CN109647394B - Catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof - Google Patents
Catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof Download PDFInfo
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- CN109647394B CN109647394B CN201811511993.3A CN201811511993A CN109647394B CN 109647394 B CN109647394 B CN 109647394B CN 201811511993 A CN201811511993 A CN 201811511993A CN 109647394 B CN109647394 B CN 109647394B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 30
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 37
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 69
- 150000001299 aldehydes Chemical class 0.000 claims description 43
- 239000012018 catalyst precursor Substances 0.000 claims description 39
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- 230000009467 reduction Effects 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000011068 loading method Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 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 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 16
- 239000012279 sodium borohydride Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 229940043350 citral Drugs 0.000 claims description 14
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical group CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 13
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 claims description 12
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 9
- 239000005792 Geraniol Substances 0.000 claims description 9
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229940113087 geraniol Drugs 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 8
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003303 ruthenium Chemical class 0.000 claims description 4
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 2
- 229910052745 lead Inorganic materials 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007806 chemical reaction intermediate Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 235000013599 spices Nutrition 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000012298 atmosphere Substances 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 5
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- WVYSWPBECUHBMJ-UHFFFAOYSA-N 2-methylprop-1-en-1-ol Chemical compound CC(C)=CO WVYSWPBECUHBMJ-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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- B01J35/613—
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/89—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
- B01J23/8953—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 zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/8966—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 germanium, tin or lead
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- B01J35/40—
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- B01J35/615—
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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
- C07C29/14—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 a —CHO group
- C07C29/141—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 a —CHO group with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde, which comprises a carrier, an active component, an auxiliary agent and an inhibitor, wherein the carrier is CeO 2 The active component is Ru, the auxiliary agent is one of Fe, Co, Mn and Sn, and the inhibitor is one of Zn, Pb and Bi. The catalyst has better conversion rate and selectivity when being used for hydrogenating the alpha, beta-unsaturated aldehyde with the general formula I to obtain the corresponding alcohol with the general formula II, can be repeatedly used, and can be used in the synthesis process of important raw materials and reaction intermediates in the production of spices, medicaments and other fine chemical products.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, and relates to a catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde, and a preparation method and application thereof.
Background
Alpha, beta-unsaturated alcohols, such as geraniol and nerol, cinnamyl alcohol and isobutenol, are important raw materials and reaction intermediates in the production of perfumes, medicaments and other fine chemical products.
Currently, NaBH is mostly used in industrial production of alpha, beta-unsaturated alcohols 4 Or AlLiH 4 Directly reducing alpha, beta-unsaturated aldehyde to obtain the product. Although this method can obtain α, β -unsaturated alcohols in high yields, it has serious drawbacks: not only the reaction condition is difficult to control and the product is difficult to separate, but also a large amount of three wastes are generated to pollute the environment, which does not meet the requirements of modern industrial production.
The method for preparing the alpha, beta-unsaturated alcohol by directly and selectively hydrogenating the alpha, beta-unsaturated aldehyde by adopting the solid catalyst is more environment-friendly compared with a homogeneous reaction, and the product is easy to separate and recycle, so that the defects in the industry can be overcome.
The α, β -unsaturated aldehyde molecule contains conjugated C = C bonds and C = O bonds. Thermodynamically, the bond energy of the C = O bond (715 kJ/mol) is larger than the bond energy of the C = C bond (615 kJ/mol); the hydrogenation activity of C = C bond is higher than that of C = O bond, and it is more difficult to select C = O bond than C = C bond. Therefore, the development of a C = O bond selective hydrogenation catalyst with high selectivity and high stability is key.
Patent US4100180 describes a process for hydrogenating unsaturated aldehydes in the presence of a PtO/Zn/Fe catalyst to give unsaturated alcohols, citral being hydrogenated at a conversion of 70% to give geraniol and nerol in an amount of 85.5%. In the technical scheme of patent CN107056566A, a series of catalysts are disclosed for hydrogenating alpha, beta-unsaturated aldehyde to alpha, beta-unsaturated alcohol, and the better result is that the catalyst 9% Ag-2% Ir-5% Ca/SiO is used in a fixed bed 2 When the conversion rate of the citral is 92.3%, the selectivity of the unsaturated alcohol is 86.2%; in the kettle reactor, 0.1 percent of Rh to 2 percent of Ru to 4 percent of Mn/TiO catalyst is used 2 When the conversion of cinnamaldehyde was 81.3%, the selectivity for unsaturated alcohol was 61.3%. The above techniques have problems that the conversion of unsaturated aldehydes is low and the selectivity of unsaturated alcohols is unsatisfactory.
