CN103787829A - 一种钴银催化剂羧酸加氢制备醇的方法 - Google Patents
一种钴银催化剂羧酸加氢制备醇的方法 Download PDFInfo
- Publication number
- CN103787829A CN103787829A CN201210429960.0A CN201210429960A CN103787829A CN 103787829 A CN103787829 A CN 103787829A CN 201210429960 A CN201210429960 A CN 201210429960A CN 103787829 A CN103787829 A CN 103787829A
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- Prior art keywords
- catalyzer
- carboxylic acid
- acid
- cobalt
- catalyst
- Prior art date
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 35
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 26
- SQWDWSANCUIJGW-UHFFFAOYSA-N cobalt silver Chemical compound [Co].[Ag] SQWDWSANCUIJGW-UHFFFAOYSA-N 0.000 title description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 36
- 239000010941 cobalt Substances 0.000 claims abstract description 36
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001556 precipitation Methods 0.000 claims description 31
- 150000001735 carboxylic acids Chemical class 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 150000002148 esters Chemical class 0.000 abstract description 2
- 235000013495 cobalt Nutrition 0.000 description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- 239000000499 gel Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 235000021463 dry cake Nutrition 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- -1 teos hydrolysis Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- BSYNFGPFPYSTTM-UHFFFAOYSA-N 2-hydroxypropanoic acid;hydrate Chemical compound O.CC(O)C(O)=O BSYNFGPFPYSTTM-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- SXFQDYORBVIULR-UHFFFAOYSA-N azane;cobalt(2+) Chemical compound N.