CN107073457A - 挤出的Cu‑Al‑Mn氢化催化剂 - Google Patents
挤出的Cu‑Al‑Mn氢化催化剂 Download PDFInfo
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- CN107073457A CN107073457A CN201580048617.3A CN201580048617A CN107073457A CN 107073457 A CN107073457 A CN 107073457A CN 201580048617 A CN201580048617 A CN 201580048617A CN 107073457 A CN107073457 A CN 107073457A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 178
- 238000001125 extrusion Methods 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 28
- 238000000465 moulding Methods 0.000 claims abstract description 85
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 73
- 239000010949 copper Substances 0.000 claims description 52
- 239000013049 sediment Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 239000005749 Copper compound Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 23
- 150000001880 copper compounds Chemical class 0.000 claims description 23
- 150000002697 manganese compounds Chemical class 0.000 claims description 22
- 150000001399 aluminium compounds Chemical class 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 20
- 229910001593 boehmite Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001935 peptisation Methods 0.000 claims description 12
- 125000005587 carbonate group Chemical group 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052753 mercury Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 210000002320 radius Anatomy 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000007561 laser diffraction method Methods 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 17
- 150000002148 esters Chemical class 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001299 aldehydes Chemical class 0.000 abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 6
- 150000002576 ketones Chemical class 0.000 abstract description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 22
- -1 copper aluminate Chemical class 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 229910000765 intermetallic Inorganic materials 0.000 description 18
- 229910001868 water Inorganic materials 0.000 description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229960004643 cupric oxide Drugs 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 235000012222 talc Nutrition 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910018131 Al-Mn Inorganic materials 0.000 description 4
- 229910018461 Al—Mn Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
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- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical group CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910018576 CuAl2O4 Inorganic materials 0.000 description 2
