CN103787827B - 羧酸选择加氢制备醇的方法 - Google Patents
羧酸选择加氢制备醇的方法 Download PDFInfo
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- CN103787827B CN103787827B CN201210429218.XA CN201210429218A CN103787827B CN 103787827 B CN103787827 B CN 103787827B CN 201210429218 A CN201210429218 A CN 201210429218A CN 103787827 B CN103787827 B CN 103787827B
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- Prior art keywords
- carboxylic acid
- alcohol
- catalyzer
- cobalt
- prepares
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- 238000000034 method Methods 0.000 title claims abstract description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 51
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 43
- 239000010941 cobalt Substances 0.000 claims abstract description 43
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 28
- 239000010970 precious metal Substances 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 77
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 238000001556 precipitation Methods 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 229910052728 basic metal Inorganic materials 0.000 claims description 5
- 150000003818 basic metals Chemical class 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
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 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 group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 229910052796 boron Inorganic materials 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
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000654 additive Substances 0.000 abstract description 7
- 230000000996 additive effect Effects 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000009467 reduction Effects 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
- 239000002253 acid Substances 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 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
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 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
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000243 solution Substances 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
- 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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000178 monomer Substances 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
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000010025 steaming 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
- 238000005406 washing Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- 230000004913 activation Effects 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 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
- 239000002244 precipitate Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007493 shaping process Methods 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
- 238000010792 warming Methods 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand 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
- 238000013019 agitation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 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
- 238000013461 design Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 235000021463 dry cake Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption 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
- 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
- BSABBBMNWQWLLU-UHFFFAOYSA-N lactaldehyde Chemical compound CC(O)C=O BSABBBMNWQWLLU-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-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