Patent CN1258506C discloses the use of a Ru/Fe/C suspension catalyst in a bubble column reactor for the hydrogenation of citral with a selectivity of 92% for geraniol and nerol at 96% conversion, whereas methanol and trimethylamine are added in the catalytic reaction, making an additional separation step necessary in the work-up process. The patent CN106824182A adopts a composite catalyst 3% Ir-2% Ru/C to be applied to selective hydrogenation of citral to synthesize geraniol or nerol, the conversion rate of raw materials is 100%, and the selectivity of target products can be more than 98%. However, the catalyst is expensive, and the isopropanol used as a solvent in the reaction process increases the burden of the product separation process.
In the technical scheme of patent CN1422693, a carbon-supported iron-doped ruthenium catalyst is used for hydrogenating citral in a suspension bed or a fixed bed to produce geraniol and nerol. When the conversion rate of citral is 96.1%, the total selectivity of geraniol and nerol is 97.6%, but the fixed bed reactor requires a long service life of the catalyst.
Patent CN104974016B describes the use of Pt-Ru-Sn/TiO in a solvent-free system 2 The catalyst is cinnamyl alcohol, the selectivity of cinnamyl alcohol is 93-95% under the condition that cinnamyl aldehyde is nearly completely converted, but the catalyst mainly aims at specific alpha, beta-unsaturated aldehyde, and therefore the catalyst has certain limitation on application.
In summary, the catalysts disclosed in the prior publications have the problems of low selectivity to unsaturated alcohols, organic solvent pollution, high catalyst life requirements, and effectiveness for only a specific α, β -unsaturated aldehyde. There is no selective hydrogenation catalyst suitable for different kinds of alpha, beta-unsaturated aldehyde, and the catalyst has both activity and selectivity and environment friendly process.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde, and a preparation method and application thereof, so as to realize the following purposes:
(1) the catalyst of the invention is suitable for the selective hydrogenation of different kinds of alpha, beta-unsaturated aldehyde;
(2) the selectivity of the catalyst is high;
(3) the selectivity is not influenced by repeatedly applying the catalyst;
(4) eliminating organic solvent pollution.
In order to solve the technical problem, the invention adopts the following technical scheme:
a catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde is composed of carrier (CeO), active component, assistant and inhibitor 2 The active component is ruthenium (Ru), the auxiliary agent is one of Fe, Co, Mn and Sn, and the inhibitor is one of Zn, Pb and Bi.
The loading capacity of the active component Ru is 1% -10%, the loading capacity of the auxiliary agent is 0.05% -10%, and the loading capacity of the inhibitor is 0.01% -1%.
In the catalyst, the particle size of the carrier is 150-500 meshes, and the specific surface area is 10-300m 2 /g。
The specific preparation steps of the catalyst are as follows:
(1) preparation of the support
Dropwise adding 1-5% sodium bicarbonate water solution into 5-20% cerous nitrate solution to obtain suspension, standing and aging at room temperature for 5-24h, filtering to obtain filter cake, drying at 60-120 deg.C for 2-12h, and calcining at 300-500 deg.C for 2-4h to obtain CeO 2 A carrier;
(2) preparation of catalyst precursor
The CeO obtained in the step (1) 2 Soaking the carrier in a salt solution containing soluble ruthenium salt, salt of an auxiliary agent and an inhibitor, stirring and adsorbing for 4-24h at the temperature of room temperature to 80 ℃, and then drying for 6-12h at the temperature of 60-120 ℃ to obtain a catalyst precursor;
(3) first stage reduction
Adding an alkaline solution into a catalyst precursor, adjusting the pH value of the slurry to 10-12, reducing the solution by adopting a sodium borohydride solution at the reduction temperature of 20-80 ℃ for 0.5-4h, filtering, washing, and drying at the temperature of 60-120 ℃ for 12 h;
(4) second stage reduction
And (4) introducing hydrogen into the sample dried in the step (3) at the temperature of 300 ℃ and 500 ℃ for reduction treatment for 2-4h to obtain the catalyst.