[Co+2] SXFQDYORBVIULR-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- AVMBSRQXOWNFTR-UHFFFAOYSA-N cobalt platinum Chemical compound [Pt][Co][Pt] AVMBSRQXOWNFTR-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
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- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 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
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开将一种至少含钴银催化剂应用于羧酸加氢制备为醇的方法。在本发明中,使用的催化剂至少含有占催化剂总重的15wt%~50wt%的钴和0.1wt%~10.0wt%的银。通过该催化剂,在220~300℃和0.5~4.0MPa条件下,羧酸可以以高于90%的选择性转化为相应的醇和酯,使用的催化剂活性高,稳定性好并且成本较低,并且使用的反应条件不苛刻,因此较易实现商业化操作。
Description
技术领域
本发明涉及一种羧酸选择加氢制备醇的方法,具体地说,本发明为应用一种钴银催化剂使羧酸高收率加氢转化为醇的方法。
技术背景
羧酸加氢制备醇是一类重要的化学反应,如乙酸加氢制备乙醇、乳酸加氢制备丙二醇均存在着迫切地需求。这是由于多个原因造成的:由于工艺进步,导致羧酸的制造成本降低,如醋酸随着甲醇羰基法的成熟,制造成本降低;或者由于原料变更,使得羧酸的制造具有可持续性,如乳酸、3-羟基丙酸等生物质衍生物。
羧酸的加氢制备醇的研究由来已久,如早在1950年,Ford等就申请了使用钌催化剂将羧酸转化为醇的方法,但是由于上世纪石油资源成本较为低廉以及人类的可持续发展重视程度较低,因此醇类的生产多采用烯烃水合、氧化-水合等技术。进入21世纪后,人们对可再生体系和石油替代资源(煤炭、天然气、页岩气、煤层气)等的大规模开发,使得羧酸加氢制备醇成为醇类生产的更具经济性和可持续的方法。
事实上羧酸加氢制备醇具有极高的挑战性,主要的技术难度在于开发出具有高活性和选择性的催化剂,降低所需的反应压力,并且催化剂需要具备有长时间使用的稳定性,当然催化剂的成本需要在合理的范围内,以保证其商业价值。
US4104478公开一种羧酸加氢催化剂及其应用方法,使用的催化剂为M-铼双金属催化剂,M为钌、铑、铂和钯中的一种,在170~250℃和2.0~14.0MPa的条件下,将相应的羧酸转化为脂肪醇。公开的实施例压力都非常地高(>7.0MPa)。
US4517391公开一种醋酸气相加氢制备乙醇的催化剂,催化剂含有不少于50wt%的钴,以及铜、锰、钼、铬和磷酸中的一种或者多种。在唯一的实施例中,钴含量更高达70%,使用的反应压力为300bar,乙醇收率为97%。虽然该专利催化剂钴金属含量极高,但是由于不使用贵金属,成本具有一定的优势,不过该催化剂活性较低,乙醇收率仅0.09kg/kg Cat/h,综合考虑催化剂成本依然较高,并且反应器将会非常庞大,因此并不具有商业化价值。同时实施例未公开尾气中不凝性气相的含量而物料收率低于理论值。