- 229910016526 CuMn2O4 Inorganic materials 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000011646 cupric carbonate Substances 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 229910001677 galaxite Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002477 CuCr2O4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- WPEMTESADRAQNQ-UHFFFAOYSA-L [Cu].O[Cr](O)=O Chemical compound [Cu].O[Cr](O)=O WPEMTESADRAQNQ-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 description 1
- FULFYAFFAGNFJM-UHFFFAOYSA-N oxocopper;oxo(oxochromiooxy)chromium Chemical compound [Cu]=O.O=[Cr]O[Cr]=O FULFYAFFAGNFJM-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
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- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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Abstract
本发明涉及挤出形式的Cu‑Al‑Mn催化剂成形体及其制备方法。所述催化剂成形体适用于氢化包含羰基官能的有机化合物,特别是适用于氢化醛、酮以及羧酸或其酯。所述催化剂成形体非常特别适合于将脂肪酸或其酯如脂肪酸甲酯氢化成相应的醇,并且适合于将二羧酸酐如马来酸酐(MSA)或二元酸的酯氢化成二元醇如丁二醇。
Description
本发明涉及挤出形式的Cu-Al-Mn催化剂成形体及其制备方法。所述催化剂成形体适用于氢化包含羰基官能的有机化合物,特别是氢化醛、酮以及羧酸或其酯。优选将脂肪酸或其酯如脂肪酸甲酯氢化成相应的醇,和将二羧酸酐如马来酸酐(MSA)或二元酸的酯氢化成二元醇如丁二醇。
背景技术
通常将片状催化剂用于氢化反应。片状催化剂的特征在于以侧压强度的形式确定的高机械稳定性。稳定性源于压片时的相对高的压力。由此使粉末状起始材料紧密压实并且产生具有相对高的堆积密度的片剂。此外,通过紧密压实使得孔体积减小,因此难以到达活性中心。因此只有一部分活性金属组分可以用于反应。
现有技术中已知挤出形式的催化剂,其中通过添加一定量的合适粘结剂并且借助挤出成相应的催化剂成形体从而加工粉末状起始材料。相比于由相同粉末状起始材料制备的片剂,挤出物通常具有更高的孔体积。
现有技术中已知的挤出形式的催化剂与根据本发明的催化剂的区别特别在于组成,例如所使用的金属和粘结剂类型,以及物理化学性质。
US 5 977 010描述了一种催化剂成形体,所述催化剂成形体包含(i)至少一种选自铜、锰、锌、镍、钴和铁的金属和此外的(ii)硅酸钙和(iii)至少一种粘土材料。所述成形的催化剂用于氢化醛、酮、羧酸和羧酸酯。
WO 92/10290公开了亚铬酸铜催化剂的成形体,所述成形体由约20至80重量%的亚铬酸铜和20至80重量%的至少一种可挤出的无机粘结剂材料的混合物形成。所述催化剂具有20至225m2/g的表面积和介于0.35和1cm3/g之间的总孔体积。所述文献描述了通过挤出亚铬酸铜、可挤出的无机粘结剂材料、胶溶剂和水的混合物并且煅烧挤出物从而制备成形的亚铬酸铜催化剂的方法。获得的成形体用于氢化醛、酮、羧酸和羧酸酯。
US 4 666 879描述了一种挤出的亚铬酸铜-氧化铝催化剂,所述催化剂通过混合40至82重量%的亚铬酸铜和18至60%的典型地具有拟勃姆石结构或α-羟基勃姆石结构的可挤出的氧化铝而制得。挤出的催化剂可以在煅烧之后用于氢化各种液相或气相羰基化合物。所述催化剂具有介于20和225m2/g之间的表面积和介于0.70和1.20g/cm3之间的堆积密度。
WO 2006/005505描述了使用含铜催化剂片剂或催化剂挤出物氢化有机羰基官能的化合物的方法,所述片剂或挤出物具有<2.5mm的直径。通过成形然后煅烧50至80重量%氧化铜、15至35重量%氧化铝、2至20重量%氧化镧和铜片的混合物制备所述催化剂。
在卡尔斯鲁厄大学(TH)Steffen P.Müller的2005年的博士论文中描述了挤出形式的Cu/Zn催化剂,所述催化剂通过使用基于勃姆石的粘结剂而制得。
WO 2005/058491中公开了挤出物形式的含CuO/Al2O3的催化剂成形体。通过混合用甲酸浸蚀的勃姆石与含CuO/Al2O3的活性物料和水制备所述催化剂。然后将混合物挤出成条并且在600℃煅烧。所述催化剂具有介于790和960g/l之间的堆积密度和0.31至0.59cm3/g范围内的孔体积。
相比于催化剂片剂,挤出物通常具有例如体现为低侧压强度的低机械稳定性。此外,挤出物中使用的粘结剂通常对催化剂效率具有负面影响。主要影响参数是粘结剂基质的固有活性、表面酸度的变化和基质中的扩散效应。例如K.P.de Jong的“Synthesis ofsolid catalysts”(2009,Wiley-VCH出版社,第175页)或J.Freiding的博士论文“Extrusion von technischen ZSM-5-Kontakten und ihre Anwendung im MTO-Prozess”(卡尔斯鲁厄大学(TH),2009,特别是第2.5章和第5.6章)中描述了所述效应。因此DE 102006 058800中明确要求保护尽可能纯的催化剂成形体,从而避免源自催化剂基质的负面效应。
本发明的目的是提供催化剂成形体,所述催化剂成形体不具有催化剂片剂和催化剂挤出物的上述缺点,即相比于常规压片的催化剂具有明显更高的孔体积和明显更低的堆积密度和至少相当的稳定性和活性。
根据本发明通过如下方式实现所述目的,在将粉末状催化剂材料加工成挤出物时使用特定粘结剂,所述特定粘结剂造成稳定的催化剂成形体。通过使用粘结剂(所述粘结剂造成稳定的成形体同时产生高的孔体积)将粉末状催化剂材料加工成挤出物,可以产生相比于常规压片催化剂具有相当的稳定性和明显更高孔体积的催化剂成形体。
发明简述
本发明涉及挤出形式的催化剂成形体,包含在20-43重量%范围内,优选在25-42重量%范围内的量的Cu,在20-40重量%范围内,优选在25-34重量%范围内的量的Al,和在1-10重量%范围内,优选在2-8重量%范围内,特别优选在3-6重量%范围内的量的Mn,基于挤出形式的催化剂成形体的总重量计,其中催化剂成形体具有根据DIN 66133通过压汞法测定的在250至700mm3/g范围内,优选在400至650mm3/g范围内,特别优选在450至600mm3/g范围内的孔体积。