The ruthenium salt is one of ruthenium chloride, ruthenium nitrate and ruthenium acetate.
The salt of the auxiliary agent is one of chloride, nitrate and acetate of the auxiliary agent;
the salt of the inhibitor is one of chloride, nitrate and acetate of the inhibitor;
the alkali is Na 2 CO 3 、NaHCO 3 、(NH 4 ) 2 CO 3 、NH 4 HCO 3 NaOH or NH 3 ·H 2 O。
The invention also provides the application of the catalyst in the selective hydrogenation of alpha, beta-unsaturated aldehyde to prepare corresponding unsaturated alcohol, the alpha, beta-unsaturated aldehyde (formula I) and the catalyst are put into a reactor, anda certain H 2 Carrying out selective hydrogenation reaction under pressure and temperature, after the reaction is finished, cooling and filtering the catalyst to obtain corresponding unsaturated alcohol (formula II), wherein the reaction process is as follows:
wherein R is 1 And R 2 Are identical or different and are each independently hydrogen or a C1-C20 hydrocarbon group or a phenyl group, R 3 Hydrogen or C1-C4 alkyl (e.g., citral, cinnamaldehyde, methacrolein, etc.).
Wherein, the alkyl group comprises alkyl, alkenyl or alkynyl, preferably alkyl or alkenyl.
Said H 2 The pressure is 0.5-5MPa, the reaction temperature is 30-180 ℃, and the reaction time is 2-24 h.
The catalyst obtained by filtering can be used mechanically, and the test result shows that the activity and the selectivity of the catalyst are not obviously reduced after the catalyst is used mechanically for many times.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the reaction is carried out in a solvent-free system, thereby eliminating the pollution of organic solvents, lightening the burden of separation procedures and being beneficial to reducing the production cost.
(2) The catalyst has the advantages of low price, high activity and good selectivity, the activity and the selectivity of the catalyst are not obviously reduced after the catalyst is reused for 50 times, the catalyst can be separated by a filtering method, the operation is simple, and the large-scale production is facilitated.
(3) The catalyst shows higher selectivity in the selective hydrogenation process of different alpha, beta-unsaturated aldehydes, and the conversion rate of the unsaturated aldehydes is 99.0-99.8%; the selectivity of the unsaturated alcohol is 88.5-98.5%;
the catalyst can be used for selective hydrogenation of citral, cinnamaldehyde and methacrolein, and when the catalyst is used for preparing geraniol and nerol by selective hydrogenation of citral, the conversion rate of unsaturated aldehyde is 99.0-99.8%; the selectivity of the unsaturated alcohol is 97.1-98.5%; when the method is used for preparing cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde, the conversion rate of unsaturated aldehyde is 99.1-99.7%; the selectivity of the unsaturated alcohol is 97.8-98.2%; when the method is used for preparing the isobutenol by selectively hydrogenating the methacrolein, the conversion rate of the unsaturated aldehyde is 99.2 percent; the selectivity to unsaturated alcohol was 88.5%.
The present invention will be further described with reference to the following examples.
Detailed Description
Example 1
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
Dropwise adding 8g of 3% sodium bicarbonate water solution into 378.5g of 10% cerium nitrate solution to obtain a suspension, standing and aging the suspension for 8 hours at room temperature, filtering to obtain a filter cake, drying the filter cake at 120 ℃ for 12 hours, and roasting the filter cake at 500 ℃ for 4 hours to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium chloride, ferric chloride and zinc acetate, wherein the mass contents of ruthenium, iron and zinc in the impregnation liquid are respectively 3.0%, 5.0% and 0.5%. And (2) soaking 10g of the carrier in 10g of the soaking solution, stirring and adsorbing at room temperature for 24h, naturally drying, and then drying at 60 ℃ for 12h to prepare a catalyst precursor, wherein the prepared catalyst precursor has 3.0% of Ru load, 5.0% of Fe load and 0.5% of Zn load.
(3) First stage reduction
Adding a sodium carbonate solution into a catalyst precursor, adjusting the pH of the slurry to 10, reducing the solution by using a sodium borohydride solution, wherein the using amount of the sodium borohydride solution is more than 100% of the theoretical using amount, reducing the solution for 4 hours at 20 ℃, filtering, washing and drying the solution for 12 hours at 120 ℃.
