WO2024062209A1 - Copper-containing hydrogenation catalysts for the hydrogenolysis of esters - Google Patents
Copper-containing hydrogenation catalysts for the hydrogenolysis of esters Download PDFInfo
- Publication number
- WO2024062209A1 WO2024062209A1 PCT/GB2023/051692 GB2023051692W WO2024062209A1 WO 2024062209 A1 WO2024062209 A1 WO 2024062209A1 GB 2023051692 W GB2023051692 W GB 2023051692W WO 2024062209 A1 WO2024062209 A1 WO 2024062209A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- copper
- alumina
- hydrogenolysis
- ester
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 239000010949 copper Substances 0.000 title claims abstract description 87
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 150000002148 esters Chemical class 0.000 title claims abstract description 40
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 title description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011701 zinc Substances 0.000 claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 3
- 238000005470 impregnation Methods 0.000 claims description 29
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 10
- 229940116318 copper carbonate Drugs 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000011667 zinc carbonate Substances 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004876 x-ray fluorescence Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000004164 Wax ester Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000019386 wax ester Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 150000003751 zinc Chemical class 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- XMUJIPOFTAHSOK-UHFFFAOYSA-N undecan-2-ol Chemical compound CCCCCCCCCC(C)O XMUJIPOFTAHSOK-UHFFFAOYSA-N 0.000 description 2
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- JPEWDCTZJFUITH-UHFFFAOYSA-N 1-methoxydecane Chemical compound CCCCCCCCCCOC JPEWDCTZJFUITH-UHFFFAOYSA-N 0.000 description 1
- JWCACDSKXWPOFF-UHFFFAOYSA-N 1-methoxydodecane Chemical compound CCCCCCCCCCCCOC JWCACDSKXWPOFF-UHFFFAOYSA-N 0.000 description 1
- RIAWWRJHTAZJSU-UHFFFAOYSA-N 1-methoxyoctane Chemical compound CCCCCCCCOC RIAWWRJHTAZJSU-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 208000016444 Benign adult familial myoclonic epilepsy Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- 239000005641 Methyl octanoate Substances 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- IZDJJEMZQZQQQQ-UHFFFAOYSA-N dicopper;tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O IZDJJEMZQZQQQQ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 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
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 208000016427 familial adult myoclonic epilepsy Diseases 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
- B01J2523/17—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
- B01J2523/27—Zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/31—Aluminium
Definitions
- the present invention relates to copper-containing hydrogenation catalysts and their use in the hydrogenolysis of esters.
- Fatty alcohols are useful feedstocks, in particular for the production of surfactants and detergents.
- One process for the production of fatty alcohols is through the hydrogenolysis of acid methyl esters (FAMEs) which are usually derived from triglycerides found in animal fats and vegetable oils.
- FAMEs acid methyl esters
- JPH1045645A describes a process for the production of cyclohexanedimethanol (CH DM) by a two-stage process.
- the first stage involves hydrogenating a dialkyl terephthalate in the presence of a noble metal-based nuclear hydrogenation catalyst to produce 1 ,4- cyclohexanedicarboxylic dialkyl ester.
- the second stage involves hydrogenolysis of the 1 ,4- cyclohexanedicarboxylic dialkyl ester in the presence of a copper-zinc-alumina-based catalyst.
- a preferred catalyst for the second stage comprises, in oxidic form, 30-70 wt% copper oxide, 20-60 wt% zinc oxide and 3-20 wt% alumina.
- the article “Cu-Zn/AhOs Catalyst for the Hydrogenation of Esters to Alcohols” (Chin J Catal, 2010, 31 : 769-775) describes a catalyst with a molar ratio of copper : zinc : alumina of 30 : 40 : 30 which is produced by a high speed collision co-precipitation method.
- the catalyst contained approximately 51 wt% copper, 10 wt% zinc and 7 wt% aluminium after calcination. The catalyst was tested for its performance in the hydrogenolysis of natural palm oil which has first been transesterified with methanol.
- W02005/070537A1 describes chromium-free catalysts comprising copper and at least one second metal which are obtainable through a method involving addition of a solution comprising Cu ions and ions of at least one other second metal to an inert carrier, optional drying, calcining and reduction of at least part of the oxidic copper.
- the examples use silica, magnesia, zirconia or titania as the support.
- the catalysts may be used for a number of duties, including the hydrogenation of fatty acids, fatty esters, esters and diesters to fatty alcohols, alcohols and dialcohols respectively.
- WO2016/059431 A1 describes catalysts comprising copper, zinc and a silica-alumina material that is not a zeolite.
- catalysts are prepared by precipitating copper nitrate and zinc nitrate with sodium carbonate in the presence of a silica-alumina support. The catalysts are tested for their activity in the hydrogenolysis of methyl laurate.
- WO2016/154514A1 describes catalysts comprising a mixed metal oxide comprising copper and at least one of manganese, zinc, nickel or cobalt; an alumina; silica; and calcium.
- the catalysts may be used for a number of duties, including the hydrogenolysis of FAMEs and free fatty acids.
- CN1036576567B describes hydrogenation catalysts comprising 3-10 mass% boron oxide, 6-20 mass% zinc oxide, 4-12 mass% copper, on a carrier of gamma alumina with a specific surface area of 180-400 m 2 /g and a pore volume of 0.2-0.8 cm 3 /g.
- the catalysts may be used for a variety of duties including the hydrogenation of FAMEs.
- CN105363454B describes hydrogenation catalysts comprising: (a) 10-50 wt% copper or its oxides; (b) 0-20 wt% of a mixture of ZnO and CdO; (c) ⁇ 5 wt% of a mixture of P2O5 and Bi2Os; and (d) 40-70 wt% of a carrier selected from at least one of silica, alumina, and a molecular sieve, on the condition that the amount of component (c) is not zero.
