CN109647394A - A kind of catalyst and its preparation method and application for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol - Google Patents
A kind of catalyst and its preparation method and application for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol Download PDFInfo
- Publication number
- CN109647394A CN109647394A CN201811511993.3A CN201811511993A CN109647394A CN 109647394 A CN109647394 A CN 109647394A CN 201811511993 A CN201811511993 A CN 201811511993A CN 109647394 A CN109647394 A CN 109647394A
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- China
- Prior art keywords
- catalyst
- beta
- unsaturated
- selective hydrogenation
- carrier
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 12
- 238000002360 preparation method Methods 0.000 title claims description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 239000000470 constituent Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 39
- 230000009467 reduction Effects 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 35
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 21
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-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
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000003303 ruthenium Chemical class 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
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 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
- 235000003642 hunger Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 13
- 229910052745 lead Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007806 chemical reaction intermediate Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003205 fragrance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 36
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 30
- 239000000284 extract Substances 0.000 description 24
- 238000002803 maceration Methods 0.000 description 24
- 239000011701 zinc Substances 0.000 description 13
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 12
- 229940043350 citral Drugs 0.000 description 12
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 9
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 8
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 8
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 8
- GLZPCOQZEFWAFX-JXMROGBWSA-N Nerol Natural products CC(C)=CCC\C(C)=C\CO GLZPCOQZEFWAFX-JXMROGBWSA-N 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 229930016911 cinnamic acid Natural products 0.000 description 8
- 235000013985 cinnamic acid Nutrition 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
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 8
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 7
- 239000005792 Geraniol Substances 0.000 description 7
- 229940113087 geraniol Drugs 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-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
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 carrier Chemical compound 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 230000021615 conjugation Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000007774 longterm Effects 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride 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
- 239000000758 substrate Substances 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
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
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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
- B01J23/89—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
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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
- B01J23/89—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
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Abstract
The present invention provides one kind for α, and the catalyst of beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol, the catalyst includes carrier, active constituent, auxiliary agent, and the catalyst further includes inhibitor, and the carrier is CeO2, the active constituent is Ru, and the auxiliary agent is one of Fe, Co, Mn and Sn, and the inhibitor is one of Zn, Pb and Bi.The catalyst is used for the α of general formula I, when beta-unsaturated aldehyde adds hydrogen to obtain the correspondent alcohol of general formula II, it can apply with preferable conversion ratio and selectivity and repeatedly, can be used in the synthesis process of fragrance, drug and important source material and reaction intermediate in the production of other fine chemical products.
Description
Technical field
The invention belongs to field of chemical technology, are related to a kind of for α, beta-unsaturated aldehyde selective hydrogenation insatiable hunger
With the catalyst of alcohol and its preparation method and application.
Background technique
α, beta unsaturated alcohol are fragrance, drug and other are fine such as geraniol and nerol, cinnamyl alcohol, isobutene alcohol
Important source material and reaction intermediate in chemical products production.
Currently, α, beta unsaturated alcohol mostly use greatly NaBH in the industrial production4Or AlLiH4It is reduced directly α, β-unsaturation
Aldehyde obtains.Although the higher α of the available yield of this method, beta unsaturated alcohol, there are serious drawbacks: not only anti-
It answers that condition is difficult to control, product is difficult to separate, and generates a large amount of three-waste pollution environment, does not meet modernization industry production requirement.
Using solid catalyst directly by α, beta-unsaturated aldehyde selective hydrogenation prepares α, beta unsaturated alcohol, compared to equal
Phase reaction, more environment-friendly, product is easily separated and reuses, and can overcome disadvantage present in the above industry.
C=C key and C=O key containing conjugation in alpha, beta-unsaturated aldehyde molecule.From thermodynamically, the bond energy (715 of C=O key
KJ/mol) bigger than the bond energy of C=C key (615 kJ/mol)；From kinetically, the hydrogenation activity of C=C key is higher than C=O key, selection
Add the more of hydrogen C=O key ratio C=C key difficulty.Therefore exploitation has highly selective, high stability C=O key selective hydrogenation catalyst
It is crucial.