(4) Second stage reduction
Reducing at 500 deg.C for 4h in hydrogen atmosphere to obtain 3.0% Ru-5.0% Fe-0.5% Zn/CeO 2 A catalyst.
Example 2
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
Dropwise adding 8g of 3% sodium bicarbonate water solution into 378.5g of 10% cerium nitrate solution to obtain a suspension, standing and aging the suspension for 8 hours at room temperature, filtering to obtain a filter cake, drying the filter cake at 120 ℃ for 12 hours, and roasting the filter cake at 500 ℃ for 4 hours to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
And preparing impregnation liquid containing ruthenium nitrate, ferric nitrate and zinc nitrate, wherein the mass contents of ruthenium, iron and zinc in the impregnation liquid are respectively 5.0%, 1.5% and 1.0%. And (2) soaking 10g of the carrier in 10g of the soaking solution, stirring and adsorbing at room temperature for 24h, naturally drying, and then drying at 60 ℃ for 6h to prepare a catalyst precursor, wherein in the prepared catalyst precursor, the loading capacity of Ru is 5.0%, the loading capacity of Fe is 1.5%, and the loading capacity of Zn is 1.0%.
(3) First stage reduction
Adding a sodium carbonate solution into a catalyst precursor, adjusting the pH of the slurry to 10, reducing the solution by using a sodium borohydride solution, wherein the using amount of the sodium borohydride solution is more than 100% of the theoretical using amount, reducing the solution for 4 hours at 20 ℃, filtering, washing and drying the solution for 12 hours at 120 ℃.
(4) Second stage reduction
Then reducing for 2 hours at 500 ℃ in the hydrogen atmosphere to obtain 5.0 percent of Ru, 1.5 percent of Fe, 1.0 percent of Zn/CeO 2 A catalyst.
Example 3
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
Dropwise adding 8g of 3% sodium bicarbonate water solution into 378.5g of 10% cerium nitrate solution to obtain a suspension, standing and aging the suspension for 8 hours at room temperature, filtering to obtain a filter cake, drying the filter cake at 120 ℃ for 12 hours, and roasting the filter cake at 500 ℃ for 2 hours to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium acetate, ferric nitrate and zinc nitrate, wherein the mass contents of ruthenium, iron and zinc in the impregnation liquid are respectively 1.0%, 0.05% and 0.1%. And (2) soaking 10g of the carrier in 10g of the soaking solution, stirring and adsorbing at room temperature for 24h, naturally drying, and then drying at 60 ℃ for 12h to prepare a catalyst precursor, wherein the prepared catalyst precursor has the Ru loading of 1.0%, the Fe loading of 0.05% and the Zn loading of 0.1%.
(3) First stage reduction
Adding a sodium carbonate solution into the catalyst precursor, adjusting the pH of the slurry to 12, reducing the solution by using a sodium borohydride solution, wherein the using amount of the sodium borohydride solution is more than 100% of the theoretical using amount, reducing the solution at 20 ℃ for 4 hours, filtering, washing and drying the solution at 60 ℃ for 12 hours.
(4) Second stage reduction
Reducing at 500 deg.C for 2h in hydrogen atmosphere to obtain 1.0% Ru-0.05% Fe-0.1% Zn/CeO 2 A catalyst.
Example 4
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
8g of 3% sodium bicarbonate aqueous solution is dropwise added into 378.5g of 10% cerium nitrate solution, the obtained suspension is stood and aged for 8 hours at room temperature, a filter cake is filtered, dried for 12 hours at 120 ℃, and roasted for 2 hours at 500 ℃ to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium acetate, ferric nitrate and lead nitrate, wherein the mass contents of ruthenium, iron and lead in the impregnation liquid are respectively 10.0%, 1.5% and 0.1%. And (2) soaking 10g of the carrier in 10g of the soaking solution, stirring and adsorbing at room temperature for 24h, naturally drying, and then drying at 60 ℃ for 12h to prepare a catalyst precursor, wherein in the prepared catalyst precursor, the loading capacity of Ru is 10.0%, the loading capacity of Fe is 1.5%, and the loading capacity of Pb is 0.1%.