- Comparative catalyst C1 is 10CuO-15ZnO-75Al2Os and is prepared by co-impregnation of an alumina carrier with a solution containing copper nitrate trihydrate and zinc nitrate hexahydrate.
- the catalysts may be used for a variety of duties including the hydrogenation of esters.
- an ester hydrogenolysis catalyst should satisfy the following properties. Firstly, the catalyst should have high activity for the conversion of the ester substrate. Secondly, the catalyst should retain high activity for the conversion of the ester substrate, so that the catalyst does not need to replaced too frequently. Thirdly, the catalyst should have high selectivity for the desired ester hydrogenolysis reaction and produce low levels of by-products. Fourthly, the catalyst should have high crush strength and retain high crush strength during the course of the reaction. The reason for this is that if the crush strength is too low, the catalyst may disintegrate in the reactor resulting in an increase in pressure drop through the reactor, which can cause blockages and requires premature catalyst discharge.
- the present invention relates to a catalyst having a good balance of the above properties, and a process of using the catalyst in the hydrogenolysis of esters.
- Figure 1 is a plot showing substrate conversion (methyl laurate) against copper surface area (m 2 /mL cat)
- a catalyst containing copper and zinc on an alumina support provides a catalyst having a good balance between: high activity for ester hydrogenation, retention of activity, low by-product production and good retention of crush strength.
- the invention relates to a process for the hydrogenolysis of an ester substrate, comprising the step of carrying out hydrogenolysis of the ester substrate in the presence of a heterogeneous catalyst, wherein the catalyst comprises:
- oxidic catalyst means a catalyst in which substantially all of the Zn and Cu are present as oxides.
- the catalyst used in the process is in reduced form and is preferably prepared by reducing an oxidic catalyst as defined in the second aspect of the invention.
- the oxidic catalyst is typically activated in situ by reducing some or all of the CuO to Cu metal using a feed containing H2. However, the ZnO and alumina are not reduced. The activation may be carried out in the gas phase or the liquid phase. The result is a catalyst in which some or all of the Cu is present as crystallites of Cu(0). Such catalyst is referred to as a “reduced catalyst” herein.
- An exemplary method for the liquid phase activation of a catalyst is described in W02020/053555 (Johnson Matthey Davy Technologies Limited).
- the substrate is an ester of a saturated or unsaturated fatty acid.
- the invention relates to an oxidic catalyst for the hydrogenolysis of an ester substrate, wherein the catalyst comprises:
- the catalyst has a copper surface area of 10-20 m 2 /mL ca t; wherein the total content of elements other than Cu, Zn, Al and O is ⁇ 1 wt%.
- the copper content, zinc content and copper surface area are measured on the oxidic catalyst by the method described in the examples section.
- the invention relates to a method for preparing an oxidic catalyst according to the second aspect, comprising the steps of:
- step (ii) drying the product of step (i); and (iii) calcining the product of step (ii).
- any aspect described as being preferred in connection with the catalyst also applies to the catalyst used in the process of the first aspect or prepared by the method of the third aspect.
- the catalyst comprises 5-20 wt% copper. This loading of copper is lower than many known precipitated copper catalysts. A low content of copper is preferred from a cost perspective. A preferred copper content is 5-12 wt% as this gives a good balance between activity and cost.
- the catalyst comprises 5-12 wt% zinc.
- the inclusion of zinc not only improves the catalyst activity in absolute terms, but also reduces the drop-off in catalyst activity over time, and decreases the levels of by-products produced.
- the total content of elements other than Cu, Zn, Al and O in the catalyst is ⁇ 1 wt%.
- the content of elements can be determined by inductively coupled plasma mass spectrometry (ICP) or by X-ray fluorescence (XRF).
- the catalyst has a copper surface area of 10-20 m 2 /mL ca t. Copper surface area is measured by the procedure in the examples section. Whilst this surface area per unit volume is lower than some known precipitated catalysts, it is higher than many known catalysts of copper on an alumina support. A supported alumina catalyst containing copper and zinc, with a copper surface area per unit volume within this range has a high activity for the hydrogenolysis of esters. In a preferred embodiment the catalyst has a copper surface area of 11-17 m 2 /mL ca t.
- alumina is not intended to encompass silica-aluminas.
- the silicon content of the alumina used herein is ⁇ 5 wt%, preferably ⁇ 2 wt% such as ⁇ 1 wt%.
- Alumina takes on various different forms depending on the temperature to which it has been calcined.
- the support is preferably a-alumina, y-alumina or 0-alumina, or a mixture thereof.
- the alumina may be a single form or a mixture of different forms.
- the alumina support is y-alumina.
- the catalyst is in the form of granules, spheres or multi-lobe shapes such as trilobes.
- Such catalysts can be prepared by impregnating an alumina support in the form of granules, spheres or multi-lobe shapes such as trilobes. It is preferred that the support (and the catalyst) is in the form of trilobes.
- the catalysts described herein may be prepared by impregnation of an alumina support.
- the catalysts may be manufactured by co-impregnation using a solution containing a copper salt and a zinc salt, or by sequential impregnation using a solution containing a copper salt and a separate solution containing a zinc salt (in any order).
- the coimpregnation method is preferred.
- Impregnation techniques will be well known to those skilled in the art. Typically, an impregnation involves preparing an impregnation solution comprising the salt(s) to be impregnated and adding a volume of impregnation solution to the support, in which the volume of impregnation solution is approximately equal to the absorption volume of the support.
- a preferred copper salt is copper carbonate, which may be provided as a solution of copper carbonate in ammonium hydroxide for impregnation.
- a preferred zinc salt is zinc carbonate, which may be provided as a solution of zinc carbonate in ammonium hydroxide for impregnation. It is particularly preferred that the copper salt and zinc salt are provided in the same solution and that the metals are applied on the support using a co-impregnation method.