Patent US4100180 is described in the presence of PtO/Zn/Fe catalyst, and unsaturated aldehyde adds hydrogen to obtain unsaturated alcohol
Method, under citral is 70% in its conversion ratio plus hydrogen obtains 85.5% geraniol and nerol.Patent CN107056566A's
In technical solution, discloses a series of catalyst and obtained preferable for hydrogenating α, beta-unsaturated aldehyde to α, beta unsaturated alcohol
It as a result is that catalyst 9%Ag-2%Ir-5%Ca/SiO is used in fixed bed2, when citral conversion ratio is 92.3%, unsaturated alcohol
Selectivity is 86.2%；Catalyst 0.1%Rh-2%Ru-4%Mn/TiO is used in tank reactor2, when cinnamic acid conversion ratio is
When 81.3%, unsaturated alcohol is selectively 61.3%.The above technology is there are unsaturated aldehyde conversion ratio is low, and unsaturated alcohol selectivity is not
Satisfactory problem.
Patent CN1258506C discloses the Ru/Fe/C suspended catalyst in bubble-column reactor and adds in hydrogen in citral
Using being 92% to the selectivity of geraniol and nerol under 96% conversion, however be catalyzed in reaction and joined methanol and front three
Base amine, so that required additional separating step in last handling process.Patent CN106824182A then uses composite catalyst 3%Ir-
2%Ru/C is applied to citral selective hydrogenation synthesis geraniol or nerol, feed stock conversion 100%, the selection of target product
Property can be greater than 98%.But catalyst price is costly, and increases product separation process by solvent of isopropanol in reaction process
Burden.
A kind of ruthenium catalyst of doping iron that carbon loads is used for suspension bed in the technical solution of patent CN1422693 or is consolidated
Hydrogenating citral generates geraniol and nerol in fixed bed.When citral conversion ratio is 96.1%, geraniol and nerol are always selected
Selecting property is 97.6%, but fixed bed reactors require catalyst to have long-term service life.
Patent CN104974016B is described in solvent-free system, with Pt-Ru-Sn/TiO2For catalyst, cinnamic acid exists
In the case where conversion completely, the selectivity of cinnamyl alcohol is 93 ~ 95%, but the catalyst, primarily directed to specific α, β-is no
Saturated aldehyde, therefore above have certain limitation in application.
In conclusion the catalyst in publication at present, having plenty of there is a problem of selectively low to unsaturated alcohol, have
Be the presence of organic solvent pollution, having plenty of has higher requirement to catalyst life, has plenty of just for specific
A kind of alpha, beta-unsaturated aldehyde is effective.The selective hydrogenation that variety classes alpha, beta-unsaturated aldehyde can be applicable in there are no one kind is urged
Agent, takes into account active selectable and process environments are friendly.
Summary of the invention
To solve the shortcomings of the prior art, the present invention provides a kind of for α, beta-unsaturated aldehyde selective hydrogenation system
Catalyst of unsaturated alcohol and its preparation method and application, to realize following goal of the invention:
(1) catalyst of the invention is suitable for the selective hydrogenation of different types of alpha, beta-unsaturated aldehyde；
(2) selectivity of catalyst is high；
(3) catalyst, which is repeatedly applied, does not influence selectivity；
(4) organic solvent pollution is eliminated.
In order to solve the above technical problems, the invention adopts the following technical scheme:
One kind being used for α, the catalyst of beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol, including carrier, active constituent, auxiliary agent
And inhibitor, the carrier are CeO2, the active constituent is ruthenium (Ru), and the auxiliary agent is in Fe, Co, Mn, Sn
One kind, the inhibitor are one of Zn, Pb, Bi.
The load capacity of the active constituent Ru is 1%-10%, and the load capacity of auxiliary agent is 0.05%-10%, inhibitor
Load capacity is 0.01-1%.