CN1008088公开一种羧酸加氢制备醇的负载型催化剂,催化剂的第一组分为钨和钼,第二组分为钯、钌和铂中的一种,载体为活性炭。该催化剂含有1~10wt%的贵金属,成本高昂;并且反应空速较低(实施例中的LHSV仅为0.35h-1,意味着时空收率低于0.26kg/m3 Cat/h),在实施例中的反应压力为1.0Mpa左右。CN201110104763.7和CN201110103802.1公开一种醋酸加氢催化剂及其应用方法,催化剂的第一活性组分为钨和钼,第二组分为钌、铑、铂和钯中的一种,载体为活性炭或者石墨,在其公开的实施例中,反应压力为7.0~10.0MPa。
Zhang等研究了乳酸水相加氢制备丙二醇,使用负载的钌催化剂和滴流床反应器,其中水含量一般为40~80%的水(Aqueous-phase hydrogenation of lactic acidto propylene glycol,Applied CatalysisA:General 219(2001)89-98)。在该方法中,较高含量的水这无疑会大幅增加分离时的能耗;使用的催化剂为5wt%的Ru/C,高昂的催化剂成本使得其不适应于商业化操作。
CN102149662公开一种用于醋酸加氢的钴催化剂,钴的负载量低于20wt%,并且催化剂中还含有1wt%左右的钯和铂。在公开的实施例中钴含量均低于10wt%。
US7863489公开一种醋酸加氢催化剂,催化剂活性组分为铂,助剂为锡。催化剂可以将乙酸以较高的收率转化为乙醇,但是铂含量较高,在公布的实施例中,铂含量超过1wt%,众所周知,铂的价格非常昂贵而且储量非常有限,因此在商业化应用中将会使得催化剂的成本极高。同样的问题也存在于另一专利US7608744中,钴催化剂含量较低(~10wt%),同时催化剂需要使用贵金属助剂,如铂和钯,助剂含量高于1wt%。
综上所述,现有羧酸技术方案中,存在一些技术和商业化问题:催化剂成本高昂而且生产催化剂的原料供给量有限、时空收率低、选择性较低、反应压力较高使得操作条件过于苛刻、能耗过高。
本发明所述的方法,在较温和的反应条件下,能够以较高的收率将醋酸转化为乙醇,并且催化剂具有较高的时空收率和低廉的制造成本。
发明内容
本发明涉及一种羧酸气相加氢制备醇的方法,并涉及使用仅含有银金属助剂的钴金属加氢催化剂将一元羧酸加氢为醇的方法,该催化剂不仅具有活性高、选择性高和稳定性好的特点,而且成本较现有技术低廉许多,并且组成较为环保。
本发明一种羧酸气相加氢制备醇的方法,在固定床反应器中,羧酸蒸汽与含氢气体混合与加氢催化剂接触反应后转化为醇和水,氢气与羧酸的摩尔比为4:1~40:1,反应温度为180~350℃,反应压力为0.3~8.0MPa,羧酸的体积空速为0.1~5.0h-1;
所述的加氢催化剂包括如下组分:
(1)含有钴和银,其中钴金属含量占催化剂总重的15wt%~50wt%,银金属占催化剂总重的0.1wt%~10.0wt%;
(2)氧化物;所述的氧化物选自氧化硅、硅藻土、硅酸钙、氧化锆、氧化钛的一种或者多种,其含量占催化剂总重的20wt%~80wt%;
所述的催化剂是采用共沉淀、沉积-沉淀、蒸氨沉淀或者溶胶-凝胶方法中的一种或者多种结合制备的;所述的羧酸为一元羧酸。
本发明详细说明如下:
本发明的催化剂主活性组分为钴,其中钴金属含量占催化剂总重的15wt%~50wt%,更优选的含量为20~40wt%;所述的钴金属含量是指元素钴的含量。钴催化剂的含量是经过发明人仔细筛选出的:在较低钴含量时催化剂的活性较低,而更高含量的钴不仅使得催化剂的成本上升,而且并不能够提高催化剂的活性,甚至使活性有所下降,在较高含量时下降明显。这一结果是出乎意料的:因为往往人们认为提高金属含量会提高催化剂的活性。并且,发明人发现在钴含量高于50wt%时候催化剂的制备难度增加,如成型过程等,这将会使得催化剂的商业化较为困难。
