) * | 2020-03-11 | 2023-11-28 | 朗泽科技有限公司 | 用于纯化产物的方法 |
Also Published As
Publication number | Publication date |
---|---|
BR112022013249B1 (pt) | 2023-03-14 |
CA3163619A1 (en) | 2021-09-16 |
US20230357112A1 (en) | 2023-11-09 |
CA3163619C (en) | 2023-04-11 |
CN113387773A (zh) | 2021-09-14 |
JP7440643B2 (ja) | 2024-02-28 |
TW202144314A (zh) | 2021-12-01 |
MY193502A (en) | 2022-10-17 |
KR102508039B1 (ko) | 2023-03-08 |
EP4065722A4 (en) | 2023-10-04 |
AU2021234241B2 (en) | 2023-02-02 |
KR20220100091A (ko) | 2022-07-14 |
AU2021234241A1 (en) | 2022-07-21 |
JP2023503181A (ja) | 2023-01-26 |
EP4065722A1 (en) | 2022-10-05 |
CN113387773B (zh) | 2023-11-28 |
TWI760140B (zh) | 2022-04-01 |
BR112022013249A2 (pt) | 2022-09-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11441116B2 (en) | Integrated process for filtering constituents from a gas stream | |
KR101588052B1 (ko) | 발효액으로부터 부티르산을 추출하고 부티르산을 바이오연료로 화학적으로 전환하는 방법 | |
EP2609206A1 (en) | Process for producing ethanol and ethylene via fermentation | |
JP2019503702A (ja) | 内部ディバイダを有する低圧分離器及びそのための使用 | |
US11807592B2 (en) | Process for recovering close boiling products | |
US20230357112A1 (en) | Process for purification of products | |
KR102524251B1 (ko) | 피루베이트 유래 생성물의 생성 및 제어를 위한 발효 공정 | |
US11731926B2 (en) | Process for purification of products | |
EA042329B1 (ru) | Способ очистки продуктов | |
WO2022101182A1 (en) | Sustainable biomass production | |
CA1192141A (en) | Concentration of organic chemicals from dilute aqueous solutions | |
EA045094B1 (ru) | Способ извлечения продуктов с близкими температурами кипения |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GR01 | Patent grant | ||
GR01 | Patent grant | ||
AV01 | Patent right actively abandoned | ||
AV01 | Patent right actively abandoned | ||
AV01 | Patent right actively abandoned |
Granted publication date: 20220322 Effective date of abandoning: 20231128 |
|
AV01 | Patent right actively abandoned |
Granted publication date: 20220322 Effective date of abandoning: 20231128 |