- step (ii) Following the impregnation step (i) the product is dried (step (ii)). If desired steps (i) and (ii) may be repeated two or more times; this may be desirable if loadings of Cu and Zn towards the higher end of the range are required.
- a calcination step (step (iii)) is carried out once all of the required metal(s) have been impregnated onto the support.
- Typical calcination conditions are 200-400 °C for 4 h ⁇ 2 h. The skilled person will readily be able to determine calcination conditions, which may vary depending on scale and equipment used.
- the catalysts described herein are suitable for the hydrogenolysis of ester substrates to the corresponding acid and alcohol.
- Preferred substrates are the esters of C6-C22 fatty acids, such as the esters of C8-C20 fatty acids.
- the fatty acid component of the ester may be saturated or unsaturated and may be linear or branched.
- the ester is preferably a methyl ester.
- ⁇ 40 g of catalyst was weighed into a 3 cm diameter measuring cylinder and tapped 2000 times using a jolt bulk density meter, the volume of the catalyst was then recorded. The density was calculated by dividing the mass charged with the volume recorded.
- Copper surface areas were determined using reverse frontal chromatography as follows: oxidic catalyst particles were crushed and sieved to a particle size of 0.6 to 1.0 mm. About 2.0 g of the crushed material was weighed into a stainless-steel tube and heated to 68°C and purged with helium for 2 minutes. Then, the catalyst was reduced by heating it in a flow of 5 %vol hydrogen in helium, at 4°C/min up to 230 °C and holding at this temperature for 30 minutes until fully reduced. The reduced catalyst was cooled to 68 °C under helium. The reduced catalyst then had a 2.5%vol N2O in helium gas mixture passed over the catalyst. The evolved gases were passed through a gas chromatograph and the N2 evolution measured.
- the copper surface area per gram of charged catalyst was calculated (m 2 /g ca t) and then multiplied by the tapped bulk density (g ca t/mL) to give copper surface area per mL (m 2 /mL ca t).
- Crush strength was measured using an Engineering systems CT6 instrument. A crush speed of 22 mm/min was used with a 50 kg load cell. 20 catalyst particles were analysed radially and the average value calculated.
- the gas was changed to 100% hydrogen and metered into the rig at 2.8 L/min.
- Methyl laurate was introduced at a flow rate of 0.375 mL/min once a reactor pressure of 250 barg was achieved. This equates to a 82: 1 H 2 :ester molar ratio and an LHSV of 2.25 hr 1 .
- the reactor oil jacket temperature was maintained at 215°C. These conditions were held for 168 hours with online GC analysis completed throughout.
- the flow of hydrogen and methyl laurate was then reduced to 1.2 L/min and 0.167 mL/min respectively resulting in an LHSV of 1.0 hr 1 but with retention of the H2 : ester ratio.
- the temperature of the oil jacket was increased and allowed to stabilise at the following temperatures for ⁇ 5 hours with online GC analysis of the product completed at each temperature: 215, 220 and 225°C.
- Oven 50°C for 0.5 min, 220°C @10°C/min, 300°C @5°C/min with a 15 min hold Detector: 325°C.
- C3 was prepared following a procedure adapted from WO99/51340A1.
- An impregnation solution was prepared by dissolving 211.39 g of ammonium carbonate, 253.57 g of basic copper carbonate in 800 mL of ammonium hydroxide. 50 g of 2.5 mm diameter gamma alumina trilobes were impregnated with the solution until all pores were filled. This was dried at 120°C for four hours before being impregnated a second time. Once all of the pores were filled with the impregnation solution the sample was dried at 120°C for four hours and then calcined at 300°C for four hours. The sample was analysed to contain 14.5 wt.% Cu and 41 .1 wt.% Al by XRF and have a copper surface area of 5.8 m 2 /mL ca t.
- the catalyst was prepared in the same manner as C3 with an impregnation solution consisting of 317.09 g of ammonium carbonate, 194.20 g of basic copper carbonate and 189.47 g of basic zinc carbonate in 1200 mL of ammonium hydroxide.
- the sample was analysed to contain 8.5 wt.% Cu, 8.4 wt.% Zn and 37.6 wt.% Al by XRF and have a copper surface area of 12.0 m 2 /mL ca t.
- Example 5 (Comparative) - Cu and Zn on zinc oxide prepared by impregnation (C5)
- the catalyst was prepared following the same procedure as E4 but using KATALCOTM 32- 4, a 3-4 mm zinc oxide sphere, instead of the alumna trilobes.
- the sample was analysed to contain 7.0 wt.% Cu, 60.2 wt.% Zn and 1.4 wt.% Al by XRF and have a copper surface area of 8.2 m 2 /mL ca t.
- the catalyst was prepared in the same manner as C3 with an impregnation solution consisting of 52.85 g of ammonium carbonate, 26.54 g of basic copper carbonate and 37.26 g of basic zinc carbonate in 200 mL of ammonium hydroxide. Three impregnations were applied instead of two. The sample was analysed to contain 9.0 wt.% Cu, 13.0 wt.% Zn and 35.3 wt.% Al by XRF and have a copper surface area of 10.3 m 2 /mL ca t.
- Example 7 (Comparative) - Cu and Zn on silica prepared by impregnation (C7)
- the catalyst was prepared in the same manner as C3 but using CARiACT Q-20C, a 4 mm silica dioxide sphere supplied by Fuji Silysia, instead of the alumna trilobes.
- the sample was analysed to contain 8.3 wt.% Cu, 8.7 wt.% Zn and 34.3 wt.% Si by XRF and have a copper surface area of 2.5 m 2 /mL C at.