钴金属的来源可选自硝酸盐、硫酸盐、氯盐、醋酸盐、草酸盐和溴盐;所选的钴金属盐需具备水溶性。更具体而言,选自硝酸钴、氯化钴、草酸钴、硫酸钴、醋酸钴中的一种或者多种,更优选为硝酸钴、醋酸钴和草酸钴中的一种或者多种。
本发明公开了发明人意外的发现:适量银助剂的加入极大地提高了催化剂的活性和稳定性,并且通过特定的制备方法得到的催化剂更加体现本发明技术方案的优越性。
银金属含量占催化剂总重的0.1~10wt%,更优选的范围为0.2~5wt%。银金属的来源为硝酸银、碳酸银。银的添加方式可以是多样的,如在沉淀、沉积-沉淀或者溶胶-凝胶过程中与钴盐一起溶解后加入;在催化剂前驱体中加入,如沉淀、沉积-沉淀或者溶胶-凝胶中获得的干燥后滤饼或干凝胶中,或者焙烧分解后的材料中;或者在打片或者挤条等成型阶段加入;或者在与钴溶液浸渍时加入,或者与钴盐分步浸渍。
银助剂加入后,催化剂活性和稳定性等代表催化剂反应性能的指标大幅提高,其中的原因可能是多方面的:银促进了钴的还原或者活化了羧酸。更意外的,本发明人发现,相对于浸渍法,在通过共沉淀、沉积-沉淀或者溶胶-凝胶方法制备的钴催化剂,银助剂改善催化剂反应性能的效果更加明显。
本发明中所述的催化剂可以通过现有催化剂制备技术获得,如浸渍法、离子交换法、共混法、捏合法、共沉淀、沉积-沉淀、蒸铵沉淀和溶胶-凝胶等方法。这些制备催化剂方法大多作为现有成熟技术为本领域技术人员所熟知,在本领域书籍中均有详细的介绍,如黄仲涛所著的<工业催化剂设计与开发>,GerhardErtl教授等所著的<Preparation of Solid Catalysts>。其中本发明所述的蒸铵沉淀方法,简要步骤如下:(一)将钴盐和第二金属盐溶解于水中,也可能含有其他金属或者非金属盐;(二)将氨水逐步加入上述盐溶液中,与氨形成络合物,如铜铵络合物、钴铵络合物、银铵络合物等;(三)加入其他组分;(四)升温逐步将氨蒸发,钴与第二金属等组分沉淀下来;(五)洗涤、过滤;(六)干燥、焙烧。上述步骤只是列举了其中的一些必要步骤,并且次序没有严格的要求,本专业的技术人员可以根据需要添加一些步骤或者改变次数不改变发明的本质。
本发明进一步优选的催化剂制备方法是共沉淀、沉积-沉淀、蒸铵沉淀和溶胶-凝胶方法中的一种或者多种组合而成。
本发明中的催化剂还可以还含有碱金属或碱土金属,所述的碱金属或碱土金属含量占催化剂总量的0.1wt~30wt%。更具体而言,所述的碱金属或碱土金属选自钾、钠、钙、镁、钡中的一种或多种,含量占催化剂总量的0.5wt~15wt%,进一步优选的范围为1wt%~10wt%。碱金属和碱土金属来源可以为水溶性的硝酸盐、碳酸盐、氯盐、磷酸盐、硫酸盐、醋酸盐、氟化物、氢氧化物等。更具体而言,碱金属和碱土金属来源选自氢氧化钾、硝酸钾、碳酸钾、醋酸钾、氟化钾、磷酸钾、氢氧化钠、硝酸钠、碳酸钠、碳酸氢钠、氯化钠、硫酸钠、醋酸钠、硝酸钙、磷酸二氢钙、硝酸镁、磷酸镁、硝酸钡中的一种或多种。
碱金属和碱土金属元素的加入方式可以选自以下方式中的任意一种:在浸渍、捏合、沉淀、沉积-沉淀或者溶胶-凝胶过程中与钴盐一起溶解后加入;在共混、球磨等方法中与钴盐一起加入;在浸渍、沉淀、沉积-沉淀或者溶胶-凝胶过程中与钴盐分别或者分步加入;在催化剂前驱体中加入,如沉淀、沉积-沉淀或者溶胶-凝胶中获得的干燥后滤饼或干凝胶中,或者焙烧分解后的材料中;或者在打片或者挤条等成型阶段加入。
