CN116375566B - Catalytic synthesis method of 2, 3-butanedione, catalyst and preparation method - Google Patents
Catalytic synthesis method of 2, 3-butanedione, catalyst and preparation method Download PDFInfo
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- CN116375566B CN116375566B CN202310351621.3A CN202310351621A CN116375566B CN 116375566 B CN116375566 B CN 116375566B CN 202310351621 A CN202310351621 A CN 202310351621A CN 116375566 B CN116375566 B CN 116375566B
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- cerium
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- catalyst
- iron
- butanedione
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- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 35
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 16
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 claims abstract description 48
- ZGMCLEXFYGHRTK-UHFFFAOYSA-N [Fe].[Ce] Chemical compound [Fe].[Ce] ZGMCLEXFYGHRTK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 25
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000000703 Cerium Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 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 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 244000061520 Angelica archangelica Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 240000007154 Coffea arabica Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000001287 Guettarda speciosa Nutrition 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 244000273928 Zingiber officinale Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000020224 almond Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010620 bay oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UWJQRYVWXZGVQT-UHFFFAOYSA-N butane-2,3-dione Chemical compound CC(=O)C(C)=O.CC(=O)C(C)=O UWJQRYVWXZGVQT-UHFFFAOYSA-N 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000021022 fresh fruits Nutrition 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000009935 nitrosation Effects 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- -1 nitrous acid ester Chemical class 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of organic synthesis catalysts, and particularly relates to a catalyst for synthesizing 2, 3-butanedione, and a preparation method and application thereof. The invention prepares a new iron-cerium composite oxide catalyst, the catalyst is filled in a fixed bed, air is introduced to oxidize acetoin into butanedione at a certain temperature, and the butanedione crude product is directly rectified and purified to more than 99 percent of qualified products; the iron-cerium composite oxide catalyst is used, and the reaction mode of directly introducing air for catalytic oxidation is adopted, so that other oxidants such as hydrogen peroxide, nitric acid and the like are not needed, the cost is saved, and a large amount of wastewater is avoided. The prepared catalyst can be recycled after being passivated and roasted for a plurality of times, and the production cost is further reduced; meanwhile, the fixed bed reaction can realize continuous production, improve productivity and reduce manpower.
Description
Technical Field
The invention belongs to the technical field of organic synthesis catalysts, and particularly relates to a catalytic synthesis method of 2, 3-butanedione, a catalyst and a preparation method.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
2, 3-butanedione (butane-2, 3-dione), which is an important perfume and a main raw material for producing pyrazine perfumes; butanedione is widely present in a variety of plant essential oils in nature, such as iris oil, angelica oil, bay oil, etc., and is the main component of butter and some other natural product flavors; is a main spice of cream essence, and can be used in milk, cheese and other flavors. Such as in berries, caramel, chocolate, coffee, cherries, vanilla chemical book beans, honey, cocoa, fruit, bouquet, smoke, lamb, nuts, almonds, ginger, and the like. Can also be used in cosmetics with fresh fruit fragrance or novel essence.
At present, the method for preparing butanedione is reported at home and abroad and mainly comprises the following steps: 1. the plant extraction method adopts an extraction method to extract trace butanedione from plant seeds containing butanedione, has complex extraction operation, deficient raw materials and high preparation cost, and is not suitable for mass production; 2. in the microbial fermentation method, citric acid, glucose and the like are often used as substrates for microbial fermentation, specific bacteria are needed for fermentation synthesis of butanedione, the efficiency is low, generally 2-4g/L, and large-scale production is difficult to realize; 3. the butanone oxidation method adopts selenium dioxide as a catalyst and an ozone oxidation method, or adopts metals such as nickel or vanadium as a catalyst, butanone is oxidized into butanedione through air, the catalyst is expensive, the yield is low, and industrialization cannot be realized; 4. the nitrosation method uses butanone as raw material, reacts with nitrous acid ester to produce butanone oxime, then hydrolyzes to produce butanedione, is the main method for domestic enterprises to produce butanedione, but has serious environmental pollution, and has large toxicity of nitrite substances, and a large amount of three wastes are produced in the production process. The preparation method of the butanedione has the defects of low yield, complex operation, high cost, serious pollution and the like, and cannot meet the requirements of large-scale, green, low cost and the like of industrialized butanedione preparation.