In the catalyst, the partial size of the carrier is 150-500 mesh, and specific surface area is 10-300 m2/g。
Specific preparation process is as follows for above-mentioned catalyst:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 1-5% is added dropwise in the cerous nitrate solution of 5-20%, obtained suspension is at room temperature
Aging 5-24h is stood, filter cake is filtered out, then the dry 2-12h at 60-120 DEG C, 2-4h is roasted under the conditions of 300-500 DEG C, obtains
To CeO2Carrier；
(2) catalyst precursor is prepared
The CeO that step (1) is obtained2Carrier impregnation in containing soluble ruthenium salt, the salt of auxiliary agent and the salting liquid of inhibitor,
Room temperature is to stirring and adsorbing 4-24h at 80 DEG C, and then the dry 6-12h at 60-120 DEG C, obtains catalyst precursor；
(3) first stage of reduction
Alkaline solution is added into catalyst precursor, adjusts slurries pH to 10-12, then using in sodium borohydride solution reduction
Solution is stated, reduction temperature is 20-80 DEG C, then recovery time 0.5-4h is filtered, washed, dry 12h at 60-120 DEG C；
(4) second stage restores
The sample of step (3) after dry, which is led to reduction treatment 2-4h at 300-500 DEG C of hydrogen, can be obtained the catalyst.
The ruthenium salt is one of ruthenic chloride, nitric acid ruthenium and acetic acid ruthenium.
The salt of the auxiliary agent is one of chloride, nitrate and the acetate of auxiliary agent；
The salt of the inhibitor is one of chloride, nitrate and the acetate of inhibitor；
The alkali is Na2CO3、NaHCO3、(NH4)2CO3、NH4HCO3, NaOH or NH3·H2O。
The present invention also provides the catalyst described in one kind to prepare corresponding unsaturation in alpha, beta-unsaturated aldehyde selective hydrogenation
Application in alcohol, by α, in beta-unsaturated aldehyde (Formulas I) and catalyst investment reactor, in certain H2Pressure and temperature
Lower carry out selective hydrogenation, reaction are finished, and cool down simultaneously filtration catalytic agent, are obtained corresponding unsaturated alcohol (Formula II), are reacted
Journey is as follows:
Wherein R1And R2It is identical or different and be each independently hydrogen or C1-C20 alkyl or phenyl, R3For hydrogen or C1-C4 alkyl
(such as citral, cinnamic acid, methacrolein etc.).
Wherein, the alkyl includes alkyl, alkenyl or alkynyl, preferably alkyl or alkenyl.
The H2Pressure is 0.5-5 MPa, and reaction temperature is 30-180 DEG C, and the reaction time is 2-24 h.
The catalyst being obtained by filtration can be applied, and test result shows after repeatedly applying, the activity of catalyst
It is substantially reduced with selectivity nothing.
The invention adopts the above technical scheme, compared with prior art, has the advantages that
(1) reaction carries out in solvent-free system, eliminates organic solvent pollution, alleviates the burden of separation process, be conducive to
Reduce production cost.
(2) catalyst price is relatively inexpensive, and activity is highly selective good and after 50 times are applied, the activity and selection of catalyst
Property without being substantially reduced, and can be separated by the method for filtering, it is easy to operate, be conducive to large-scale production.
(3) catalyst shows higher selectivity in different α, the selective hydrogenation process of beta-unsaturated aldehyde, no
The conversion ratio of saturated aldehyde is 99.0-99.8%；Unsaturated alcohol is selectively 88.5-98.5%；
Catalyst of the present invention can be used for the selective hydrogenation of citral, cinnamic acid, methacrolein, the selectivity for citral
When hydrogen being added to prepare geraniol and nerol, the conversion ratio of unsaturated aldehyde is 99.0-99.8%；Unsaturated alcohol is selectively 97.1-
98.5%；When selective hydrogenation for cinnamic acid prepares cinnamyl alcohol, the conversion ratio of unsaturated aldehyde is 99.1-99.7%；It is unsaturated
Alcohol is selectively 97.8-98.2%；When preparing isobutene alcohol for methacrolein selective hydrogenation, the conversion ratio of unsaturated aldehyde is
99.2%；Unsaturated alcohol is selectively 88.5%.
The present invention is further illustrated combined with specific embodiments below.
Specific embodiment
Embodiment 1
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 8g3% is added dropwise in the cerous nitrate solution of 378.5g10%, obtained suspension is in room
Temperature is lower to stand aging 8h, filters out filter cake, 4h is roasted at 120 DEG C of dry 12h, 500 DEG C, obtain CeO2Carrier.