(3) First stage reduction
Adding a sodium hydroxide solution into a catalyst precursor, adjusting the pH of the slurry to 12, reducing the solution by using a sodium borohydride solution, wherein the using amount of the sodium borohydride solution is more than 100% of the theoretical using amount, reducing the solution at 20 ℃ for 4 hours, filtering, washing and drying the solution at 60 ℃ for 12 hours.
(4) Second stage reduction
Reducing at 300 deg.C for 2h in hydrogen atmosphere to obtain 10% Ru-1.5% Fe-0.1% Pb/CeO 2 A catalyst.
Example 5
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
24g of 1 percent sodium bicarbonate aqueous solution is dropwise added into 757g of 5 percent cerium nitrate solution, the obtained suspension is stood and aged for 5h at room temperature, filter cake is filtered, dried for 12h at 60 ℃ and roasted for 4h at 300 ℃ to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium nitrate, ferric nitrate and lead nitrate, wherein the mass contents of ruthenium, iron and lead in the impregnation liquid are respectively 10.0%, 10.0% and 1.0%. Soaking 10g of carrier in 10g of impregnation liquid, stirring and adsorbing for 4h at 80 ℃, naturally drying, and then drying for 12h at 120 ℃ to prepare a catalyst precursor, wherein in the prepared catalyst precursor, the loading capacity of Ru is 10.0%, the loading capacity of Fe is 10.0%, and the loading capacity of Pb is 1.0%.
(3) First stage reduction
Adding a sodium bicarbonate solution into the catalyst precursor, adjusting the pH of the slurry to 10, reducing the solution by using a sodium borohydride solution, wherein the using amount of the sodium borohydride solution is more than 100% of the theoretical using amount, reducing the solution at 80 ℃ for 0.5h, filtering, washing and drying at 120 ℃ for 12 h.
(4) Second stage reduction
Reducing at 300 deg.C for 4h in hydrogen atmosphere to obtain 10.0% Ru-10.0% Fe-1.0% Pb/CeO 2 A catalyst.
Example 6
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
24g of 1 percent sodium bicarbonate aqueous solution is dropwise added into 757g of 5 percent cerium nitrate solution, the obtained suspension is stood and aged for 5h at room temperature, filter cake is filtered, dried for 12h at 60 ℃ and roasted for 4h at 300 ℃ to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium nitrate, cobalt nitrate and lead acetate, wherein the mass contents of ruthenium, cobalt and lead in the impregnation liquid are respectively 5.0%, 1.5% and 1.0%. Soaking 10g of carrier in 10g of soaking solution, stirring and adsorbing for 4h at 80 ℃, naturally drying, and then drying for 12h at 120 ℃ to prepare a catalyst precursor, wherein the prepared catalyst precursor has 5.0% of Ru load, 1.5% of Co load and 1.0% of Pb load.
(3) First stage reduction
Adding an ammonia carbonate solution into a catalyst precursor, adjusting the pH value of the slurry to 10, reducing the solution by using a sodium borohydride solution, wherein the using amount of the solution is more than 100% of the theoretical using amount, reducing the solution at 80 ℃ for 0.5h, filtering, washing and drying at 120 ℃ for 12 h.
(4) Second stage reduction
Reducing at 300 deg.C for 4 hr in hydrogen atmosphere to obtain 5.0% Ru-1.5% Co-1.0% Pb/CeO 2 A catalyst.
Example 7
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
5g of 5 percent sodium bicarbonate aqueous solution is dropwise added into 190g of 20 percent cerium nitrate solution, the obtained suspension is stood and aged for 24 hours at room temperature, filter cake is filtered, dried for 12 hours at 60 ℃ and roasted for 4 hours at 300 ℃ to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium nitrate, manganese nitrate and bismuth nitrate, wherein the mass contents of ruthenium, manganese and bismuth in the impregnation liquid are respectively 5.0%, 1.5% and 1.0%. And (2) soaking 10g of the carrier in 10g of the soaking solution, stirring and adsorbing for 4h at 80 ℃, naturally drying, and then drying for 12h at 120 ℃ to prepare a catalyst precursor, wherein the prepared catalyst precursor has 5.0% of Ru load, 1.5% of Mn load and 1.0% of Bi load.
(3) First stage reduction
Adding an ammonium bicarbonate solution into a catalyst precursor, adjusting the pH of the slurry to 10, reducing the solution by using a sodium borohydride solution, wherein the using amount of the sodium borohydride solution is more than 100% of the theoretical using amount, reducing the solution at 80 ℃ for 0.5h, filtering, washing and drying at 120 ℃ for 12 h.