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 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
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000000967 suction filtration 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
- VBWYZPGRKYRKNV-UHFFFAOYSA-N 3-propanoyl-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(C(=O)CC)C2=C1 VBWYZPGRKYRKNV-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- 240000001414 Eucalyptus viminalis Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ULSAYCVVCOFSKH-UHFFFAOYSA-N N.[Re+4] Chemical compound N.[Re+4] ULSAYCVVCOFSKH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 239000004115 Sodium Silicate Substances 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—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
- B01J23/8896—Rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/61—Surface area
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Abstract
本发明涉及一种羧酸加氢制备为醇的方法,使用的加氢催化剂至少含钴和痕量级的贵金属助剂。在本发明中,使用的催化剂至少含有占催化剂总重的10wt%~40wt%的钴,而贵金属含量与钴的比率为1∶150以上,远远低于1wt%。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催化剂将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/m3Cat/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 oflactic acid to propylene glycol,Applied Catalysis A: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%。
CN102149662公开一种含钴的醋酸加氢催化剂,制备方法为浸渍法,钴的负载量为0.1wt%~20wt%,在其公开的实施例中,钴负载量在5wt%~10wt%,而使用的助剂使用贵金属助剂,如铂和钯,助剂含量高于1wt%,这将使得催化剂的成本极其高昂,或者为具有较高污染性的铬助剂;并且醋酸的转化率较低,尽管发明者未公开其时空收率,但是通过其提供的实施例数据,可计算出其时空收率较低,如其公开的钴-铬催化剂,乙醇的时空收率仅在82g/L/h~258g/L/h。
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,并涉及使用仅含有痕量级贵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,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)至少含有钴和痕量的贵金属,其中钴金属含量占催化剂总重的15wt%~45wt%,所述的痕量的贵金属选自钯、铂和铼中的一种或多种,其重量与钴金属重量的比率在1:100~1:300;
(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10wt%~80wt%;
所述的加氢催化剂是通过共沉淀、沉积-沉淀、蒸氨沉淀、溶胶-凝胶和球磨方法中的一种或者多种结合制备的;所述的用于加氢的羧酸为一元羧酸。
本发明详细叙述如下:
本发明的加氢催化剂主活性组分为钴,其中钴金属含量占催化剂总重的10wt%~50wt%,更优选的含量占催化剂总重的15wt%~45wt%,进一步优选占催化剂总重的10wt%~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,这会使得催化剂的乙醇时空收率处于较低的水平,由于羧酸具有较强的腐蚀性,因此其直接加氢制备醇的反应器一般需要使用较为昂贵的不锈钢材料,因此时空收率较低时会使得反应器的成本极高;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,甚至有所下降,在较高含量时候有明显的下降。这一结果是出乎意料的:因为人们往往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水溶性的金属盐如硝酸盐、硫酸盐、氯盐、醋酸盐、草酸盐和溴盐,或者选自金属钴,如钴金属板等。更具体的水溶性金属盐选自硝酸钴、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。
贵金属是本发明催化剂中另一种重要的组成组分,贵金属助剂的加入可以极大地提高了催化剂的选择性和稳定性,所述的贵金属具体而言为钯、铂或者铼,但是贵金属的成本极高,因此降低其含量具有极其重要的意义。本发明人发现通过特定的制备方法得到的催化剂和特定的催化剂组成情况下,虽然贵金属的含量极低,但是依然可以保持极高的催化剂活性、选择性和稳定性,可体现本发明技术方案的优越性:较为低廉的催化剂成本和优异的反应性能。
贵金属助剂加入后,催化剂活性、选择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:贵金属改善了钴的电子形态、抑制了积碳的产生、促进了催化剂的还原、抑制了钴的氧化等。更意外的,发明人发现,在通过本发明所述的方法制备的钴催化剂,贵金属助剂改善催化剂反应性能的效果更加明显。
贵金属含量与钴含量之间的比率在1:100~1:300,优选范围为1:150~1:250,实际含量远远低于1wt%;所述的贵金属是指钯、铂和铼中的一种或者多种。
对所述的贵金属来源没有限制,可以是所知的所有贵金属化合物。进一步优化的贵金属的来源有单质钯、单质铂、单质铼、氯化钯、硝酸钯、醋酸钯、氯亚钯酸钾、二氯四氨钯、氯亚钯酸铵、四亚硝基钯酸钾、氯亚钯酸钾、氯铂酸、四氯化铂、溴铂酸、氯铂酸钾、氯铂酸钠、氯亚铂酸铵、氯亚铂酸钾、氯化四铵合铂、四亚硝基铂酸钾、二亚硝基二氨铂、二氯二氨铂、溴铂酸铵、硝酸铂、氯铂酸铵、铼酸铵、氧化铼等。
本发明所述的催化剂制备方法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、熔融-抽滤、球磨和溶胶-凝胶等方法。更优选的方法包括共沉淀、沉积-沉淀、蒸氨沉淀、溶胶-凝胶和球磨方法中的一种或者多种结合制备,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,与氨形成钴铵络合物;(三)加入其他组分;(四)升温逐步将氨蒸发,钴沉淀下来;(五)洗涤、过滤;(六)干燥、焙烧。本发明中的熔融-抽滤法的步骤实质是指Raney催化剂的制备过程:(一)通过在熔炉中将具有催化活性的金属钴、铋和铝(或者硅)熔合,得到的熔体进行淬火冷却,然后粉碎成为均匀的细颗粒,溶化步骤中还可能添加其他的助剂;(二)将催化剂细颗粒成型,成型技术可以采用现有所周知的技术,如打片、捏合挤条、滚球等;(三)将所得的上述成型催化剂在碱液中抽滤,即得到获得催化剂。