(2) catalyst precursor is prepared
The maceration extract for preparing chloride containing ruthenium, iron chloride, zinc acetate, ruthenium in maceration extract, iron, zinc mass content be respectively 3.0%,
5.0%,0.5%.By 10g carrier impregnation in the maceration extract of 10g, absorption is stirred at room temperature for 24 hours, natural air drying, then at 60 DEG C
Dry 12h, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is that 3.0%, Fe load capacity is 5.0%,
Zn load capacity is 0.5%.
(3) first stage of reduction
Sodium carbonate liquor is added into catalyst precursor, adjusts slurries pH to 10, then using in sodium borohydride solution reduction
Solution is stated, dosage is 100% or more, 20 DEG C of reduction 4h of theoretical amount, is then filtered, washed, dry 12h at 120 DEG C.
(4) second stage restores
3.0%Ru-5.0%Fe-0.5%Zn/CeO can be obtained in 500 DEG C of reduction treatment 4h under an atmosphere of hydrogen again2Catalyst.
Embodiment 2
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 8g3% is added dropwise in the cerous nitrate solution of 378.5g10%, obtained suspension is in room
Temperature is lower to stand aging 8h, filters out filter cake, 4h is roasted at 120 DEG C of dry 12h, 500 DEG C, obtain CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing nitric acid, the maceration extract of ferric nitrate and zinc nitrate, ruthenium in maceration extract, iron, zinc mass content be respectively 5.0%,
1.5%,1.0%.By 10g carrier impregnation in the maceration extract of 10g, absorption is stirred at room temperature for 24 hours, natural air drying, then at 60 DEG C
Dry 6h, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is that 5.0%, Fe load capacity is 1.5%, Zn
Load capacity is 1.0%.
(3) first stage of reduction
Sodium carbonate liquor is added into catalyst precursor, adjusts slurries pH to 10, then using in sodium borohydride solution reduction
Solution is stated, dosage is 100% or more, 20 DEG C of reduction 4h of theoretical amount, is then filtered, washed, dry 12h at 120 DEG C.
(4) second stage restores
5.0%Ru-1.5%Fe-1.0%Zn/CeO can be obtained in 500 DEG C of reduction treatment 2h under an atmosphere of hydrogen again2Catalyst.
Embodiment 3
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 8g3% is added dropwise in the cerous nitrate solution of 378.5g10%, obtained suspension is in room
Temperature is lower to stand aging 8h, filters out filter cake, 2h is roasted at 120 DEG C of dry 12h, 500 DEG C, obtain CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing acetic acid, the maceration extract of ferric nitrate and zinc nitrate, ruthenium in maceration extract, iron, zinc mass content be respectively 1.0%,
0.05%,0.1%.By 10g carrier impregnation in the maceration extract of 10g, absorption is stirred at room temperature for 24 hours, natural air drying, then at 60 DEG C
Dry 12h, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is that 1.0%, Fe load capacity is 0.05%,
Zn load capacity is 0.1%.
(3) first stage of reduction
Sodium carbonate liquor is added into catalyst precursor, adjusts slurries pH to 12, then using in sodium borohydride solution reduction
Solution is stated, dosage is 100% or more, 20 DEG C of reduction 4h of theoretical amount, is then filtered, washed, dry 12h at 60 DEG C.
(4) second stage restores
1.0%Ru-0.05%Fe-0.1%Zn/CeO can be obtained in 500 DEG C of reduction treatment 2h under an atmosphere of hydrogen again2Catalyst.
Embodiment 4
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 8g3% is added dropwise in the cerous nitrate solution of 378.5g10%, obtained suspension is in room
Temperature is lower to stand aging 8h, filters out filter cake, 2h is roasted at 120 DEG C of dry 12h, 500 DEG C, obtain CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing acetic acid, the maceration extract of ferric nitrate and plumbi nitras, ruthenium in maceration extract, iron, lead mass content be respectively
10.0%,1.5%,0.1%.By 10g carrier impregnation in the maceration extract of 10g, absorption is stirred at room temperature for 24 hours, then natural air drying exists
Dry 12h at 60 DEG C, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is 10.0%, Fe load capacity
It is 0.1% for 1.5%, Pb load capacity.