催化剂还含有一些氧化物组分,尽管不想做任何限制,但发明人认为这些氧化物主要起到载体的作用,所述的氧化物组分选自氧化硅、硅藻土、硅酸钙、氧化锆、氧化钛的一种或者多种,其含量占催化剂总重的10wt%~80wt%。实际上,这些载体不仅仅是起到支撑作用,还能够协助活性组分的分散或羧酸的活化,因此这些载体影响着催化剂的织构性能、产物和原料在其中的扩散、机械强度、活性和稳定性等关键性指标。
载体氧化硅可以选自水玻璃沉淀法、二氧化硅粉末、正硅酸乙酯水解、硅溶胶等。所述的二氧化硅粉末可以是通过化学沉积法、水玻璃沉淀后干燥后球磨获得、或者是硅溶胶喷雾干燥等方法获得,其尺寸选自10nm~500μm;如青岛海洋化工厂生产的粗孔微球二氧化硅(平均孔径为8.0-12.0nm,比表面积为300~600m2/g,孔容为0.8~1.1ml/g),又如广州人民化工厂生产的沉淀二氧化硅(二氧化硅(SiO2)含量%≥95.0,细度(325目筛余物)%≤1.8,比表面积为400~600m2/g)或者活性白炭黑,又如德固赛公司的气相二氧化硅AEROSIL200,其比表面为200m2/g,又如自制喷雾干燥获得的二氧化硅微球,比表面为400~500m2/g,尺寸为2~30μm。二氧化硅粉末可以在沉淀或者沉积-沉淀法中作为载体加入。所述的水玻璃直接沉淀法是指以水玻璃为原料,在水玻璃中加入酸性沉淀剂或者离子沉淀剂,如硫酸、盐酸、硝酸、醋酸、硝酸钙、硝酸氧锆、氧氯化锆、硝酸镁、硝酸钴等。沉淀剂加入后形成白色胶状物,洗涤数次后使用或者在此基础之上进行其他组分的沉淀法加入。正硅酸乙酯是在溶胶-凝胶法制备本发明的催化剂中使用。硅溶胶作为液态硅源,可直接使用进入沉淀、沉积-沉淀法的沉淀物系中。
所述的氧化锆材料来源为粉体氧化锆材料或者通过锆盐的沉淀。粉体氧化锆尺寸选自10nm~500μm,比表面大于20m2/g。锆盐的沉淀可按照以下途径实现:首先将氧氯化锆溶解在水中,随后加入苛性钠等强碱,最后将沉淀物洗涤过滤得到的凝胶;或者使用硝酸氧锆作为锆源,加入苛性钠沉淀后洗涤过滤获得的凝胶。将上述的凝胶加入到其他沉淀物中,或者将上述的凝胶经过干燥后磨成粉体后作为沉积-沉淀的载体加入。
本发明中的氧化钛可以是一些符合要求的市售二氧化钛,如德固赛公司的P25,也可以采用液相沉淀的方法制备,如采用四氯化钛或者硫酸钛作为钛源,加入尿素、氨水、碳酸钠或者苛性钠等作为沉淀剂,也可以采用有机钛酸如钛酸丁酯水解制备。
催化剂还可能含有稀土金属元素,其氧化物含量占催化剂总量的0.1wt~8wt%;所述的稀土元素选择镧或者铈中的一种,其氧化物含量占催化剂总量的0.5wt~5wt%。加入微量的稀土元素可以通过降低不凝性气体含量而使得钴催化剂的选择性得到一定程度的提高。
催化剂还含有一种或多种无机非金属元素,含量占催化剂总量的0.1wt~5wt%。更具体而言,所述的无机非金属元素选自磷、硼、氟中的一种,含量占催化剂总量的0.3wt~2wt%。这些无机非金属元素的加入,有的伴随着其他助剂的加入而进入催化剂体系,如氟化钾。有的是通过额外的方式加入,如硼的加入可采用将硼酸水溶液加入滤饼中的方式。
本发明中所述的将有机羧酸加氢转化为脂肪醇的方法,其具体原理是是将一元羧酸气化并与氢气混合,或者将一元羧酸在氢气中气化后进入加氢反应器内,并与本发明所述的催化剂接触转化为脂肪醇和水,发生的主反应方程式如下所述。
催化剂装填的反应器为固定床反应器,更优选为列管式反应器,更具体而言,是将催化剂装填在管内,而管间充填导热介质,如导热油或者水等,这样更利于反应热的移出。本领域的技术人员均熟知该项技术要领,如每根管装填量需保持一致等。