贵金属的添加方式可以是多样的:如在沉淀、沉积-沉淀、蒸铵沉淀法或者溶胶-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、蒸铵沉淀法或者溶胶-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,在球磨过程中与含钴化合物一起加入。
本发明中的催化剂还可以含有碱金属或碱土金属,其含量占催化剂总量的0wt~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,其含量优选占催化剂总量的0wt~15wt%,进一步优选的范围为0wt%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,其来源选自氢氧化钾、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、熔融等方法中与钴盐一起加入或者分步加入;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。
催化剂中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,选自氧化硅、氧化铝、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结构性能、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AEROSIL 200,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。
载体氧化硅或者氧化铝也可能是在作为熔融-抽滤法制备的催化剂中作为粘结剂加入,使得所得的催化剂粉末能够成型为本发明所需的形状。
本发明所述的催化剂的形状可以是多种多样的,如球状、条状、柱状、环状等等,尺寸在0.3~15mm之间,更优选在1~10mm之间,这个尺寸的要求主要是根据本发明所述的固定床反应器设计,以便利于安装、降低床层压力等要求。这些知识均为本专业的技术人员所熟知。
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。
催化剂还可以含有稀土金属元素,其氧化物含量占催化剂总量的0wt~8wt%;所述的稀土元素选择镧或者铈中的一种,其氧化物含量优选占催化剂总量的0wt~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。
催化剂还任选含有一种或多种无机非金属元素,其含量占催化剂总量的0wt~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0wt~5wt%,优选0wt~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。
本发明中所述的将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。
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醇的反应,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,羧酸与氢气的摩尔比例为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。空速实际是由工厂希望采出产品的组成和后续分离能力决定的,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,所述的羧酸为乙酸和丙酸中的一种或者混合物。进一步优选的羧酸为乙酸。
本发明所述的方法,当氢气和羧酸与催化剂接触后,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1mol/L的硝酸钴水溶液1升,加入硝酸镧3.0g和硝酸钙6.0g,铼铵酸0.45g,在其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),升温至60度,在激烈搅拌的情况下加入20wt%的碳酸钠水溶液至PH值为8.0。逐步升温至80℃,恒温保持2小时后,继续恒温2小时后降温至室温,慢慢加入硼酸4.0g。洗涤过滤,并干燥过夜得到干燥滤饼。将粒子焙烧分解后打片成型,得到催化剂CHZ-101。
实施例2
取1.2mol/L的硝酸钴水溶液1升,在其中加入氯亚铂酸铵0.6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80℃,恒温2小时后,缓慢地加入到400g稀释的水玻璃水溶液中(二氧化硅含量约12wt%)中,在上述浆态物种,再滴加硝酸镁溶液150ml(硝酸钙浓度0.5mol/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,加入氟化钾水溶液(含氟化钾5wt%)20g。将滤饼焙烧分解后打片成型,得到催化剂CHZ-102。
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-103。
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-104。
实施例3
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;
实施例4
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1
表2
Claims (9)
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,其中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)钴和痕量的贵金属,其中钴金属含量占催化剂总重的15wt%~45wt%,所述的痕量的贵金属选自钯、铂和铼中的一种或多种,其重量与钴金属重量的比率为1:100~1:300;
(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10wt%~80wt%;
所述的加氢催化剂是通过共沉淀、沉积-沉淀、蒸氨沉淀、溶胶-凝胶和球磨方法中的一种或者多种结合制备的;所述的用于加氢的羧酸为一元羧酸;
所述的催化剂中还含有碱金属或碱土金属、稀土金属元素和无机非金属元素中的至少一种,其中,所述碱金属或碱土金属的含量占催化剂总量的0wt~30wt%,所述稀土金属元素的氧化物含量占催化剂总量的0wt~8wt%,所述无机非金属元素的含量占催化剂总量的0wt~5wt%。
2.根据权利要求1所述的羧酸气相加氢制备醇的方法,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所述的羧酸气相加氢制备醇的方法,其特征在于,所述的催化剂中贵金属重量与钴金属重量的比率在1:150~1:250。
4.根据权利要求1所述的羧酸气相加氢制备醇的方法,其特征在于,所述的催化剂中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%。
5.根据权利要求1所述的羧酸气相加氢制备醇的方法,其特征在于,所述的稀土金属元素为镧或铈,其氧化物含量占催化剂总量的0wt~5wt%。
6.根据权利要求1所述的羧酸气相加氢制备醇的方法,其特征在于,所述的无机非金属元素为磷、硼或氟,含量占催化剂总量的0wt~2wt%。
7.根据权利要求1所述的羧酸气相加氢制备醇的方法,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它们的混合物。
8.根据权利要求7所述的羧酸气相加氢制备醇的方法,其特征在于,所述的羧酸为乙酸和/或丙酸。
9.根据权利要求8所述的羧酸气相加氢制备醇的方法,其特征在于,所述的羧酸为乙酸。
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