本发明还涉及用于制备挤出形式的含Cu、Al和Mn的催化剂成形体(Cu-Al-Mn催化剂成形体)的方法,其中所述方法包括如下步骤:
(a)组合(i)铜化合物、铝化合物、锰化合物和任选的过渡金属化合物的至少一种水溶液和(ii)至少一种含碳酸盐的水溶液从而形成沉淀物,分离沉淀物,任选洗涤分离的沉淀物并且干燥分离的沉淀物从而获得干燥的沉淀物,
(b)混合步骤(a)中获得的干燥的沉淀物与含铝粘结剂,所述含铝粘结剂选自勃姆石和拟勃姆石,
(c)挤出步骤(b)中获得的混合物从而获得挤出物,并且
(d)在300℃至750℃范围内,优选在600℃至750℃范围内,特别是约750℃的温度下煅烧步骤(c)中获得的挤出物从而获得挤出的成形体。
本发明还涉及根据本发明的Cu-Al-Mn催化剂用于氢化有机化合物(特别是包含羰基官能的化合物)的用途。
发明详述
根据本发明的挤出的催化剂成形体包含在20-43重量%范围内,优选在25-42重量%范围内,更优选在30-35重量%范围内的量的铜,基于挤出形式的催化剂成形体的总重量计。铜基本上以氧化铜(CuO)、铜铝尖晶石(如CuAl2O4)、铜锰尖晶石(如CuMn2O4或Cu1.5Mn1.5O4)、单质铜(Cu)和/或其混合物的形式存在。
根据本发明的挤出的催化剂成形体包含在20-40重量%范围内,优选在25-34重量%范围内的量的铝,基于挤出形式的催化剂成形体的总重量计。铝在这种情况下基本上以氧化铝(Al2O3)、铜铝尖晶石(如CuAl2O4)和/或其混合物的形式存在。
根据本发明的挤出的催化剂成形体包含在1-10重量%范围内,优选在2-8重量%范围内,特别优选在3-6重量%范围内的量的锰,基于挤出形式的催化剂成形体的总重量计。锰在这种情况下基本上以氧化锰(MnO、Mn2O3、Mn3O4、MnO2、Mn2O7)、铜锰尖晶石(如CuMn2O4或Cu1.5Mn1.5O4)和/或其混合物的形式存在。
特别优选地,根据本发明的挤出的催化剂成形体包含在25-42重量%范围内,特别是在30-35重量%范围内的量的铜,在25-34重量%范围内的量的铝,和在2-8重量%范围内,特别是在3-6重量%范围内的量的锰,基于挤出形式的催化剂成形体的总重量计。
根据本发明的催化剂成形体具有根据DIN 66133通过压汞法测定的在250至700mm3/g范围内,优选在400至650mm3/g范围内,特别优选在450至600mm3/g范围内的孔体积。
在一个特别优选的实施方案中,根据本发明的挤出的催化剂成形体包含在25-42重量%范围内,特别是在30-35重量%范围内的量的铜,在25-34重量%范围内的量的铝,和在2-8重量%范围内,特别是在3-6重量%范围内的量的锰,基于挤出形式的催化剂成形体的总重量计,并且具有根据DIN 66133通过压汞法测定的在400至650mm3/g范围内,特别优选在450至600mm3/g范围内的孔体积。
在本发明中,术语“催化剂成形体”可以与术语“催化剂”互换使用,特别是当讨论其本身的功能时。
在一个优选的实施方案中,催化剂成形体具有单峰孔半径分布,其中50%或更多,优选70%或更多,特别优选80%或更多的孔体积由孔半径为在7至40nm范围内的孔形成,其中孔半径分布和孔体积根据DIN66133通过压汞法测定。
优选地,催化剂成形体具有根据DIN ISO 903确定的在300至800g/L范围内,优选在400至700g/L范围内,特别优选在450至650g/L范围内的堆积密度。
在另一个实施方案中,根据本发明的挤出的催化剂成形体包含不同于铜、铝和锰的至少一种另外的金属。所述至少一种另外的金属优选选自碱金属、碱土金属、稀土、Fe、Ni、Cr、Co、Zn、Zr、W、Mo及其混合物,特别选自Na、Mg、Ce、Co、Zn、Zr及其混合物。至少一种另外的金属可以以上述金属的金属氧化物形式包含在根据本发明的催化剂成形体中。金属氧化物可以包含一种或多种上述金属的氧化物。至少一种另外的金属以在0.1-12重量%范围内,优选在1-7重量%范围内,特别优选在3-5重量%范围内的量包含在催化剂成形体中,基于挤出形式的催化剂成形体的总重量。特别优选地,基于挤出形式的催化剂成形体的总重量,催化剂成形体以在3-5重量%范围内的量包含至少一种选自Na、Mg、Ce、Co、Zn、Zr及其混合物的另外的金属。
另外的金属可以在金属氧化物中以与氧的不同的化学计量组成和/或以一种或多种不同的氧化态存在。因此例如Fe以铁氧化物(如FeO、Fe2O3、Fe3O4、Fe2O或其混合物)的形式存在,Ni以镍氧化物(如NiO、Ni2O3、NiO2、Ni3O4或其混合物)的形式存在,Cr以铬氧化物(如Cr2O3)、铜铬酸盐(如CuCrO4或CuCr2O7)、铜亚铬酸盐(如CuCr2O4)或其混合物的形式存在,Co以氧化钴(如CoO、Co2O3或Co3O4)的形式存在,Zn以锌氧化物(如ZnO)的形式存在,Zr以锆氧化物(如ZrO2)的形式存在。
在一个优选的实施方案中,根据本发明的含Cu、Al和Mn的催化剂成形体在还原形式下具有在20m2/gCu至60m2/gCu范围内,优选在25m2/gCu至50m2/gCu范围内,特别优选在30m2/gCu至45m2/gCu范围内的Cu金属表面积,基于催化剂成形体中包含的Cu量计。催化剂成形体的Cu金属表面积通过例如G.C.Chinchen,C.M.Hay,H.D.Vandervell,K.C.Waugh的“Themeasurement of copper surface areas by reactive frontal chromatography”(Journal of Catalysis,第103卷,第1期,1987年1月,第79-86页)中描述的N2O脉冲化学吸附原理测定。由可以通过热导检测器测定的形成的N2量得到Cu金属表面积。
基于挤出形式的催化剂成形体的长度,根据本发明的催化剂成形体优选具有根据DIN EN 1094-5测量的在5至40N/mm范围内,优选在10至30N/mm范围内的侧压强度。根据本发明的挤出形式的催化剂成形体通常具有在2至12mm范围内,优选在3至10mm范围内,特别是在4至7mm范围内的长度。可以例如使用市售仪器(如Retsch)测定挤出形式的催化剂成形体的长度。典型地测定多个催化剂成形体(如30至200,优选50至120,例如100个催化剂成形体)的侧压强度和长度。由获得的侧压强度的值(以N计)得到算术平均值。通过使用挤出形式的催化剂成形体的算数平均长度对侧压强度的算术平均值进行标准化从而获得基于催化剂成形体的长度的侧压强度(单位为N/mm)。
挤出物优选具有在0.5至10mm范围内,更优选在1至6mm范围内,特别优选在1.5至3.5mm范围内的直径。可以例如使用Retsch分析催化剂成形体的直径。