- Example 8 (Comparative) - Cu on alumina prepared by impregnation using copper nitrate (C8)
- An impregnation solution was prepared by dissolving 27.9 g of copper nitrate hemipentahydrate in deionised water to a volume of 26.6 mL . 50 g of 2.5 mm diameter delta/theta alumina trilobes were impregnated with the solution until all pores were filled. This was dried at 120°C for four hours and then calcined at 300°C for four hours. The sample was analysed to contain 15.8 wt.% Cu by XRF and have a copper surface area of 4.4 m 2 /mLcat.
- Example 9 (Comparative) - Cu on alumina prepared by impregnation using copper carbonate (C9)
- the catalyst was prepared following the same procedure as E4 but using 2.5 mm diameter delta/theta alumna trilobes, instead of gamma alumina.
- the sample was analysed to contain 17.8 wt.% Cu by XRF and have a copper surface area of 5.4 m 2 /mL ca t.
- the Cu loading of C9 was -13% higher than C8 but the Cu surface area was -23% higher. This demonstrates that the use of copper carbonate instead of copper nitrate as the salt for the impregnation may be used to produce catalysts with comparably higher copper surface area.
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Abstract
The specification describes a process for the hydrogenolysis of an ester substrate, comprising the step of carrying out hydrogenolysis of the ester substrate in the presence of a heterogeneous catalyst, wherein the catalyst comprises: 5-20 wt% copper and 5-12 wt% zinc; on an alumina support; wherein the total content of elements other than Cu, Zn, Al and O is ≤ 1 wt%. Also described are oxidic catalyst for the hydrogenolysis of an ester substrate, wherein the catalyst comprises: 5-20 wt% copper and 5-12 wt% zinc; on an alumina support; wherein the catalyst has a copper surface area of 10-20 m2/mLcat; and wherein the total content of elements other than Cu, Zn, Al and O is ≤ 1 wt%. Also described is a method of preparing such oxidic catalysts.
Description
Copper-containing hydrogenation catalysts for the hydrogenolysis of esters
Field of the Invention
The present invention relates to copper-containing hydrogenation catalysts and their use in the hydrogenolysis of esters.
Background
Catalytic hydrogenolysis of esters is a commercially important reaction. The hydrogenolysis reaction is:
RCOOR’ + 2H2 RCH2OH + R’OH
Fatty alcohols are useful feedstocks, in particular for the production of surfactants and detergents. One process for the production of fatty alcohols is through the hydrogenolysis of acid methyl esters (FAMEs) which are usually derived from triglycerides found in animal fats and vegetable oils.
The hydrogenolysis or hydrogenation of FAME feedstocks using catalysts containing copper and chromium has been described in the prior art, for example in US2091800. WO91/04789 describes an acid-resistant copper chromite catalyst material containing promoter metal compounds as well as colloidal silicic acid, and a process for their production and use for direct fixed-bed hydration of fatty acids to produce fatty alcohols of appropriate chain-length. Due to the toxicity of some chromium species, there has been much research into chromium-free catalysts for ester hydrogenolysis.
JPH1045645A describes a process for the production of cyclohexanedimethanol (CH DM) by a two-stage process. The first stage involves hydrogenating a dialkyl terephthalate in the presence of a noble metal-based nuclear hydrogenation catalyst to produce 1 ,4- cyclohexanedicarboxylic dialkyl ester. The second stage involves hydrogenolysis of the 1 ,4- cyclohexanedicarboxylic dialkyl ester in the presence of a copper-zinc-alumina-based catalyst. A preferred catalyst for the second stage comprises, in oxidic form, 30-70 wt% copper oxide, 20-60 wt% zinc oxide and 3-20 wt% alumina.
The article “Cu-Zn/AhOs Catalyst for the Hydrogenation of Esters to Alcohols” (Chin J Catal, 2010, 31 : 769-775) describes a catalyst with a molar ratio of copper : zinc : alumina of 30 : 40 : 30 which is produced by a high speed collision co-precipitation method. The catalyst contained approximately 51 wt% copper, 10 wt% zinc and 7 wt% aluminium after calcination. The catalyst was tested for its performance in the hydrogenolysis of natural palm oil which has first been transesterified with methanol.
W02005/070537A1 describes chromium-free catalysts comprising copper and at least one second metal which are obtainable through a method involving addition of a solution comprising Cu ions and ions of at least one other second metal to an inert carrier, optional drying, calcining and reduction of at least part of the oxidic copper. The examples use silica, magnesia, zirconia or titania as the support. The catalysts may be used for a number of duties, including the hydrogenation of fatty acids, fatty esters, esters and diesters to fatty alcohols, alcohols and dialcohols respectively.
WO2016/059431 A1 describes catalysts comprising copper, zinc and a silica-alumina material that is not a zeolite. In the examples catalysts are prepared by precipitating copper nitrate and zinc nitrate with sodium carbonate in the presence of a silica-alumina support. The catalysts are tested for their activity in the hydrogenolysis of methyl laurate.
WO2016/154514A1 describes catalysts comprising a mixed metal oxide comprising copper and at least one of manganese, zinc, nickel or cobalt; an alumina; silica; and calcium. The catalysts may be used for a number of duties, including the hydrogenolysis of FAMEs and free fatty acids.
CN1036576567B describes hydrogenation catalysts comprising 3-10 mass% boron oxide, 6-20 mass% zinc oxide, 4-12 mass% copper, on a carrier of gamma alumina with a specific surface area of 180-400 m2/g and a pore volume of 0.2-0.8 cm3/g. The catalysts may be used for a variety of duties including the hydrogenation of FAMEs.
CN105363454B describes hydrogenation catalysts comprising: (a) 10-50 wt% copper or its oxides; (b) 0-20 wt% of a mixture of ZnO and CdO; (c) < 5 wt% of a mixture of P2O5 and Bi2Os; and (d) 40-70 wt% of a carrier selected from at least one of silica, alumina, and a molecular sieve, on the condition that the amount of component (c) is not zero. Comparative
catalyst C1 is 10CuO-15ZnO-75Al2Os and is prepared by co-impregnation of an alumina carrier with a solution containing copper nitrate trihydrate and zinc nitrate hexahydrate. The catalysts may be used for a variety of duties including the hydrogenation of esters.