(4) Second stage reduction
Reducing at 300 deg.C for 4 hr in hydrogen atmosphere to obtain 5.0% Ru-1.5% Mn-1.0% Bi/CeO 2 A catalyst.
Example 8
Preparation method of catalyst for preparing unsaturated alcohol by selective hydrogenation of alpha, beta-unsaturated aldehyde
The method comprises the following steps:
(1) preparation of the support
5g of 5% sodium bicarbonate aqueous solution is dropwise added into 190g of 20% cerium nitrate solution, the obtained suspension is stood and aged for 24 hours at room temperature, a filter cake is filtered out, the filter cake is dried for 12 hours at 60 ℃, and is roasted for 4 hours at 300 ℃ to obtain CeO 2 And (3) a carrier.
(2) Preparation of catalyst precursor
Preparing impregnation liquid containing ruthenium nitrate, tin chloride and bismuth nitrate, wherein the mass contents of ruthenium, tin and bismuth in the impregnation liquid are respectively 5.0%, 1.5% and 1.0%. Soaking 10g of carrier in 10g of soaking solution, stirring and adsorbing for 4h at 80 ℃, naturally drying, and then drying for 12h at 120 ℃ to prepare a catalyst precursor, wherein the prepared catalyst precursor has 5.0% of Ru load, 1.5% of Sn load and 1.0% of Bi load.
(3) First stage reduction
Adding ammonia water into the catalyst precursor, adjusting the pH value of the slurry to 10, reducing the solution by using a sodium borohydride solution, wherein the using amount of the solution is more than 100% of the theoretical using amount, reducing the solution for 0.5h at 80 ℃, filtering, washing and drying the solution for 12h at 120 ℃.
(4) Second stage reduction
Reducing at 300 deg.C for 2h in hydrogen atmosphere to obtain 5% Ru-1.5% Sn-1.0% Bi/CeO 2 A catalyst.
Comparative examples 9 to 13:
example 9
The preparation method is the same as example 1, except that only Ru is loaded to obtain 3.0% Ru/CeO 2 A catalyst.
Example 10
The preparation method is the same as example 1, except that only Ru and Fe are loaded to obtain 3.0% Ru-5.0% Fe/CeO 2 A catalyst.
Example 11
The preparation method is the same as example 8, except that only Ru and Sn are loaded to obtain 5% Ru-1.5% Sn/CeO 2 A catalyst.
Example 12
The preparation method is the same as that of example 1, except that the carrier is changed into active carbon, and the catalyst with the concentration of 3.0 percent Ru-5.0 percent Fe-0.5 percent Zn/C is prepared.
Example 13
The preparation method is the same as example 1, except that the carrier is changed into TiO 2 To prepare 3.0 percent of Ru-5.0 percent of Fe-0.5 percent of Zn/TiO 2 A catalyst.
Example 14 evaluation of catalyst Performance:
A1L autoclave was charged with 500g of an α, β -unsaturated aldehyde (citral, cinnamaldehyde or methacrolein) and 5g of a catalyst. The autoclave was replaced 3 times with nitrogen and hydrogen. Continuously introducing hydrogen, keeping the hydrogen pressure at 3.0-4.0MPa, and controlling the reaction temperature at 80-100 ℃. After the reaction end point is reached, sampling is carried out to analyze the composition of the product. Then the temperature is reduced, and the catalyst is separated by filtration and can be recycled. The specific reaction results are shown in Table 1.
TABLE 1 hydrogenation of alpha, beta-unsaturated aldehydes on catalysts
Remarking: the unsaturated alcohols corresponding to the alpha, beta-unsaturated aldehyde reaction substrates, namely citral, cinnamaldehyde and methacrolein, refer to geraniol, nerol, cinnamyl alcohol and isobutylene respectively.