在一个特别优选的实施方案中,挤出形式的催化剂成形体在纵向方向上具有深度在0.3mm至0.9mm范围内,优选约0.7mm并且宽度在1.0至1.5mm范围内,优选约1.2mm的凹槽。
本发明还涉及用于制备挤出形式的含Cu、Al和Mn的催化剂成形体的方法。
在根据本发明的用于制备挤出的催化剂成形体的方法中,首先提供铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液和至少一种含碳酸盐的水溶液。
在本发明的意义上,表述“铜化合物、铝化合物、锰化合物和任选另外的金属化合物的水溶液”不仅包括铜化合物、铝化合物、锰化合物和任选另外的金属化合物的水溶液而且包括水悬浮液和水浆液,其中优选水溶液。铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液例如通过如下方式制得,在水中在酸性、中性或碱性pH值下(优选在酸性或中性pH值下)溶解、悬浮和/或浆化(优选溶解)至少一种铜化合物、至少一种铝化合物、至少一种锰化合物和任选的一种或多种另外的金属化合物。
作为铜化合物、铝化合物和锰化合物,原则上可以使用所有易溶于水、酸或碱的铜、铝和锰的化合物,特别是所述金属的盐,非常特别是其硝酸盐、碳酸盐、氧化物、氢氧化物、碱式碳酸盐(Hydroxycarbonate)、其卤化物,如氯化物、溴化物和/或碘化物,和/或其硫酸盐。当使用金属的氧化物(如铜氧化物和/或铝氧化物和/或锰氧化物)制备水溶液时,优选通过添加合适的无机酸使其部分或完全溶解。铜氧化物中的铜可以以一种或多种不同的氧化态(如氧化铜(I)、氧化铜(II)或其混合物)存在。无机酸优选选自HNO3、HCl、H2SO4及其混合物。
优选的铜化合物为铜氧化物(Cu2O和/或CuO)、硝酸铜、氯化铜、碳酸铜、碱式碳酸铜(CuCO3·Cu(OH)2和/或(CuCO3)2·Cu(OH)2)、乙酸铜和硫酸铜,特别是硝酸铜。
优选的铝化合物为硝酸铝、氢氧化铝、水合氧化铝(勃姆石)、氯化铝、碱金属铝酸盐和氧化铝(Al2O3),特别是硝酸铝和铝酸钠。
优选的锰化合物为硝酸锰、氢氧化锰、氧化锰、氯化锰(MnCl2)和硫酸锰、碳酸锰,特别是硝酸锰和碳酸锰。
另外的金属化合物优选选自碱金属化合物、碱土金属化合物、稀土金属化合物和(不同于铜化合物和锰化合物的)过渡金属化合物。特别优选的碱金属化合物为锂、钠、钾、铷的化合物及其混合物,特别是钠的化合物。特别优选的碱土金属化合物为镁、钙、锶、钡的化合物及其混合物,特别是钙、钡的化合物及其混合物。特别优选的稀土金属化合物为钪、镧、铈、钇、钕的化合物及其混合物,特别是铈的化合物。特别优选的不同于铜化合物和锰化合物的过渡金属化合物是锌、硅、钛、镍、铬、铁、钴、钼、锆的化合物及其混合物,特别是锌、钴、锆的化合物及其混合物。所使用的另外的金属化合物优选为所述金属的易溶于水、酸或碱的化合物。特别使用金属的盐。特别优选使用其硝酸盐,如硝酸锌、硝酸铈和/或硝酸锆,其卤化物,如锌、铈和/或锆的氯化物、溴化物和/或碘化物,其氧化物,如锌氧化物、铈氧化物和/或锆氧化物,和/或其硫酸盐,如硫酸锌、硫酸铈和/或硫酸锆。更优选地,另外的金属化合物选自硝酸铈、氯化锌、氯化锆及其混合物。在使用所述另外的金属的氧化物时,氧化物中的金属可以以一种或多种不同的氧化态存在。当使用金属和/或其氧化物(如氧化锌、氧化铈和/或氧化锆)制备另外的金属化合物的水溶液时,优选通过加入合适的无机酸使其部分或完全溶解。
铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液可以以铜化合物、铝化合物、锰化合物和任选另外的金属化合物的多个单独的水溶液的形式提供。例如可以提供铜化合物的一种或多种水溶液、铝化合物的一种或多种水溶液、锰化合物的一种或多种水溶液和任选另外的金属化合物的一种或多种水溶液。替代性地还可以提供一种或多种共有的水溶液。可以通过在共有容器中溶解铜化合物和/或铝化合物和/或锰化合物和/或任选另外的金属化合物从而制备共有的水溶液。同样有可能组合上述单独的溶液从而形成共有的溶液。
优选通过将至少一种碱金属碳酸盐(如碳酸锂、碳酸钠、碳酸钾、碳酸铷或碳酸铯)、碱土金属碳酸盐(如碳酸镁、碳酸钙、碳酸锶或碳酸钡)或碳酸铵或其混合物溶解在水中从而制备含碳酸盐的水溶液。同样地,可以连同碳酸盐或替代碳酸盐使用相应的碳酸氢盐或碳酸盐和碳酸氢盐的任何混合物。
优选使用碱金属碳酸盐、碳酸铵、碱金属碳酸氢盐、碳酸氢铵或其混合物,特别优选使用碱金属碳酸盐和/或碱金属碳酸氢盐。
优选的碱金属碳酸盐为碳酸钠和碳酸钾,特别是碳酸钠。优选的碱金属碳酸氢盐为碳酸氢钠和碳酸氢钾,特别是碳酸氢钠。特别优选使用碳酸钠和/或碳酸氢钠。
通过组合铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液和至少一种含碳酸盐的水溶液从而形成沉淀物。分离沉淀物,任选洗涤和/或干燥,然后在与含铝粘结剂混合之后转变成挤出成形体。
在一个实施方案中,可以以如下方式进行步骤(a)中的组合:在共有的容器(如沉淀容器)中同时加入铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液(单独的溶液和/或一种或多种共有的溶液和/或溶液混合物的形式)和至少一种含碳酸盐的水溶液。在此优选将至少两种溶液连续引入沉淀混合器的反应体积。
在另一个实施方案中,还可以以如下方式进行步骤(a)中的组合:向(例如一个或多个容器,如一个或多个沉淀容器)中预置的至少一种含碳酸盐的水溶液中计量加入铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液(单独的溶液和/或一种或多种共有的溶液和/或溶液混合物的形式)。
在再一个实施方案中,还可以以如下方式进行步骤(a)中的组合:向(例如一个或多个容器,如一个或多个沉淀容器)中预置的铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液中计量加入至少一种含碳酸盐的水溶液。
在组合之前将铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液优选加热至高于20℃的温度,例如在50℃至90℃范围内,特别是约80℃的温度并且在这种情况下优选搅拌。
同样地,优选在组合之前将至少一种含碳酸盐的溶液加热至高于20℃的温度,例如在50℃至90℃范围内,特别是约80℃的温度并且在这种情况下优选搅拌。
在一个优选的实施方案中,将铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液以及至少一种含碳酸盐的溶液加热至在50℃至90℃范围内,特别是约80℃的温度并且在这种情况下优选搅拌。