There is a need for further, improved, ester hydrogenolysis catalysts. Ideally an ester hydrogenolysis catalyst should satisfy the following properties. Firstly, the catalyst should have high activity for the conversion of the ester substrate. Secondly, the catalyst should retain high activity for the conversion of the ester substrate, so that the catalyst does not need to replaced too frequently. Thirdly, the catalyst should have high selectivity for the desired ester hydrogenolysis reaction and produce low levels of by-products. Fourthly, the catalyst should have high crush strength and retain high crush strength during the course of the reaction. The reason for this is that if the crush strength is too low, the catalyst may disintegrate in the reactor resulting in an increase in pressure drop through the reactor, which can cause blockages and requires premature catalyst discharge.
The present invention relates to a catalyst having a good balance of the above properties, and a process of using the catalyst in the hydrogenolysis of esters.
Description of the Figures
Figure 1 is a plot showing substrate conversion (methyl laurate) against copper surface area (m2/mL cat)
Summary of Invention
The present inventors have now found that a catalyst containing copper and zinc on an alumina support provides a catalyst having a good balance between: high activity for ester hydrogenation, retention of activity, low by-product production and good retention of crush strength.
In a first aspect the invention relates to a process for the hydrogenolysis of an ester substrate, comprising the step of carrying out hydrogenolysis of the ester substrate in the presence of a heterogeneous catalyst, wherein the catalyst comprises:
5-20 wt% copper; and
5-12 wt% zinc;
on an alumina support; wherein the total content of elements other than Cu, Zn, Al and O is < 1 wt%.
The copper and zinc contents are measured on the oxidic catalyst by the method described in the examples section. The term “oxidic catalyst” means a catalyst in which substantially all of the Zn and Cu are present as oxides. The catalyst used in the process is in reduced form and is preferably prepared by reducing an oxidic catalyst as defined in the second aspect of the invention.
Once installed in a reactor the oxidic catalyst is typically activated in situ by reducing some or all of the CuO to Cu metal using a feed containing H2. However, the ZnO and alumina are not reduced. The activation may be carried out in the gas phase or the liquid phase. The result is a catalyst in which some or all of the Cu is present as crystallites of Cu(0). Such catalyst is referred to as a “reduced catalyst” herein. An exemplary method for the liquid phase activation of a catalyst is described in W02020/053555 (Johnson Matthey Davy Technologies Limited).
In preferred embodiments the substrate is an ester of a saturated or unsaturated fatty acid.
In a second aspect the invention relates to an oxidic catalyst for the hydrogenolysis of an ester substrate, wherein the catalyst comprises:
5-20 wt% copper; and
5-12 wt% zinc; on an alumina support; wherein the catalyst has a copper surface area of 10-20 m2/mLcat; wherein the total content of elements other than Cu, Zn, Al and O is < 1 wt%.
The copper content, zinc content and copper surface area are measured on the oxidic catalyst by the method described in the examples section.
In a third aspect the invention relates to a method for preparing an oxidic catalyst according to the second aspect, comprising the steps of:
(i) impregnating an alumina support with an impregnation solution comprising copper carbonate and zinc carbonate;
(ii) drying the product of step (i); and
(iii) calcining the product of step (ii).
Detailed Description
Any sub-headings are for convenience only and are not intended to limit the invention.
Any aspect described as being preferred in connection with the catalyst also applies to the catalyst used in the process of the first aspect or prepared by the method of the third aspect.
Catalyst
The catalyst comprises 5-20 wt% copper. This loading of copper is lower than many known precipitated copper catalysts. A low content of copper is preferred from a cost perspective. A preferred copper content is 5-12 wt% as this gives a good balance between activity and cost.
The catalyst comprises 5-12 wt% zinc. The inclusion of zinc not only improves the catalyst activity in absolute terms, but also reduces the drop-off in catalyst activity over time, and decreases the levels of by-products produced. High zinc contents, namely above 12 wt%, whilst still providing a more active and selective catalyst compared to a copper on alumina catalyst, lead to a decrease in catalyst activity.
The total content of elements other than Cu, Zn, Al and O in the catalyst is < 1 wt%. The content of elements can be determined by inductively coupled plasma mass spectrometry (ICP) or by X-ray fluorescence (XRF).
Whilst the contents copper, zinc and alumina will not be identical between the oxidic form and reduced form of the catalyst, given the relatively low levels of Cu and Zn in the catalysts of the present invention, they will be similar. The values of Cu, Zn and “total content of elements other than Cu, Zn, Al and O” therefore apply to both the oxidic catalyst and the reduced catalyst.
In a preferred embodiment the catalyst has a copper surface area of 10-20 m2/mLcat. Copper surface area is measured by the procedure in the examples section. Whilst this surface area per unit volume is lower than some known precipitated catalysts, it is higher than many known catalysts of copper on an alumina support. A supported alumina catalyst containing
copper and zinc, with a copper surface area per unit volume within this range has a high activity for the hydrogenolysis of esters. In a preferred embodiment the catalyst has a copper surface area of 11-17 m2/mLcat.
The copper and zinc are supported on an alumina support. As used herein, the term “alumina” is not intended to encompass silica-aluminas. The silicon content of the alumina used herein is < 5 wt%, preferably < 2 wt% such as < 1 wt%.
Alumina takes on various different forms depending on the temperature to which it has been calcined. The support is preferably a-alumina, y-alumina or 0-alumina, or a mixture thereof. The alumina may be a single form or a mixture of different forms. In a preferred embodiment the alumina support is y-alumina.