本发明的催化剂在应用于羧酸加氢中时,需要将其充分地还原活化使得绝大部分钴在进行加氢反应前都被还原为零价状态,活化的方式可以是在升温条件下通入氢气、使用还原剂如硼酸钠等、或者采用电离辐照的方法。这些方法都为本领域的技术人员所熟知。
本发明所述的加氢方法,反应温度为180~350℃,更优选为220~300℃,在该范围内催化剂的选择性变化较小,维持较高的水平。反应温度较低时,羧酸转化率较低,这使得循环能耗增大;而反应温度继续升高时,副产物尤其是不凝性气体产物如乙烷的量大幅增加。
对于一元羧酸加氢制备为醇,理论上氢气消耗量与羧酸的摩尔比为2,但为维持后续反应压力和催化剂寿命,氢气与羧酸的摩尔比例为4:1~40:1,更优比为6:1~25:1,进一步的优化比率为8:1~20:1。从反应器出来的粗产品经过气液分离器后,过量的氢气可以循环使用。
本发明中使用的催化剂选择性较高,因此副产物中不凝性气体的选择性低于15%,更优的情况下低于10%,进一步优化情况下低于5%。
羧酸的加氢是典型的加压反应,本发明使用的反应压力为0.3~8.0MPa,更优选的反应压力为0.5~4.0MPa,进一步优化的反应压力为1.0~2.5MPa。本发明使用的反应压力,相对于之前许多加氢技术公开的反应压力低许多,这使得反应条件更加温和,并且降低了成本。
在本方法中,羧酸的体积空速为0.1~5.0h-1;更优选的体积空速为0.2~2.0h-1。空速实际是根据工厂希望采出产品组成和后续分离能力有关,本发明在实施中不作限制,这是由于:在空速较高时,虽然醋酸转化率较低,但是乙醇和醋酸乙酯的产率和反而会增加,特别是醋酸乙酯选择性会提高;在空速较低时,醋酸转化率极高,但是乙醇的产率可能会降低,因此对于有分离能力并且希望多产醋酸乙酯的工厂,可以采用高空速操作模式,而对于后续分离能力较小的工厂,可采用低空速操作。本发明所述的催化剂,在0.3~1.0h-1内可以保证醋酸的转化率高于50%,更优选的高于75%,进一步优选的高于90%。
本发明可广泛应用于一元羧酸的加氢制备醇,具体而言,所述的一元羧酸选自乙酸、丙酸、丁酸、乳酸、3-羟基丙酸、衣康酸中的一种或者混合物。这些羧酸来源于可再生的生物质资源,如乳酸、3-羟基丙酸、苯甲酸、醋酸/丙酸等混合酸液等,也可以来源于其他石油替代资源,如醋酸。更优选的,所述的有机酸为乙酸和丙酸中的一种或者混合物。进一步优选的有机酸为乙酸。
本发明所述的方法,当羧酸和氢气与催化剂接触后,反应产物除醇外,还有微量其他副产物,主要来源于(1)脱羧/脱羰产物包括一氧化碳、二氧化碳、烷烃;(2)酮基化产物;(3)醇酸/醛缩合产物;(4)脱水产物等。举例而言,对于醋酸加氢制备乙醇,产物除主要由乙醇和醋酸乙酯外,还有乙醛、乙醚、丁醇、丙酮、异丙醇、甲缩醛、甲烷、乙烷、丙烷、一氧化碳、二氧化碳等。本发明描述的催化剂及其方法可以保证羧酸转化为醇和相应的酯的总选择大于70%,更优化情况大于85%,进一步优化的情况大于90%。
相对于现有技术,本发明的羧酸加氢催化剂及其方法同时具有以下优点:
(1)催化剂活性较高,目的产物选择性高;
(2)催化剂制造成本较为低廉,使得投资和运行成本降低;
(3)反应条件较温和,可以在较宽的反应操作条件下运行,增宽了操作窗口。
实施例
以下实施例是对本发明更为详细的举例描述,但本发明并不局限于这些实施例。
实施例1
取1.5mol/L的硝酸钴水溶液0.8升,在其中加入硝酸银2.0克和硝酸铜5.8克,充分溶解后,在激烈搅拌的情况下加入浓氨水(含NH3质量百分数约为28%)0.6L,形成透明的络合物溶液。升温至70℃,恒温2小时后,缓慢地加入到500g稀释的水玻璃水溶液中(二氧化硅含量约10wt%)中,在上述浆态物种,再滴加硝酸钙溶液100ml(硝酸钙浓度1.0mol/L),并继续搅拌恒温12小时。将上述浆态物过滤洗涤,并干燥过夜得到干燥滤饼。将滤饼焙烧分解后打片成型,得到催化剂CHZ-51。