在组合铜化合物、铝化合物、锰化合物和任选另外的金属化合物的至少一种水溶液和至少一种含碳酸盐的水溶液时,在混合物(下文也被称为含沉淀物的溶液混合物)中形成沉淀物。通常在搅拌的容器中进行溶液的组合。容器优选用倾斜叶片搅拌器、螺旋桨搅拌器或其它市售搅拌器搅拌。
在一个优选的实施方案中,通过在沉淀容器中向含碳酸盐的水溶液中计量加入一定体积流量的铜化合物、铝化合物、锰化合物和任选另外的金属化合物的水溶液从而进行步骤(a)中的溶液的组合。铜化合物、铝化合物、锰化合物和任选另外的金属化合物的水溶液可以在此以单独存在的溶液的形式和/或以一种或多种共有的溶液的形式计量加入。
优选将含沉淀物的溶液混合物保持在高于20℃的温度,特别是在50℃至90℃范围内,优选约80℃的温度。在本发明的一个特别优选的实施方案中,将含沉淀物的溶液混合物在50℃至90℃范围内的温度,优选约80℃的温度保持至少30分钟,优选1至36小时,特别是约2小时,从而任选完成沉淀物的形成或通过老化升高沉淀物的结晶度。
在整个时间内优选将混合物的pH值保持在5.0至8.5范围内,特别是在6.0至7.5范围内,优选约6.8的值。
优选通过过滤分离沉淀物。替代性地,也可以通过倾析或离心分离沉淀物。然后使分离的沉淀物经受干燥。干燥可以例如通过喷雾干燥进行。为此,由分离的沉淀物(如滤饼)与水制备固体含量为10至40重量%的悬浮液。然后优选通过喷嘴将所述悬浮液计量加入喷雾干燥器。在干燥的过程中,喷雾干燥器中的温度优选在75℃至130℃范围内,特别是在90℃至120℃范围内。表征干燥的出口温度优选在90℃至120℃范围内,并且通常通过参数控制,所述参数例如为悬浮液的喷雾量、悬浮液的固体含量(以及因此必须蒸发的水量)或喷雾干燥器中的温度。通过用喷雾干燥器处理材料特别形成干燥的粉末。
任选地,分离的沉淀物可以在干燥之前经受一个或多个洗涤步骤。在此可以首先通过使用压滤机从含沉淀物的溶液混合物中分离沉淀,然后用水流过压滤机并且由此洗涤。替代性地,在通过过滤、倾析或离心分离含沉淀物的溶液混合物之后,可以在容器中浆化分离的沉淀物,然后借助于压滤机、离心机或倾析机从液相中重新分离。所述过程通常进行一次或多次直至达到一定的滤液电导率。在这种情况下,电导率通常与钠离子的浓度相关。
最后一次洗涤过程的滤液的电导率优选为0.5mS/cm或更小,特别是0.2mS/cm或更小。电导率根据DIN 38404第8部分测定。
然后将上述步骤(a)中获得的干燥的沉淀物在步骤(b)中与含铝粘结剂混合。
在另一个实施方案中,步骤(b)包括步骤(b1)、(b2)和(b3)。在此使一部分步骤(a)中获得的干燥的沉淀物在步骤(b1)中经受煅烧。所述在步骤(b1)中获得的煅烧的沉淀物然后在步骤(b2)中与另一部分步骤(a)中获得的干燥的(未煅烧的)沉淀物混合,然后获得的混合物在步骤(b3)中与含铝粘结剂混合。
通过热处理进行步骤(b1)中的煅烧,其中温度在250℃至900℃范围内,优选在300℃至750℃范围内,特别优选在600℃至750℃范围内。煅烧可以在空气、保护气体(例如氩气或氮气)、氧气或其混合物中进行。煅烧可以例如在盘式炉中以间歇方式或者例如在旋转炉中以连续方式进行。旋转炉中的煅烧能够通过停留时间和不同加热区域进行控制。优选地,旋转炉具有1至10个不同的加热区域,特别是约5个加热区域。不同加热区域中的温度例如为第一加热区域在300℃至400℃范围内,第二加热区域在500℃至600℃范围内,第三加热区域在600℃至750℃范围内,第四加热区域在650℃至800℃范围内,和第五加热区域500℃至700℃范围内。不同加热区域中的停留时间优选在5min至60min范围内,特别是在10min至30min范围内。在使用盘式炉时,步骤(a)中获得的干燥的沉淀物通常分布在板上。在盘式炉中,可以通过相应的炉控制实现温度曲线。温度曲线可以例如包括以2℃/min的加热速率从20℃加热至750℃,在750℃下保持3h,并且以2℃/min的冷却速率冷却至20℃。
在(b2)中以未煅烧的沉淀物与煅烧的沉淀物的在2:98至98:2范围内,优选在10:90至90:10范围内,更优选在15:85至85:15范围内,特别优选在20:80至50:50范围内的重量比例混合通过步骤(b1)中的煅烧获得的煅烧的沉淀物与步骤(a)中获得的干燥的未煅烧的沉淀物。然后将获得的未煅烧的沉淀物和煅烧的沉淀物的混合物在步骤(b3)中与含铝粘结剂混合。
对于根据本发明的催化剂,优选使用基于氧化铝的含铝粘结剂。基于氧化铝的含铝粘结剂在这种情况下特别优选选自勃姆石(AlO(OH))和拟勃姆石(凝胶状/胶质勃姆石)。勃姆石特别描述于第9版Strunz'schen Mineralsystematik;E.Schweizerbart'scheVerlagsbuchhandlung(u.Obermiller),斯图加特2001:第4.FE.15组。
将在步骤(b)或(b3)中与步骤(a)中获得的干燥的沉淀物或步骤(b2)中获得的混合物混合的基于氧化铝的含铝粘结剂用酸进行胶溶,其中在混合之前和/或在混合过程中进行胶溶。胶溶过程是用于产生孔体积的基本步骤。可以使用无机酸(如HNO3、H2SO4或HCl)和有机酸进行胶溶。使用无机强酸或有机强酸(如甲酸)通常造成较低孔体积。为了进行根据本发明的胶溶,优选使用不同于甲酸的有机酸,优选乙酸或柠檬酸。基于含铝粘结剂的量,酸以在0.5至0.01重量%范围内的量使用。对于稀释的酸(例如50%的乙酸),未稀释的酸的含量充当用于计算酸量/粘结剂比例的基础。
所使用的勃姆石和/或拟勃姆石优选以粉末的形式使用。粉末优选具有根据DINISO 13320按照激光衍射方法测定的在10至40μm范围内,优选在15至35μm范围内,特别优选在20至30μm范围内的粒度D50。所使用的勃姆石或拟勃姆石优选具有在300-700mm3/g范围内,优选在400-600mm3/g范围内,特别优选在450-550mm3/g范围内的孔体积。在一个优选的实施方案中,使用粒度D50在10至40μm范围内、孔体积在300-700mm3/g范围内,更优选粒度D50在15至35μm范围内、孔体积在400-600mm3/g范围内,特别是粒度D50在20至30μm范围内、孔体积在450-550mm3/g范围内的粉末形式的勃姆石和/或拟勃姆石。
合适的勃姆石粉末或拟勃姆石粉末例如由Sasol公司以名称Pural销售,或者由Akzo Nobel或Nabaltec公司销售。
可以通过本领域技术人员已知的保证混合的方法混合步骤(a)中获得的干燥的沉淀物或步骤(b2)中获得的煅烧沉淀物和未煅烧沉淀物的混合物与上述含铝粘结剂。例如,混合可以在强力混合器如Eirich混合器中进行,或者借助Pflugschar混合器或混合器进行。还能够使用用于混合粉末的捏合机。
然后将步骤(b)或步骤(b3)中获得的混合物在步骤(c)中通过本领域技术人员已知的方法挤出成催化剂成形体从而获得挤出物。挤出物例如为条和肋纹条。