It is preferred that the catalyst is in the form of granules, spheres or multi-lobe shapes such as trilobes. Such catalysts can be prepared by impregnating an alumina support in the form of granules, spheres or multi-lobe shapes such as trilobes. It is preferred that the support (and the catalyst) is in the form of trilobes.
Manufacture of the catalyst
The catalysts described herein may be prepared by impregnation of an alumina support. The catalysts may be manufactured by co-impregnation using a solution containing a copper salt and a zinc salt, or by sequential impregnation using a solution containing a copper salt and a separate solution containing a zinc salt (in any order). The coimpregnation method is preferred.
Impregnation techniques will be well known to those skilled in the art. Typically, an impregnation involves preparing an impregnation solution comprising the salt(s) to be impregnated and adding a volume of impregnation solution to the support, in which the volume of impregnation solution is approximately equal to the absorption volume of the support.
A preferred copper salt is copper carbonate, which may be provided as a solution of copper carbonate in ammonium hydroxide for impregnation.
A preferred zinc salt is zinc carbonate, which may be provided as a solution of zinc carbonate in ammonium hydroxide for impregnation.
It is particularly preferred that the copper salt and zinc salt are provided in the same solution and that the metals are applied on the support using a co-impregnation method.
Following the impregnation step (i) the product is dried (step (ii)). If desired steps (i) and (ii) may be repeated two or more times; this may be desirable if loadings of Cu and Zn towards the higher end of the range are required.
A calcination step (step (iii)) is carried out once all of the required metal(s) have been impregnated onto the support. Typical calcination conditions are 200-400 °C for 4 h ± 2 h. The skilled person will readily be able to determine calcination conditions, which may vary depending on scale and equipment used.
Hydrogenolysis process
The catalysts described herein are suitable for the hydrogenolysis of ester substrates to the corresponding acid and alcohol. Preferred substrates are the esters of C6-C22 fatty acids, such as the esters of C8-C20 fatty acids. The fatty acid component of the ester may be saturated or unsaturated and may be linear or branched. The ester is preferably a methyl ester.
Examples
Analytical procedures
Tapped bulk density
~40 g of catalyst was weighed into a 3 cm diameter measuring cylinder and tapped 2000 times using a jolt bulk density meter, the volume of the catalyst was then recorded. The density was calculated by dividing the mass charged with the volume recorded.
Copper surface area
Copper surface areas were determined using reverse frontal chromatography as follows: oxidic catalyst particles were crushed and sieved to a particle size of 0.6 to 1.0 mm. About 2.0 g of the crushed material was weighed into a stainless-steel tube and heated to 68°C and purged with helium for 2 minutes. Then, the catalyst was reduced by heating it in a flow of 5 %vol hydrogen in helium, at 4°C/min up to 230 °C and holding at this temperature for 30 minutes until fully reduced. The reduced catalyst was cooled to 68 °C under helium.
The reduced catalyst then had a 2.5%vol N2O in helium gas mixture passed over the catalyst. The evolved gases were passed through a gas chromatograph and the N2 evolution measured.
The copper surface area per gram of charged catalyst was calculated (m2/gcat) and then multiplied by the tapped bulk density (gcat/mL) to give copper surface area per mL (m2/mLcat).
Strength
Crush strength was measured using an Engineering systems CT6 instrument. A crush speed of 22 mm/min was used with a 50 kg load cell. 20 catalyst particles were analysed radially and the average value calculated.
Catalyst testing procedure
10 mL of catalyst, based on the tapped bulk density, was charged to a stainless-steel reactor in the presence of 45 g fine (0.1 -0.3 mm) silicon carbide. Silicon carbide was also added above and below the catalyst. The catalysts were activated in a 0.5 L/min flow of 5% hydrogen in nitrogen at 0.6 barg by heating to 240°C at a rate of 1°C/min and holding at these conditions for four hours before reducing the reactor to 215°C and commencing the catalyst test program.
The gas was changed to 100% hydrogen and metered into the rig at 2.8 L/min. Methyl laurate was introduced at a flow rate of 0.375 mL/min once a reactor pressure of 250 barg was achieved. This equates to a 82: 1 H2:ester molar ratio and an LHSV of 2.25 hr1. The reactor oil jacket temperature was maintained at 215°C. These conditions were held for 168 hours with online GC analysis completed throughout. The flow of hydrogen and methyl laurate was then reduced to 1.2 L/min and 0.167 mL/min respectively resulting in an LHSV of 1.0 hr1 but with retention of the H2 : ester ratio. The temperature of the oil jacket was increased and allowed to stabilise at the following temperatures for ~5 hours with online GC analysis of the product completed at each temperature: 215, 220 and 225°C.
The liquid flow was then isolated with all other conditions maintained for ~2 hours to purge the system/catalyst of liquid. The reactors were then cooled to room temperature, purged with 5 % hydrogen in nitrogen before being vacuum discharged. The discharged catalyst was analysed for strength and compared to the fresh.
GC Analysis
Online GC analysis was completed using a Bruker 456 GC to determine concentrations of the following components:
Methanol, Octene, Octane, Hexanol, Nonane, Heptanol, Decene, Decane, Octanal, Octyl methyl ether, Octanol, 2-Nonanone, 2-Nonanol, Methyl octanoate, Octanoic acid, Nonanol, Dodecene, Dodecane, Decanal, Decyl methyl ether, Decanol, 2-Undecanone, 2- Undecanol, Methyl decanoate, Decanoic acid, Undecanol, Tetradecene, Tetradecane, Dodecanal, Dodecyl methyl ether, Dodecanol, Pentadecane, Methyl dodecanoate, Dodecanoic acid, C16 wax ether, 016 wax ester, 018 wax ether, 018 wax ester, 020 wax ether, 020 wax ester, 022 wax ether, 022 wax ester, 024 wax ether, 024 wax ester.
Each component was calibrated for using an external standard; any unknowns were estimated using the response factor for dodecanol.