(3) first stage of reduction
Sodium hydroxide solution is added into catalyst precursor, adjusts slurries pH to 12, is then restored using sodium borohydride solution
Above-mentioned solution, dosage are 100% or more, 20 DEG C of reduction 4h of theoretical amount, are then filtered, washed, dry 12h at 60 DEG C.
(4) second stage restores
10%Ru-1.5%Fe-0.1%Pb/CeO can be obtained in 300 DEG C of reduction treatment 2h under an atmosphere of hydrogen again2Catalyst.
Embodiment 5
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 24g1% is added dropwise in the cerous nitrate solution of 757g5%, obtained suspension is in room temperature
Lower standing aging 5h, filters out filter cake, roasts 4h at 60 DEG C of dry 12h, 300 DEG C, obtains CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing nitric acid, the maceration extract of ferric nitrate and plumbi nitras, ruthenium in maceration extract, iron, lead mass content be respectively
10.0%,10.0%,1.0%.By 10g carrier impregnation in the maceration extract of 10g, then 80 DEG C of stirring and adsorbing 4h, natural air drying exists
Dry 12h at 120 DEG C, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is 10.0%, Fe load capacity
It is 1.0% for 10.0%, Pb load capacity.
(3) first stage of reduction
Sodium bicarbonate solution is added into catalyst precursor, adjusts slurries pH to 10, is then restored using sodium borohydride solution
Above-mentioned solution, dosage are 100% or more, 80 DEG C of reduction 0.5h of theoretical amount, are then filtered, washed, dry 12h at 120 DEG C.
(4) second stage restores
10.0%Ru-10.0%Fe-1.0%Pb/CeO can be obtained in 300 DEG C of reduction treatment 4h under an atmosphere of hydrogen again2Catalyst.
Embodiment 6
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 24g1% is added dropwise in the cerous nitrate solution of 757g5%, obtained suspension is in room temperature
Lower standing aging 5h, filters out filter cake, roasts 4h at 60 DEG C of dry 12h, 300 DEG C, obtains CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing nitric acid, the maceration extract of cobalt nitrate and lead acetate, ruthenium in maceration extract, cobalt, lead mass content be respectively 5.0%,
1.5%,1.0%.By 10g carrier impregnation in the maceration extract of 10g, 80 DEG C of stirring and adsorbing 4h, natural air drying, then at 120 DEG C
Dry 12h, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is that 5.0%, Co load capacity is 1.5%,
Pb load capacity is 1.0%.
(3) first stage of reduction
Carbonic acid ammonia solution is added into catalyst precursor, adjusts slurries pH to 10, then using in sodium borohydride solution reduction
Solution is stated, dosage is 100% or more, 80 DEG C of reduction 0.5h of theoretical amount, is then filtered, washed, dry 12h at 120 DEG C.
(4) second stage restores
5.0%Ru-1.5%Co-1.0%Pb/CeO can be obtained in 300 DEG C of reduction treatment 4h under an atmosphere of hydrogen again2Catalyst.
Embodiment 7
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 5g5% is added dropwise in the cerous nitrate solution of 190g20%, obtained suspension is in room temperature
Lower standing aging for 24 hours, filters out filter cake, roasts 4h at 60 DEG C of dry 12h, 300 DEG C, obtains CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing nitric acid, the maceration extract of manganese nitrate and bismuth nitrate, ruthenium in maceration extract, manganese, bismuth mass content be respectively 5.0%,
1.5%,1.0%.By 10g carrier impregnation in the maceration extract of 10g, 80 DEG C of stirring and adsorbing 4h, natural air drying, then at 120 DEG C
Dry 12h, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is that 5.0%, Mn load capacity is 1.5%,
Bi load capacity is 1.0%.
(3) first stage of reduction
Ammonium bicarbonate soln is added into catalyst precursor, adjusts slurries pH to 10, is then restored using sodium borohydride solution
Above-mentioned solution, dosage are 100% or more, 80 DEG C of reduction 0.5h of theoretical amount, are then filtered, washed, dry 12h at 120 DEG C.
(4) second stage restores
5.0%Ru-1.5%Mn-1.0%Bi/CeO can be obtained in 300 DEG C of reduction treatment 4h under an atmosphere of hydrogen again2Catalyst.