优选地,基于待挤出物料的总重量,在挤出之前在步骤(b)或步骤(b3)中获得的混合物中以在0.1至5重量%范围内的量加入润滑剂。更优选地,基于待挤出物料的总重量,以在0.5至5重量%范围内,更优选在1至4重量%范围内的量加入润滑剂。润滑剂优选为石墨、油或脂肪酸盐,优选石墨或滑石油。
步骤(c)中获得的挤出物任选在步骤(c1)中进行干燥。可以例如通过在炉(如盘式炉)中加热至在75℃至130℃范围内的温度从而进行挤出物的干燥。
然后,将在步骤(c)中获得的挤出物或步骤(c1)中获得的干燥的挤出物在步骤(d)中在300℃至750℃范围内,优选在600℃至750℃范围内,特别是约750℃的温度进行煅烧从而获得挤出的成形体。
在另一个实施方案中,步骤(d)中获得的挤出的催化剂成形体在步骤(e)中进行还原。
优选通过在还原气氛中加热挤出的催化剂成形体进行还原。特别地,还原气氛为氢气。还原例如在150℃至450℃范围内,特别是在180℃至250℃范围内,优选在190℃至210℃范围内,特别优选约200℃的温度进行。还原例如进行1小时至10天的时间,特别是2小时至72小时的时间,优选24至48小时的时间。在一个优选的实施方案中,在190℃至210℃的温度下进行还原24至48小时的时间。
优选地,在还原之后湿稳定化或干稳定化催化剂成形体。在湿稳定化的情况下,用液体覆盖成形体从而尽可能避免与氧气接触。合适的液体包括有机液体和水,优选有机液体。优选的有机液体为在20℃下具有0.5hPa或更低蒸汽压的有机液体。合适的有机液体的实例为异癸醇、Nafol、脂肪醇、十六烷、2-乙基己醇、丙二醇及其混合物,特别是异癸醇。
在干稳定化的情况下,在还原反应器中计量加入氧气或含氧气体(优选空气)和惰性气体(如氩气或氮气)的混合物。氧气在混合物中的浓度优选从约0.04体积%升高至约21体积%。例如,可以计量加入空气和惰性气体的混合物,其中空气与惰性气体的初始比例为约0.2体积%空气比99.8体积%惰性气体。然后逐渐升高(如连续地或逐步地)空气与惰性气体的比例直至最终例如计量加入100体积%的空气(这对应于约21体积%的氧气浓度)。不局限于理论,猜测通过计量加入空气或氧气在催化剂表面上形成厚度为例如0.5至50nm,优选1至20nm,特别是1至10nm的薄氧化物层,所述薄氧化物层保护催化剂成形体免于进一步氧化。在干稳定化的情况下,反应器温度优选为100℃或更低,更优选20℃至70℃,特别优选30℃至50℃。在所述稳定化之后,催化剂成形体“可输送”并且可以输送至使用者/装置操作员。对于催化剂使用者在反应器中原位进行步骤(e)的情况,通常免除稳定化。
根据本发明的催化剂成形体适用于大量反应。可能的反应包括:合成气反应、甲醇合成、费托合成、吡啶合成、酯氢解、胺化反应、N-烷基化、腈至胺的氢化、丙烯腈的氢化、脂肪酸酯的氢化、二酯至二醇的氢化(特别是马来酸酯)、糖至多元醇的氢化、酚通过醇的烷基化、醇的胺化、醇的脱氢、醛的氢化、酰胺的氢化、脂肪酸的氢化(如通过酯化和然后的氢解)、脂肪的选择性氢化、油的选择性氢化、腈的氢化、硝基芳族烃的氢化、酮的氢化、糠醛的氢化、酯的氢化和一氧化碳至甲醇的氢化。
在一个优选的实施方案中,通过根据本发明的方法制得的催化剂用于氢化羰基化合物,特别是用于氢化醛、酮、羧酸和/或其酯或二羧酸和/或其二酯,非常特别优选用于氢化脂肪酸酯,特别是脂肪酸烷基酯,优选脂肪酸甲酯或马来酸酯。
根据本发明的催化剂成形体特别适合于塔底相氢化羧酸(优选具有5至24个C原子的脂肪酸或脂肪酸混合物)和/或其酯(任选与醇混合)从而形成相应的脂肪醇。在此,脂肪酸或脂肪酸混合物可以与反应混合物中存在的醇原位酯化。反应混合物中存在的优选的醇为具有5至24个C原子的脂肪醇或脂肪醇混合物。特别优选使用上述催化剂从而氢化脂肪酸甲酯。
物理参数的测定
只要没有另外说明,本申请中描述的物理参数以如下方式测定:
电导率根据DIN 38404第8部分测定。
粒度D50根据DIN ISO 13320按照激光衍射方法测定。
烧失量根据DIN EN 196-2测定。
孔体积和孔半径分布根据DIN 66133通过压汞法测定。
Cu金属表面积使用N2O脉冲化学吸附测定。
侧压强度根据DIN EN 1094-5测定。侧压强度通常得自100次测量的算数平均。
催化剂成形体的长度分布通过德国RETSCH GmbH公司的测定。催化剂成形体的指定长度通常为测量长度的算术平均。
实施例
借助以下非限制性实施例详细解释本发明。尽管这些实施例描述了本发明的特定的实施方案,但其仅用于解释本发明并且不应被理解为以任何方式限制本发明。正如本领域技术人员所知,可以进行大量改变而不偏离通过所附权利要求书限定的本发明的保护范围。
参考实施例1(未煅烧材料的制备)
通过用碳酸钠沉淀金属硝酸盐形成其碳酸盐然后过滤沉淀物、洗涤并且喷雾干燥从而制备未煅烧材料。
通过1250g Cu(NO3)2x 3H2O,220g Mn(NO3)2x 4H2O,1800g Al(NO3)3x 9H2O和9LH2O制备溶液1。由1720g Na2CO3和7.5L H2O制备溶液2。将两种溶液加热至80℃并且在此搅拌。然后将其计量加入沉淀容器。沉淀容器中的pH值为6.8。调节溶液1和2的体积流量从而调节其pH值。一旦两种溶液已经消耗,则过滤形成的沉淀物并且用水洗涤。然后将滤饼在约2L水中再悬浮并且进行喷雾干燥。所得的干燥但是未煅烧的粉末状材料是用于进一步制备的起始材料。
参考实施例2(煅烧材料的制备)
通过在空气循环炉中在730℃下煅烧未煅烧的材料(如参考实施例1所述制得)3小时从而制备煅烧材料。1000℃的烧失量(LOI)为约5%。
实施例1(催化剂成形体1的制备)
为了制备催化剂1,将17g Pural SCF 55用34g 2.5%乙酸进行胶溶,然后在双Z捏合机中与320g未煅烧材料(如参考实施例1所述制得)和165g去离子水混合。向混合物中混入10g滑石油作为润滑剂。然后将混合物挤出成直径为3.2mm并且长度为3至10mm的条。将挤出物在120℃干燥16小时然后在750℃煅烧3小时。
实施例2(催化剂成形体2的制备)
为了制备催化剂2,将125g Pural SCF 55用250g 2.5%乙酸进行胶溶,然后在双Z捏合机中与720g未煅烧材料(如参考实施例1所述制得)和370g去离子水混合。向混合物中混入20g滑石油作为润滑剂。然后将混合物挤出成直径为3.2mm并且长度为3至10mm的条。挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
实施例3(催化剂成形体3的制备)