The acetoin oxidation method is a method for preparing 2, 3-butanedione by using acetoin as a raw material through oxidation reaction, and has the advantages of easily available reactants, less side reaction and the like. In the prior art, the acetoin oxidation method is realized by taking ferric trichloride, ozone, hydrogen peroxide and the like as oxidizing agents. Converting ferric chloride into ferric dichloride, oxidizing the ferric dichloride into ferric chloride by using 60% nitric acid, dehydrating, concentrating, cooling and separating out ferric trichloride hexahydrate crystalline solid, and re-feeding. The process uses nitric acid to realize the recycling of ferric trichloride, generates a large amount of acid wastewater, increases the cost by using the nitric acid, is easy to make explosion, has strong oxidizing property, and has safety risks in industrial storage and use of a large amount of nitric acid. Ozone and hydrogen peroxide are used as oxidizing agents, on one hand, a specific solvent or compound is needed to remove excessive oxidizing agents, so that the preparation cost is increased, and on the other hand, the ozone and the hydrogen peroxide are used as strong oxidizing agents, so that safety risks exist in the storage and use processes. The existing acetoin oxidation method still has the defects of high cost, waste water generation, safety problem and the like, and cannot meet the requirements of large scale, green, low cost and the like for industrially preparing butanedione.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a catalytic synthesis method of 2, 3-butanedione, a catalyst and a preparation method. The invention prepares a new iron-cerium composite oxide catalyst, the catalyst is filled in a fixed bed, air is introduced to oxidize acetoin into butanedione at a certain temperature, and the butanedione crude product is directly rectified and purified to more than 99 percent of qualified products; the iron-cerium composite oxide catalyst is used, and the reaction mode of directly introducing air for catalytic oxidation is adopted, so that other oxidants such as hydrogen peroxide, nitric acid and the like are not needed, the cost is saved, and a large amount of wastewater is avoided. The prepared catalyst can be recycled after being passivated and roasted for a plurality of times, and the production cost is further reduced; meanwhile, the fixed bed reaction can realize continuous production, improve productivity and reduce manpower.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a method for preparing 2, 3-butanedione, comprising the following steps:
pressing, crushing and sieving the iron-cerium composite oxide catalyst by a tablet press, filling the iron-cerium composite oxide catalyst into a miniature fixed bed reactor, heating, introducing acetoin and air for reaction to obtain a butanedione crude product, and purifying the butanedione crude product to obtain 2, 3-butanedione.
In a second aspect, the present invention provides the iron-cerium composite oxide catalyst in the first aspect, wherein the mass ratio of cerium oxide is 5 to 20%.
In a third aspect, the present invention provides a method for preparing the iron-cerium composite oxide catalyst according to the second aspect, comprising the steps of:
s1, dissolving ferric salt and cerium salt in water to form an iron-cerium salt solution; dissolving a precipitant in water to form a precipitant aqueous solution;
s2, simultaneously dropwise adding an iron-cerium salt solution and a precipitant aqueous solution, and heating and aging the mixed solution after the dropwise adding is completed;
s3, filtering the aged mixed solution, collecting a solid filter cake, washing and drying to obtain a catalyst precursor;
and S4, roasting the catalyst precursor to obtain the reddish brown catalyst.
The beneficial effects obtained by one or more of the technical schemes of the invention are as follows:
(1) According to the preparation method, the solution is prepared by respectively preparing the cheap and easily available ferric salt, cerium salt and the precipitant, the catalyst precursor is obtained by a coprecipitation method, and the precursor is further subjected to air calcination to obtain the iron-cerium composite oxide catalyst.
(2) The iron-cerium composite oxide catalyst prepared by the invention has excellent catalytic activity, and the product yield of catalyzing and oxidizing acetoin to generate 2, 3-butanedione can reach 83-96%; the catalyst has long-term stability, and the yield can reach more than 95% after three times of operation.
(3) According to the invention, the air is catalyzed to oxidize acetoin to generate 2, 3-butanedione by using the iron-cerium composite oxide catalyst, no additional reagent is added except for the acetoin serving as a raw material, and the byproduct is only water, so that the preparation cost is low and the environment friendliness is high.