The embodiments 1, 5 and 8 are the most preferred embodiments, and the preferred technical scheme of the invention can be summarized by the embodiments 1, 5 and 8 as follows:
the alpha, beta-unsaturated aldehyde is preferably citral or cinnamaldehyde, and the loading amount of active ingredients in the catalyst is preferably 3-10%; the loading amount of the auxiliary agent is preferably 1.5-10%; the loading amount of the inhibitor is preferably 0.5-1%; the auxiliary agent is preferably iron and tin; when the catalyst is used for hydrogenation of alpha, beta-unsaturated aldehyde, the dosage is preferably 1 percent of that of the alpha, beta-unsaturated aldehyde; the hydrogen pressure is 3.0-4.0MPa, and the reaction temperature is controlled at 80-100 ℃. The effect obtained by the preferred scheme is that the conversion rate of the unsaturated aldehyde is 99.6-99.8%; the selectivity of unsaturated alcohol is 98.2-98.5%;
the catalyst synthesized in example 1 was selected and continuously used for 50 batches, and the reaction selectivity was not changed significantly.
The foregoing is illustrative of the preferred embodiments of the present invention. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (6)
1. The catalyst for preparing unsaturated alcohol by selectively hydrogenating alpha, beta-unsaturated aldehyde is characterized by comprising a carrier, an active ingredient, an auxiliary agent and an inhibitor;
the inhibitor is one of zinc, lead and bismuth;
the carrier is cerium dioxide, and the carrier is cerium dioxide,
the active ingredient is ruthenium, and the active ingredient is ruthenium,
the auxiliary agent is one of iron, cobalt, manganese and tin;
the loading capacity of the active ingredient Ru is 1-10%, the loading capacity of the auxiliary agent is 0.05-10%, and the loading capacity of the inhibitor is 0.01-1%;
the particle size of the carrier is 150-500 meshes, and the specific surface area is 10-300m 2 /g；
The alpha, beta-unsaturated aldehyde is citral or cinnamaldehyde;
when the alpha, beta-unsaturated aldehyde is citral, the unsaturated alcohol is geraniol and nerol;
when the α, β -unsaturated aldehyde is cinnamaldehyde, the unsaturated alcohol is cinnamyl alcohol.
2. The method for preparing the catalyst according to claim 1, comprising the steps of: preparing a carrier, preparing a catalyst precursor, and carrying out first-stage reduction and second-stage reduction.
3. The method for preparing the catalyst according to claim 2, wherein the carrier is prepared by adding 1-5% sodium bicarbonate aqueous solution dropwise into 5-20% cerium nitrate solution, standing and aging the obtained suspension at room temperature for 5-24h, filtering to obtain a filter cake, drying and roasting to obtain CeO 2 A carrier;
the preparation of the catalyst precursor, CeO 2 Soaking the carrier in a salt solution containing soluble ruthenium salt, auxiliary agent salt and inhibitor, stirring and adsorbing for 4-24h, and then drying to obtain a catalyst precursor;
the first stage reduction, adding an alkaline solution into a catalyst precursor, adjusting the pH of the slurry to 10-12, reducing the solution by using a sodium borohydride solution at the reduction temperature of 20-80 ℃ for 0.5-4h, filtering, washing and drying;
the second stage reduction, namely the catalyst can be obtained by introducing hydrogen at 300 ℃ and 500 ℃ for reduction treatment for 2-4 h.
4. The method for preparing a catalyst according to claim 3, wherein the ruthenium salt is one of ruthenium chloride, ruthenium nitrate and ruthenium acetate.
5. The method for preparing the catalyst according to claim 3, wherein the salt of the auxiliary is one of chloride, nitrate and acetate of the auxiliary; the salt of the inhibitor is one of chloride, nitrate and acetate of the inhibitor; the alkali is Na 2 CO 3 、NaHCO 3 、(NH 4 ) 2 CO 3 、NH 4 HCO 3 NaOH or NH 3 ·H 2 O。
6. Use of a catalyst according to claim 1 or a catalyst prepared by a method according to any one of claims 2 to 5 in the selective hydrogenation of α, β -unsaturated aldehydes to unsaturated alcohols, characterized in that the α, β -unsaturated aldehydes and the catalyst are fed into a reactor at a certain H 2 Carrying out selective hydrogenation reaction under pressure and temperature, after the reaction is finished, cooling and filtering the catalyst to obtain corresponding unsaturated alcohol;
said H 2 The pressure is 0.5-5MPa, the reaction temperature is 30-180 ℃, and the reaction time is 2-24 h; the dosage of the catalyst is 0.8-1.2% of the mass of the unsaturated aldehyde.
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