实施例2
取0.4mol/L的硝酸钴水溶液1升,在其中加入四水硝酸钙23.6克和硝酸镧4.33g,充分搅拌均匀后加入广州人民化工厂生产的沉淀二氧化硅40g(二氧化硅(SiO2)含量%≥95.0,细度(325目筛余物)%≤1.8,比表面积为400~600m2/g)。升温至40℃后,加入10wt%的苛性钠溶液,实时监测溶液PH值,当溶液PH值在7.5左右时停止进入苛性钠溶液,并加入10g的硅藻土后搅拌,随后升温至70℃老化三小时后洗涤至无钠离子。将浆体过滤,并将滤饼干燥过夜。在450℃条件下分解5小时后获得催化剂前驱体。取上述前驱体80g,在其中加入10ml左右的硝酸银水溶液(含银为50mg/ml),随后打片成型获得催化剂CHZ-52。
实施例3
取1mol/L的硝酸钴水溶液1升,在其中加入钼酸铵9.5克和硝酸镧7.5g,加入20wt%碳酸钠溶液进行沉淀至PH值为9.0左右,在加热的条件下搅拌2小时,得到前驱体I。
将10g浓硝酸和6g四水硝酸钙加入300ml水中,缓慢地加入到500g稀释的水玻璃水溶液中(二氧化硅含量约10wt%)中,形成白色沉淀物,使用大功率搅拌器搅拌沉淀物形成浆态物,将这些浆态物质加入到前驱体I中,在搅拌的条件继续老化1小时。洗涤过滤,并干燥过夜得到干燥滤饼,在该滤饼中喷入含有0.1wt%的硝酸银溶液15ml后造粒。将粒子焙烧分解后打片成型,得到催化剂CHZ-53。
实施例4
升温条件下将经过干燥处理的硝酸钴和硝酸铬分别为240g和15g溶解于800ml正丙醇中,温度控制在50~60℃,缓慢加入正硅酸乙酯300g,经过纯化后制备得到含钴和铬的正硅酸乙酯。取上述的含钴和铬正硅酸乙酯100g溶解于乙醇中,加入水600ml和浓硝酸5.0g后,于75℃条件下放置6小时得到凝胶。在上述凝胶中加入20ml硝酸银水溶液(60mg Ag/ml)并搅拌打浆,将浆体喷雾干燥得到细小微球。将上述微球筛分除去300μm以上的粒子后,400℃焙烧,将上述粉体打片成型后获得催化剂CHZ-54。
实施例5
升温条件下将经过干燥处理的硝酸钴240g溶解于800ml正丙醇中,温度控制在50~60℃,缓慢加入正硅酸乙酯,经过纯化后制备得到钴:硅为0.5左右的含钴正硅酸乙酯。取上述的含钴正硅酸乙酯100g溶解于乙醇中,加入水600ml和浓硝酸5.0g后,于75℃条件下放置6小时得到凝胶。在上述凝胶中加入20ml硝酸银水溶液(60mg Ag/ml)和5ml氟化钾水溶液(含量为5wt%)并搅拌打浆,将浆体喷雾干燥得到细小微球。将上述微球筛分除去300μm以上的粒子后,400℃焙烧,将上述粉体打片成型后获得催化剂CHZ-55。
实施例6
取1mol/L的硝酸钴水溶液1升,在其中加入硝酸银1.68克和硝酸锌7.5克,充分溶解后,在激烈搅拌的情况下加入浓氨水(含NH3质量百分数约为28%)0.5L,形成透明的络合物溶液。在上述络合物溶液中加入广州人民化工厂生产的沉淀二氧化硅40g(二氧化硅(SiO2)含量%≥95.0,细度(325目筛余物)%≤1.8,比表面积为400~600m2/g)。逐步升温至85℃,恒温保持2小时后,加入硝酸镧3.0g,继续恒温2小时。将上述浆态物过滤洗涤,并干燥过夜得到干燥滤饼,并在滤饼上喷淋稀释磷酸液体10ml。将滤饼焙烧分解后打片成型,得到催化剂CHZ-56。
对比实施例1
取30克二氧化硅载体(青岛海洋化工厂,吸水率约为0.9g/g),将60克硝酸钴和1g硝酸银溶于水中,通过结合多次浸渍-共浸渍-等体积浸渍的方法制备得到前驱体,并将该前驱体400℃焙烧获得催化剂CHZ-57。