GC parameters
Column: CP-Sil 8 CB 50m 0.32mm 1.2um
Injector: 250°C
Split 30:1
Column flow 2.0 ml/min (constant flow)
Oven: 50°C for 0.5 min, 220°C @10°C/min, 300°C @5°C/min with a 15 min hold Detector: 325°C.
Example 1 (Comparative) - Cu and Zn precipitated catalyst (C1)
C1 was prepared following the procedure described in Example 1 of WO2016/059431 A1.
Example 2 (Comparative) - Cu and Zn precipitated catalyst (C2)
C2 was a commercially available precipitated catalyst PRICAT™ CZ 40/18T (Johnson Matthey).
Example 3 (Comparative) - Cu on alumina prepared by impregnation (C3)
C3 was prepared following a procedure adapted from WO99/51340A1.
An impregnation solution was prepared by dissolving 211.39 g of ammonium carbonate, 253.57 g of basic copper carbonate in 800 mL of ammonium hydroxide. 50 g of 2.5 mm diameter gamma alumina trilobes were impregnated with the solution until all pores were filled. This was dried at 120°C for four hours before being impregnated a second time. Once all of the pores were filled with the impregnation solution the sample was dried at 120°C for four hours and then calcined at 300°C for four hours. The sample was analysed to contain 14.5 wt.% Cu and 41 .1 wt.% Al by XRF and have a copper surface area of 5.8 m2/mLcat.
Example 4 - Cu and Zn on alumina prepared by impregnation (E4)
The catalyst was prepared in the same manner as C3 with an impregnation solution consisting of 317.09 g of ammonium carbonate, 194.20 g of basic copper carbonate and 189.47 g of basic zinc carbonate in 1200 mL of ammonium hydroxide. The sample was analysed to contain 8.5 wt.% Cu, 8.4 wt.% Zn and 37.6 wt.% Al by XRF and have a copper surface area of 12.0 m2/mLcat.
Example 5 (Comparative) - Cu and Zn on zinc oxide prepared by impregnation (C5)
The catalyst was prepared following the same procedure as E4 but using KATALCO™ 32- 4, a 3-4 mm zinc oxide sphere, instead of the alumna trilobes. The sample was analysed to contain 7.0 wt.% Cu, 60.2 wt.% Zn and 1.4 wt.% Al by XRF and have a copper surface area of 8.2 m2/mLcat.
Example 6 - Cu and Zn on alumina prepared by impregnation (E6)
The catalyst was prepared in the same manner as C3 with an impregnation solution consisting of 52.85 g of ammonium carbonate, 26.54 g of basic copper carbonate and 37.26 g of basic zinc carbonate in 200 mL of ammonium hydroxide. Three impregnations were applied instead of two. The sample was analysed to contain 9.0 wt.% Cu, 13.0 wt.% Zn and 35.3 wt.% Al by XRF and have a copper surface area of 10.3 m2/mLcat.
Example 7 (Comparative) - Cu and Zn on silica prepared by impregnation (C7)
The catalyst was prepared in the same manner as C3 but using CARiACT Q-20C, a 4 mm silica dioxide sphere supplied by Fuji Silysia, instead of the alumna trilobes. The sample
was analysed to contain 8.3 wt.% Cu, 8.7 wt.% Zn and 34.3 wt.% Si by XRF and have a copper surface area of 2.5 m2/mLCat.
Not measured. The catalyst had low activity and conversion had dropped to 52.1% after 23 hours.
E4 and E6 showed an excellent balance between:
(1) activity for hydrogenolysis;
(2) prolonged activity, as measured by the absolute value of conversion after 150 h and % of the conversion at 10 h;
(3) level of by-products, especially when compared to an impregnated catalyst on alumina but without Zn addition (C3);
(4) good absolute strength and strength retention.
Example 8 (Comparative) - Cu on alumina prepared by impregnation using copper nitrate (C8)
An impregnation solution was prepared by dissolving 27.9 g of copper nitrate hemipentahydrate in deionised water to a volume of 26.6 mL . 50 g of 2.5 mm diameter delta/theta alumina trilobes were impregnated with the solution until all pores were filled. This was dried at 120°C for four hours and then calcined at 300°C for four hours. The sample was analysed to contain 15.8 wt.% Cu by XRF and have a copper surface area of 4.4 m2/mLcat.
Example 9 (Comparative) - Cu on alumina prepared by impregnation using copper carbonate (C9)
The catalyst was prepared following the same procedure as E4 but using 2.5 mm diameter delta/theta alumna trilobes, instead of gamma alumina. The sample was analysed to contain 17.8 wt.% Cu by XRF and have a copper surface area of 5.4 m2/mLcat.The Cu loading of C9 was -13% higher than C8 but the Cu surface area was -23% higher. This demonstrates that the use of copper carbonate instead of copper nitrate as the salt for the impregnation may be used to produce catalysts with comparably higher copper surface area.
Claims
1. A process for the hydrogenolysis of an ester substrate, comprising the step of carrying out hydrogenolysis of the ester substrate in the presence of a heterogeneous catalyst, wherein the catalyst comprises:
5-20 wt% copper; and
5-12 wt% zinc; on an alumina support; wherein the total content of elements other than Cu, Zn, Al and O is < 1 wt%.
2. A process according to claim 1 , wherein the catalyst comprises 5-12 wt% copper.
3. A process according to claim 1 or claim 2, wherein the alumina support is a- alumina, y-alumina or 0-alumina or a mixture thereof.
4. A process according to any of claims 1 to 3, wherein the alumina support is in the form of granules, spheres or multi-lobe shapes.