为了制备催化剂3,将600g Pural SCF 55用1200g 2.5%乙酸进行胶溶,然后在双Z捏合机中与1950g未煅烧材料(如参考实施例1所述制得)和1000g去离子水混合。向混合物中混入80g滑石油作为润滑剂。然后将混合物挤出成直径为3.2mm并且长度为3至10mm的条。将挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
实施例4(催化剂成形体4的制备)
为了制备催化剂4,将173g Pural SCF 55用346g 2.5%乙酸进行胶溶,然后在双Z捏合机中与320g未煅烧材料(如参考实施例1所述制得)和165g去离子水混合。向混合物中混入15g滑石油作为润滑剂。然后将混合物挤出成直径为3.2mm并且长度为3至10mm的条。将挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
实施例5(催化剂成形体5的制备)
为了制备催化剂5,将262g Pural SCF 55用520g 2.5%乙酸进行胶溶,然后在双Z捏合机中与320g未煅烧材料(如参考实施例1所述制得)和165g去离子水混合。向混合物中混入17.5g滑石油作为润滑剂。然后将混合物挤出成直径为3.2mm并且长度为3至10mm的条。将挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
实施例6(催化剂成形体6的制备)
催化剂成形体6的制备以与催化剂成形体3的制备(如实施例3所述)相似的方式进行,区别在于使用用于带槽挤出物的模具(直径约3.2mm)进行挤出。干燥和煅烧同样以与实施例3所述相似的方式进行。制成的挤出物在纵向方向上具有深度为约0.7mm并且宽度为约1.2mm的三个凹槽。
实施例7(催化剂成形体7的制备)
为了制备催化剂7,在双Z捏合机中混合600g Pural SCF 55与1950g未煅烧材料(如参考实施例1所述制得)。然后首先加入1200g 2.5%的乙酸,然后直接加入1000g去离子水,捏合所得混合物60分钟。捏合之后向混合物中混入80g滑石油作为润滑剂,然后挤出混合物(直径3.2mm)。将挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
对比实施例1(参考催化剂A的制备)
为了制备催化剂A,混合100g未煅烧材料(如参考实施例2所述制得)和3g石墨并且压片形成直径为约3mm并且高度为约3mm的成形体。
对比实施例2(参考催化剂B的制备)
为了制备参考催化剂B,混合150g Volclay SPV与450g未煅烧材料(如参考实施例1所述制得)和50g去离子水。然后挤出混合物(直径3.2mm)。将挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
对比实施例3(参考催化剂C的制备)
为了制备参考催化剂C,混合375g Ludox AS40与450g未煅烧材料(如参考实施例1所述制得)、10g Zusoplast C-92(压缩助剂和润滑助剂)和250g去离子水。然后挤出混合物(直径3.2mm)。将挤出物在120℃干燥16小时,然后在750℃下煅烧3小时。
孔体积的测定
根据DIN 66133通过压汞法测定孔体积。表1显示了根据本发明的催化剂和参考催化剂的孔体积:
表1:根据本发明的催化剂成形体和参考催化剂的孔体积
化学分析
为了化学分析催化剂,首先将催化剂与二硫酸钾熔体引入溶液,然后借助ICP方法(电感耦合等离子体)测定化学组成。表2显示了各个催化剂的化学组成。在无烧失量的情况下记录数值。根据DIN ISO 803/806测定烧失量。
表2:各个催化剂的化学组成
粒度分布的测定(粘结剂材料)
粒度的测定根据激光散射方法根据DIN ISO 13320使用Malvern Mastersizer2000根据生产商的说明进行,其中样品在测量之前在去离子水中在不加入助剂的情况下均质化并且用超声波处理5分钟。给出的D-值基于样品体积。
Cu金属表面积的测定
通过N2O分解原理(N2O脉冲化学吸附)测定催化剂的Cu金属表面积:
2Cu+N2O→Cu2O+N2
为此,在还原炉TRACE GC ULTRA(Brechbühler公司)中在240℃下用氢气(He中5%H2的合成气体)还原样品16h。然后将样品转入Thermo Electron的TPDRO 1100系列设备,用He吹扫并且开始N2O脉冲化学吸附。由通过热导检测器测定的He中形成的N2量得到Cu金属表面积。
表3:根据本发明的催化剂和参考催化剂的Cu金属表面积
堆积密度的测定
根据DIN ISO 903测定堆积密度。表4显示了各个催化剂的堆积密度。
表4:根据本发明的催化剂和参考催化剂的堆积密度
堆积密度[g/L] | |
催化剂1 | 680 |
催化剂2 | 585 |
催化剂3 | 550 |
催化剂4 | 530 |
催化剂5 | 490 |
催化剂6 | 530 |
催化剂7 | 550 |
参考催化剂A | 1500 |
参考催化剂B | 600 |
参考催化剂C | 550 |
侧压强度的测定
根据DIN EN 1094-5测定侧压强度。侧压强度得自100次测量的算数平均。基于测量的挤出物的长度以N/mm挤出物长度表示挤出物的侧压强度,其中挤出物的长度为约100个挤出形式的催化剂成形体的测量长度的算术平均。关于片剂,可以基于不变的尺寸记录侧压强度的具体值。
表5:根据本发明的催化剂和参考催化剂的侧压强度
侧压强度 | |
催化剂1 | 4.5N/mm |
催化剂2 | 11.6N/mm |
催化剂3 | 13.8N/mm |
催化剂4 | 15.1N/mm |
催化剂5 | 18.2N/mm |
催化剂6 | 10.5N/mm |
催化剂7 | 15.3N/mm |
参考催化剂A | 85.0N |
参考催化剂B | 56N/mm |
参考催化剂C | 22N/mm |
实施例8(活性测量)
关于脂肪酸甲酯(FAME)的氢化研究催化剂的活性。为此使用具有25ml的反应器体积的电加热的固定床反应器。为了测试,使用月桂酸甲酯(C12-甲酯)。为了评估酯转化率和至脂肪醇的选择性或副产物的形成,通过气相色谱分析所形成的反应产物。在此通过所使用的酯的物质量和产物中剩余的酯的物质量计算转化率。
为了通过气相色谱分析,混合6.0000g所形成的产物和0.2000g 5-壬醇(内标)。然后用气相色谱分析样品两次。
所使用的设备:
GC:具有FID的Agilent 7890A
柱:Phenomenex的ZB-1,60m x 0.25mm
软件:EZ Chrom Elite Version 3.3.2SP1
月桂酸甲酯氢化时的测试条件:
反应温度:160℃、180℃、240℃
压力:280bar
GHSV(H2):20000h-1
LHSV(酯):1.4h-1
表1中以C12-甲酯在180℃下的转化率的值的形式记录了所述催化剂的结果。清楚可见相比于对比催化剂,根据本发明的催化剂具有改进的活性和选择性。