对比实施例2
按照CN200980134837.2公开的方法,制备了一个钙改性的二氧化硅负载钴-铂催化剂,钴负载量为10wt%和铂负载量0.85wt%。该催化剂为CHZ-58。
实施例4
将上述催化剂在固定床反应器中进行评价,用于醋酸加氢制备乙醇,装填量为10ml,采用1:1的石英砂稀释,在使用前采用纯氢气还原,还原最高温度为450~500℃,具体反应条件和反应结果如表1中所示。
在本实施例中,醋酸转化率和乙醇选择性按照各组分的碳摩尔百分含量计算获得。
其他产物有:乙醛、乙烷、甲烷、一氧化碳、二氧化碳、乙酸醛、丙酮、丙
醇等;
表1
实施例5
将上述催化剂在固定床反应器中进行评价,用于乳酸(20wt%水溶液)加氢制备1,2-丙二醇,装填量为10ml,采用1:1的石英砂稀释,在使用前采用纯氢气还原,还原最高温度为450~500℃,具体反应条件和反应结果如表2中所示。
在本实施例中,乳酸转化率和1,2-丙二醇选择性按照各组分的碳摩尔百分含量计算获得。其他副产物包括:正丙醇、异丙醇、2-羟基-丙醛、丙烷、乙烷、一氧化碳、二氧化碳、乙醇、戊二酮等。
表2
Claims (12)
1.一种羧酸气相加氢制备醇的方法,其特征在于,在固定床反应器中,羧酸蒸汽与含氢气体混合与加氢催化剂接触反应后转化为醇和水,氢气与羧酸的摩尔比为4:1~40:1,反应温度为180~350℃,反应压力为0.3~8.0MPa,羧酸的体积空速为0.1~5.0h-1;
所述的加氢催化剂包括如下组分:
(1)含有钴和银,其中钴金属含量占催化剂总重的15wt%~50wt%,银金属占催化剂总重的0.1wt%~10wt%;
(2)氧化物;所述的氧化物选自氧化硅、硅藻土、硅酸钙、氧化锆、氧化钛的一种或者多种,其含量占催化剂总重的20wt%~80wt%;
所述的催化剂是采用共沉淀、沉积-沉淀、蒸氨沉淀或者溶胶-凝胶方法中的一种或者多种结合制备的;所述的羧酸为一元羧酸。
2.根据权利要求1所述的的方法,其特征在于,氢气与羧酸的摩尔比例为8:1~20:1,反应温度为220~300℃,反应压力为0.5~4.0MPa,羧酸的体积空速为0.2~2.0h-1。
3.根据权利要求1所述的方法,其特征在于,所述的催化剂中钴金属含量为20wt%~40wt%,银金属含量占催化剂总重的0.2wt%~5wt%。
4.根据权利要求1所述的方法,其特征在于,所述的催化剂还任选地含有碱金属或碱土金属,所述的碱金属或碱土金属含量占催化剂总量的0wt~30wt%。
5.根据权利要求4所述的方法,其特征在于,所述的碱金属或碱土金属选自钾、钠、钙、镁、钡中的一种或多种,含量占催化剂总量的0wt~15wt%。
6.根据权利要求1所述的方法,其特征在于,所述的催化剂任选地含有稀土金属元素,含量占催化剂总量的0wt~8wt%。
7.根据权利要求6所述的方法,其特征在于,所述的稀土元素为镧或铈,含量占催化剂总量的0wt~5wt%。
8.根据权利要求1所述的方法,其特征还在于,所述的催化剂还任选地含有一种或多种无机非金属元素,含量占催化剂总量的0wt~5wt%。
9.根据权利要求8所述的方法,其特征在于,所述的无机非金属元素选自磷、硼、氟中的一种,含量占催化剂总量的0wt~2wt%。
10.根据权利要求1所述的方法,其特征在于所述的羧酸为乙酸、丙酸、丁酸、乳酸、3-羟基丙酸、苯甲酸中的一种或者混合物。
11.根据权利要求10所述的方法,其特征在于,所述的羧酸为乙酸和/或丙酸。
12.根据权利要求11所述的方法,其特征在于,所述的羧酸为乙酸。
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