(4) According to the preparation method of the 2, 3-butanedione, disclosed by the invention, continuous feeding and continuous discharging are realized by using the fixed bed reactor, so that the reaction time is shortened, and the preparation efficiency is greatly improved; thanks to the arrangement of the fixed bed reactor, the catalyst can be regenerated through a simple shutdown roasting process, so that the preparation efficiency is further improved, and the cost is reduced.
Detailed Description
As described in the background art, the preparation method of butanedione in the prior art has the defects of low yield, complex operation, high cost, serious pollution, difficult catalyst regeneration and the like, and cannot meet the requirements of large scale, greenization, low cost and the like of industrialized butanedione preparation. According to the invention, by preparing the iron-cerium composite oxide catalyst, acetoin and air are catalyzed to react, so that 2, 3-butanedione is obtained, and the reaction equation is as follows:
in a first exemplary embodiment of the present invention, a catalytic synthesis method of 2, 3-butanedione includes the steps of:
pressing, crushing and sieving the iron-cerium composite oxide catalyst by a tablet press, filling the iron-cerium composite oxide catalyst into a miniature fixed bed reactor, heating, introducing acetoin and air for reaction to obtain a butanedione crude product, and purifying the butanedione crude product to obtain 2, 3-butanedione.
In one or more examples of this embodiment, the elevated temperature is 180-250 ℃, the acetoin space velocity is 0.1-0.4g/mL.cat.h, acetoin and O in air 2 The molar ratio of (2) is 1:2.5-5.
The space velocity in the invention is the mass of acetoin feed per milliliter of catalyst raw material per hour.
In one or more embodiments of this embodiment, the method further comprises a catalyst regeneration process:
stopping feeding when the reaction yield is reduced, cooling to 100 ℃, and simultaneously switching air to nitrogen; when the temperature of the preheater and the reaction furnace is reduced to 100 ℃, starting to feed an absolute ethyl alcohol cleaning pipeline and a reactor, cleaning until the ethyl alcohol is colorless or light yellow, closing a feed pump, and continuously purging the pipeline for 30min by using nitrogen;
switching the air path to air, and performing programmed temperature rising calcination by the reaction furnace;
and after the roasting is finished, the temperature is reduced to the reaction temperature, the air speed is adjusted to the air speed of the reaction condition, the preheater is set to the required condition, and the feeding is started.
In one or more examples of this embodiment, the temperature programmed calcination is specifically:
raising the temperature from 100 ℃ to 300 ℃ for 200min and keeping for 60min; then the temperature of the reaction furnace is increased from 300 ℃ to 450 ℃ for 150min and kept for 60min; the temperature of the reaction furnace is increased from 450 ℃ to 550 ℃ for 100min, and the reaction furnace is baked for 3h at 550 ℃.
In a second exemplary embodiment, the iron-cerium composite oxide catalyst according to the first exemplary embodiment, wherein the mass ratio of cerium oxide in the iron-cerium composite oxide catalyst is 5-20%.
According to a third exemplary embodiment of the present invention, a second exemplary embodiment, the method for preparing the iron-cerium composite oxide catalyst, is characterized by comprising the steps of:
s1, dissolving ferric salt and cerium salt in water to form an iron-cerium salt solution; dissolving a precipitant in water to form a precipitant aqueous solution;
s2, simultaneously dropwise adding an iron-cerium salt solution and a precipitant aqueous solution, and heating and aging the mixed solution after the dropwise adding is completed;
s3, filtering the aged mixed solution, collecting a solid filter cake, washing and drying to obtain a catalyst precursor;
and S4, roasting the catalyst precursor to obtain the reddish brown catalyst.
In one or more examples of this embodiment, the precipitant includes sodium hydroxide, sodium carbonate, sodium bicarbonate, and ammonia water, the iron salt includes one or more of ferric chloride, ferric acetate, ferric sulfate, and ferric nitrate, the cerium salt includes one or more of cerium chloride, cerium nitrate, cerium sulfate, and cerium acetate, and a molar ratio of iron element to cerium element in the iron salt and the cerium salt is 8.6-41:1.
In one or more embodiments of this embodiment, in step S2, the dropping temperature is room temperature, and the pH of the mixed solution is controlled to be 8 to 9 during the dropping; the aging temperature is 65-80 ℃ and the aging time is 1-2h.
In one or more embodiments of this embodiment, the washing in step S3 is performed using deionized water to a pH neutral, a drying temperature of 80-110 ℃, and a drying time of 12-24 hours.