表6:C12-甲酯的转化率和160℃、180℃和240℃下链烷烃副产物的形成
由表6可知,根据本发明制得的催化剂成形体的特征在于月桂酸甲酯的明显升高的转化率和升高的选择性,即相比于对比催化剂形成更少的链烷烃副产物。在所有三个选择的温度(160℃、180℃和240℃)下都可以观察到该升高。
总而言之可以确定的是,通过根据本发明的催化剂成形体实现经济性的改进,特别是至目标产物的转化率的升高。
Claims (18)
1.挤出形式的催化剂成形体,其包含在20-43重量%范围内,优选在25-42重量%范围内的量的Cu,在20-40重量%范围内,优选在25-34重量%范围内的量的Al,和在1-10重量%范围内,优选在2-8重量%范围内,特别优选在3-6重量%范围内的量的Mn,基于挤出形式的催化剂成形体的总重量计,
其中催化剂成形体具有根据DIN 66133通过压汞法测定的在250至700mm3/g范围内,优选在400至650mm3/g范围内,特别优选在450至600mm3/g范围内的孔体积。
2.根据权利要求1所述的催化剂成形体,其中催化剂成形体具有单峰孔半径分布并且其中50%或更多,优选70%或更多,特别优选80%或更多的孔体积由孔半径在7至40nm范围内的孔形成,其中孔半径分布和孔体积根据DIN 66133通过压汞法测定。
3.根据权利要求1或2所述的催化剂成形体,其具有根据DIN ISO 903测定的在300至800g/L范围内,优选在400至700g/L范围内,特别优选在450至650g/L范围内的堆积密度。
4.根据权利要求1、2或3所述的催化剂成形体,其包含至少一种另外的金属,所述金属选自碱金属、碱土金属、稀土、Fe、Ni、Cr、Co、Zn和Zr。
5.根据权利要求1至4任一项所述的催化剂成形体,其中基于挤出物的长度计,所述成形体具有在5至40N/mm范围内,优选在10至30N/mm范围内的侧压强度,其中侧压强度根据DIN EN 1094-5测定。
6.根据权利要求1至5任一项所述的催化剂成形体,其中成形体具有在1至6mm范围内,优选在1.5至3.5mm范围内的直径。
7.根据权利要求1至6任一项所述的催化剂成形体,其中成形体在纵向方向上具有深度在0.3mm至0.9mm范围内,优选约0.7mm并且宽度在1.0至1.5mm范围内,优选约1.2mm的凹槽。
8.根据权利要求1至7任一项所述的催化剂成形体,其中基于催化剂成形体中包含的Cu量,催化剂成形体在还原形式下具有采用N2O脉冲化学吸附测定的在20m2/gCu至60m2/gCu范围内,优选在25m2/gCu至50m2/gCu范围内,特别优选在30m2/gCu至45m2/gCu范围内的Cu金属表面积。
9.用于制备挤出的催化剂成形体的方法,所述方法包括如下步骤:
(a)组合(i)铜化合物、铝化合物、锰化合物和任选的过渡金属化合物的至少一种水溶液和(ii)至少一种含碳酸盐的水溶液从而形成沉淀物,分离沉淀物,任选洗涤分离的沉淀物并且干燥分离的沉淀物从而获得干燥的沉淀物,
(b)混合步骤(a)中获得的干燥的沉淀物与含铝粘结剂,所述含铝粘结剂选自勃姆石和拟勃姆石,
(c)挤出步骤(b)中获得的混合物从而获得挤出物,和
(d)在300℃至750℃范围内,优选在600℃至750℃范围内,特别是在约750℃的温度煅烧步骤(c)中获得的挤出物从而获得挤出的催化剂成形体。
10.根据权利要求9所述的方法,其中步骤(b)包括:
(b1)在250℃至900℃范围内的温度,优选在300℃至750℃范围内的温度,特别优选在600℃至750℃范围内的温度煅烧步骤(a)中获得的干燥的沉淀物从而获得煅烧的沉淀物,
(b2)以在2:98至98:2范围内,优选在10:90至90:10范围内,优选在15:85至85:15范围内,且特别优选在20:80至50:50范围内的干燥的沉淀物比煅烧的沉淀物的重量比例混合步骤(a)中获得的干燥的沉淀物与步骤(b1)中获得的煅烧的沉淀物从而获得混合物,和
(b3)混合步骤(b2)中获得的混合物与含铝粘结剂,所述含铝粘结剂选自勃姆石和拟勃姆石。
11.根据权利要求9或10所述的方法,其中通过添加酸,优选有机酸使含铝粘结剂胶溶,其中优选在步骤(b)之前或过程中进行胶溶。
12.根据权利要求11所述的方法,其中有机酸选自乙酸和柠檬酸。
13.根据权利要求9至12任一项所述的方法,其中基于待挤出的物料的总重量,在挤出之前向由步骤(b)或步骤(b3)获得的混合物中以在0.1至5重量%范围内的量加入润滑剂。
14.根据权利要求9至13任一项所述的方法,其中粘结剂具有在300-700mm3/g范围内,优选在400-600mm3/g范围内,且特别优选在450-550mm3/g范围内的孔体积,其中孔体积根据DIN 66133通过压汞法测定。
15.根据权利要求9至14任一项所述的方法,其中粘结剂具有根据DIN ISO 13320按照激光衍射方法测定的在10至40μm范围内,优选在15至35μm范围内,且特别优选在20至30μm范围内的粒度D50。
16.根据权利要求9至15任一项所述的方法,所述方法包括如下步骤:
(e)还原步骤(d)中获得的挤出的催化剂成形体从而获得还原的催化剂成形体。
17.通过根据权利要求9至16任一项所述的方法可获得的催化剂成形体。
18.根据权利要求1至8或17任一项所述的催化剂成形体用于氢化羰基化合物的用途。
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DE102014013530.6A DE102014013530A1 (de) | 2014-09-12 | 2014-09-12 | Extrudierter Cu-Al-Mn-Hydrierkatalysator |
DE102014013530.6 | 2014-09-12 | ||
PCT/EP2015/069349 WO2016037839A1 (de) | 2014-09-12 | 2015-08-24 | Extrudierter cu-al-mn-hydrierkatalysator |
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SG11201701892TA (en) | 2017-04-27 |
EP3191432A1 (de) | 2017-07-19 |
PH12017500420A1 (en) | 2017-07-17 |
DE102014013530A1 (de) | 2016-03-17 |
US10639616B2 (en) | 2020-05-05 |
WO2016037839A1 (de) | 2016-03-17 |
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