Embodiment 8
A kind of preparation method of the catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol
The following steps are included:
(1) carrier is prepared
The sodium bicarbonate aqueous solution of 5g5% is added dropwise in the cerous nitrate solution of 190g20%, obtained suspension is in room temperature
Lower standing aging for 24 hours, filters out filter cake, roasts 4h at 60 DEG C of dry 12h, 300 DEG C, obtains CeO2Carrier.
(2) catalyst precursor is prepared
Prepare ruthenium containing nitric acid, the maceration extract of stannic chloride and bismuth nitrate, ruthenium in maceration extract, tin, bismuth mass content be respectively 5.0%,
1.5%,1.0%.By 10g carrier impregnation in the maceration extract of 10g, 80 DEG C of stirring and adsorbing 4h, natural air drying, then at 120 DEG C
Dry 12h, is made catalyst precursor, and in the catalyst precursor of preparation, Ru load capacity is that 5.0%, Sn load capacity is 1.5%,
Bi load capacity is 1.0%.
(3) first stage of reduction
Ammonium hydroxide is added into catalyst precursor, adjusts slurries pH to 10, above-mentioned solution is then restored using sodium borohydride solution,
Dosage is 100% or more, 80 DEG C of reduction 0.5h of theoretical amount, is then filtered, washed, dry 12h at 120 DEG C.
(4) second stage restores
5%Ru-1.5%Sn-1.0%Bi/CeO can be obtained in 300 DEG C of reduction treatment 2h under an atmosphere of hydrogen again2Catalyst.
Comparative example 9-13:
Embodiment 9
The preparation method is the same as that of Example 1, and difference is only to load Ru, and 3.0%Ru/CeO is made2Catalyst.
Embodiment 10
The preparation method is the same as that of Example 1, and difference is only to load Ru, Fe, and 3.0%Ru-5.0%Fe/CeO is made2Catalyst.
Embodiment 11
For preparation method with embodiment 8, difference is only to load Ru, Sn, and 5%Ru-1.5%Sn/CeO is made2Catalyst.
Embodiment 12
The preparation method is the same as that of Example 1, and difference is that carrier is changed to active carbon, and 3.0%Ru-5.0%Fe-0.5%Zn/C catalyst is made.
Embodiment 13
The preparation method is the same as that of Example 1, and difference is that carrier is changed to TiO2, 3.0%Ru-5.0%Fe-0.5%Zn/ TiO is made2Catalysis
Agent.
14 catalyst performance evaluation of embodiment:
Alpha, beta-unsaturated aldehyde (citral, cinnamic acid or methacrolein) 500g and catalyst 5g is added in 1L autoclave.Autoclave
Successively replaced 3 times with nitrogen, hydrogen.It is continuously passed through hydrogen and keeps Hydrogen Vapor Pressure 3.0-4.0MPa, control reaction temperature in 80-
100℃.Sampling analysis product forms after reaching reaction end.Then cool down, filter to isolate catalyst, the recyclable set of catalyst
With.Specific reaction result is shown in Table 1.
The hydrogenation reaction result of alpha, beta-unsaturated aldehyde on 1 catalyst of table
Remarks: alpha, beta-unsaturated aldehyde reaction substrate citral, cinnamic acid, the corresponding unsaturated alcohol of methacrolein respectively refer to spiceleaf
Pure and mild nerol, cinnamyl alcohol, isobutene alcohol.
Embodiment 1,5,8 is most preferred embodiment, can be summarized by embodiment 1,5,8 and be obtained, of the invention is preferred
Technical solution is as follows:
The α, beta-unsaturated aldehyde are preferably citral, cinnamic acid, and the load capacity of active constituent is preferably 3-10% in catalyst；
The load capacity of auxiliary agent is preferably 1.5-10%；The load capacity of inhibitor is preferably 0.5-1%；Auxiliary agent is preferably iron, tin；Catalyst is used
In α, beta-unsaturated aldehyde plus when hydrogen, dosage is preferably α, the 1% of beta-unsaturated aldehyde；Hydrogen Vapor Pressure 3.0-4.0MPa, control are anti-
Answer temperature at 80-100 DEG C.The effect that the preferred embodiment obtains is that the conversion ratio of unsaturated aldehyde is 99.6-99.8%；Unsaturated alcohol
Selectivity is 98.2-98.5%；
It chooses the progress of catalyst synthesized by embodiment 1 and continuously applies 50 batches, reaction selectivity, which has no, to be substantially change.