5. A process according to any of claims 1 to 4, wherein the alumina support is in the form of trilobes.
6. A process according to any of claims 1 to 5, wherein the ester substrate is an ester of a fatty acid.
7. A process according to any of claims 1 to 6, wherein the ester substrate is an ester of a C6-C22 fatty acid.
8. A process according to any of claims 1 to 7, wherein the ester substrate is a methyl ester.
9. A process according to any of claims 1 to 8, wherein the catalyst is prepared by reducing an oxidic catalyst according to any of claims 10 to 14.
10. An oxidic catalyst for the hydrogenolysis of an ester substrate, wherein the catalyst comprises:
5-20 wt% copper; and
5-12 wt% zinc;
on an alumina support; wherein the catalyst has a copper surface area of 10-20 m2/mLcat; and wherein the total content of elements other than Cu, Zn, Al and O is < 1 wt%.
11. An oxidic catalyst according to claim 10, wherein the catalyst comprises 5-12 wt% copper.
12. An oxidic catalyst according to claim 10 or claim 11 , wherein the alumina support is a-alumina, y-alumina or 0-alumina or a mixture thereof.
13. An oxidic catalyst according to any of claims 10 to 12, wherein the alumina support is in the form of granules, spheres or multi-lobe shapes.
14. An oxidic catalyst according to any of claims 10 to 12, wherein the alumina support is in the form of trilobes.
15. A method for preparing an oxidic catalyst according to any of claims 10 to 14, comprising the steps of: (i) impregnating an alumina support with an impregnation solution comprising copper carbonate and zinc carbonate;
(ii) drying the product of step (i); and
(iii) calcining the product of step (ii).
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GBGB2213961.2A GB202213961D0 (en) | 2022-09-23 | 2022-09-23 | Copper-containing hydrogenation catalysts for the hydrogenolysis of esters |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2091800A (en) | 1931-09-15 | 1937-08-31 | Rohm & Haas | Method of hydrogenating esters |
WO1991004789A1 (en) | 1989-10-04 | 1991-04-18 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing acid-resistant catalysts for the direct hydration of carboxylic acids into alcohols |
WO1999051340A1 (en) | 1998-04-03 | 1999-10-14 | Imperial Chemical Industries Plc | Copper-containing materials |
WO2005070537A1 (en) | 2004-01-21 | 2005-08-04 | Avantium International B.V. | Chromium-free catalysts of metalic cu and at least one second metal |
CN103657656A (en) | 2013-12-02 | 2014-03-26 | 唐雅蓉 | Preparation method of nickel-based catalyst |
CN105363454A (en) | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst |
WO2016059431A1 (en) | 2014-10-17 | 2016-04-21 | Johnson Matthey Public Limited Company | Catalyst and process |
WO2016154514A1 (en) | 2015-03-26 | 2016-09-29 | Basf Corporation | Hydrogenolysis catalysts with high acid tolerance |
WO2020053555A1 (en) | 2018-09-10 | 2020-03-19 | Johnson Matthey Davy Technologies Limited | Process for the activation of oxidised catalysts |
Family Cites Families (1)
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CN106140172A (en) * | 2015-03-24 | 2016-11-23 | 南京博明科技有限责任公司 | A kind of catalyst pressing liquid-phase hydrogenatin fatty alcohol be applicable to fatty acid methyl ester |
-
2022
- 2022-09-23 GB GBGB2213961.2A patent/GB202213961D0/en not_active Ceased
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2023
- 2023-06-29 GB GB2309826.2A patent/GB2622667A/en active Pending
- 2023-06-29 WO PCT/GB2023/051692 patent/WO2024062209A1/en unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2091800A (en) | 1931-09-15 | 1937-08-31 | Rohm & Haas | Method of hydrogenating esters |
WO1991004789A1 (en) | 1989-10-04 | 1991-04-18 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing acid-resistant catalysts for the direct hydration of carboxylic acids into alcohols |
WO1999051340A1 (en) | 1998-04-03 | 1999-10-14 | Imperial Chemical Industries Plc | Copper-containing materials |
WO2005070537A1 (en) | 2004-01-21 | 2005-08-04 | Avantium International B.V. | Chromium-free catalysts of metalic cu and at least one second metal |
CN103657656A (en) | 2013-12-02 | 2014-03-26 | 唐雅蓉 | Preparation method of nickel-based catalyst |
CN105363454A (en) | 2014-08-27 | 2016-03-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst |
WO2016059431A1 (en) | 2014-10-17 | 2016-04-21 | Johnson Matthey Public Limited Company | Catalyst and process |
WO2016154514A1 (en) | 2015-03-26 | 2016-09-29 | Basf Corporation | Hydrogenolysis catalysts with high acid tolerance |
WO2020053555A1 (en) | 2018-09-10 | 2020-03-19 | Johnson Matthey Davy Technologies Limited | Process for the activation of oxidised catalysts |
Non-Patent Citations (3)
Title |
---|
"Cu-Zn/A1 0 Catalyst for the Hydrogenation of Esters to Alcohols", CHIN J CATAL, vol. 31, 2010, pages 769 - 775 |
LIANG SHUGUANG ET AL: "Hydrogenation of methyl laurate to produce lauryl alcohol over Cu/ZnO/Al2O3 with methanol as the solvent and hydrogen source", PURE & APPLIED CHEMISTRY, vol. 84, no. 3, 5 November 2011 (2011-11-05), GB, pages 779 - 788, XP093076372, ISSN: 0033-4545, DOI: 10.1351/PAC-CON-11-06-09 * |
LINDSTROM B ET AL: "Activity and characterization of Cu/Zn, Cu/Cr and Cu/Zr on @c-alumina for methanol reforming for fuel cell vehicles", APPLIED CATALYSIS A: GENERAL, ELSEVIER, AMSTERDAM, NL, vol. 234, no. 1-2, 8 August 2002 (2002-08-08), pages 111 - 125, XP004370580, ISSN: 0926-860X, DOI: 10.1016/S0926-860X(02)00202-8 * |
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