The above is preferred embodiments of the present invention.Implement according to the technical essence of the invention to above
Any simple modification, equivalent change and modification that example is done, fall within the protection scope of the present invention.
Claims (10)
1. one kind is used for α, the catalyst of beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol, the catalyst includes carrier, work
Property ingredient, auxiliary agent, which is characterized in that the catalyst further includes inhibitor.
2. it is according to claim 1 it is a kind of be used for α, the catalyst of beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol,
It is characterized in that, the inhibitor is one of zinc (Zn), lead (Pb), bismuth (Bi).
3. it is according to claim 1 it is a kind of be used for α, the catalyst of beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol,
It is characterized in that, the carrier is ceria (CeO2), the active constituent is ruthenium (Ru), and the auxiliary agent is iron
(Fe), one of cobalt (Co), manganese (Mn), tin (Sn).
4. catalyst according to claim 1, which is characterized in that the load capacity of active constituent Ru is 1-10%, and auxiliary agent is born
Carrying capacity is 0.05-10%, and the load capacity of inhibitor is 0.01-1%.
5. catalyst according to claim 1, which is characterized in that the partial size of the carrier is 150-500 mesh, specific surface area
For 10-300m2/g。
6. one kind is used for α, the preparation method of the catalyst of beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol, which is characterized in that
The following steps are included: preparing carrier, preparing catalyst precursor, first stage of reduction, second stage reduction.
7. a kind of catalyst for alpha, beta-unsaturated aldehyde selective hydrogenation unsaturated alcohol according to claim 6
Preparation method, which is characterized in that it is described to prepare carrier, the sodium bicarbonate aqueous solution of 1-5% is added dropwise to the nitric acid of 5-20%
In cerium solution, obtained suspension stands aging 5-24h at room temperature, filters to obtain filter cake, through drying, roasting, obtains CeO2It carries
Body；
It is described to prepare catalyst precursor, CeO2Carrier impregnation is in containing soluble ruthenium salt, the salt of auxiliary agent and the salting liquid of inhibitor
In, then stirring and adsorbing 4-24h dries, obtains catalyst precursor；
Alkaline solution is added into catalyst precursor for the first stage of reduction, adjusts slurries pH to 10-12, then uses
Sodium borohydride solution restores above-mentioned solution, and reduction temperature is 20-80 DEG C, then recovery time 0.5-4h is filtered, washed, dries；
The second stage reduction, leading to reduction treatment 2-4h at 300-500 DEG C of hydrogen can be obtained the catalyst.
8. the preparation method of catalyst according to claim 7, which is characterized in that the ruthenium salt is ruthenic chloride, nitric acid
One of ruthenium and acetic acid ruthenium.
9. the preparation method of catalyst according to claim 7, which is characterized in that the salt of the auxiliary agent is the chlorine of auxiliary agent
One of compound, nitrate, acetate；The salt of the inhibitor is in the chloride, nitrate, acetate of inhibitor
It is a kind of；The alkali is Na2CO3、NaHCO3、(NH4)2CO3、NH4HCO3, NaOH or NH3·H2O。
10. a kind of catalyst as described in any one of claims 1 to 9 is unsaturated in alpha, beta-unsaturated aldehyde selective hydrogenation system
Application in alcohol, which is characterized in that by α, in beta-unsaturated aldehyde and catalyst investment reactor, in certain H2Pressure and temperature
Lower carry out selective hydrogenation, reaction are finished, and cool down simultaneously filtration catalytic agent, obtain corresponding unsaturated alcohol, the α, β-insatiable hunger
Structural formula with aldehyde is formula (I)；The structural formula of the unsaturated alcohol is formula (II)；
Wherein R1And R2It is identical or different and be each independently hydrogen or C1-C20 alkyl or phenyl, R3For hydrogen or C1-C4 alkane
Base；
The H2Pressure is 0.5-5 MPa, and reaction temperature is 30-180 DEG C, and the reaction time is 2-24 h；The dosage of catalyst
For the 0.8-1.2% of unsaturated aldehyde quality.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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