In one or more embodiments of this embodiment, the firing temperature in step S4 is 450-550 ℃, the firing time is 3-5 hours, and the firing atmosphere is air.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
In the following examples, if not specified, the test method is adopted, the prepared iron-cerium catalyst is pressed, crushed and sieved by a tablet press to obtain a finished catalyst with 20-60 meshes, the finished catalyst is filled into a micro fixed bed reactor, and the upper end and the lower end of the catalyst layer are respectively filled with a proper amount of quartz sand and are separated by quartz cotton; the preheater is heated to 150 ℃, the reactor is heated to 220 ℃, the space velocity of the raw material is 0.3g/mL.cat.h, and the raw material air (acetoin: O) 2 ) The reaction is carried out under normal pressure according to the ratio of 1:3, the crude butanedione is obtained, and the reaction yield is used as the activity index of the catalyst.
The reaction liquid is purified by adopting the method unless otherwise specified:
transferring the butanedione crude product into a flask with a water separator, starting heating, distilling water (water generated by acetoin reaction) at normal pressure, and controlling the temperature of an oil bath to be not more than 100 ℃; when the temperature rises to 66 ℃, the fraction is extracted, the turbid fraction is still layered in the water separator, the lower water layer is separated, and the upper light yellow organic phase returns to the system to continue carrying water.
When the temperature is raised to about 75 ℃, the fraction becomes clear, no water layer is separated from the water separator, heating is stopped, and cooling is performed; the organic phase in the water separator was returned to the flask, the water separator was removed, and a 40cm high column and a rectifying device were replaced.
Starting vacuum distillation, controlling vacuum degree to about-0.075 Mpa, controlling oil bath temperature to be no more than 80deg.C, air temperature to be 48 deg.C, starting to color out fraction, controlling reflux ratio to 10:2, and collecting front fraction; with the extraction of the fraction, the gas phase purity was changed to a satisfactory product when the gas phase purity was higher than 99%, and the air temperature was about 55 ℃.
And continuously collecting qualified products, when the materials in the flask are few and the temperature rise is obvious, starting sampling analysis, and stopping rectification when the gas phase purity is lower than 99 percent. The residual materials in the bottle and the collected unqualified front cut fraction are sleeved into the next batch for rectification, the purity of the mixed product sample feeding analysis product is more than 99.5%, and the moisture is less than 0.05%.
Example 1
Weighing 96.5g of ferric trichloride and 6.31g of cerium nitrate hexahydrate, dissolving in deionized water, and stirring to completely dissolve into an iron-cerium salt solution; 45g of sodium carbonate is weighed and dissolved in deionized water, and is properly heated and stirred until the sodium carbonate is completely dissolved to form a precipitant solution; at room temperature, simultaneously dropwise adding an iron cerium salt solution and a precipitator solution, maintaining the pH value between 8 and 9, and completing dropwise adding for about 2 hours; after the coprecipitation dropwise addition is completed, the temperature of the catalyst system is raised to 75 ℃, and the catalyst system is aged for 1 hour; and (3) after the aging is finished, filtering the prepared catalyst precursor, collecting a solid filter cake, washing with deionized water until the pH value is neutral, and drying the catalyst precursor for 12 hours at the temperature of 100 ℃. And (3) placing the dried catalyst precursor into a muffle furnace, and roasting for 3 hours at 550 ℃ to obtain reddish brown solid oxide, namely the iron-cerium composite oxide catalyst with the cerium oxide mass accounting for 5%. The yield of 2, 3-butanedione was 83.38%.
Example 2
91.42g of ferric trichloride and 12.62g of cerium nitrate hexahydrate are weighed and dissolved in deionized water, and stirred to be completely dissolved into an iron-cerium salt solution; weighing 42.5g of sodium carbonate, dissolving in deionized water, and heating and stirring properly until the sodium carbonate is completely dissolved to form a precipitant solution; at room temperature, simultaneously dropwise adding an iron cerium salt solution and a precipitator solution, maintaining the pH value between 8 and 9, and completing dropwise adding for about 2 hours; after the coprecipitation dropwise addition is completed, the temperature of the catalyst system is raised to 75 ℃, and the catalyst system is aged for 1 hour; and (3) after the aging is finished, filtering the prepared catalyst precursor, collecting a solid filter cake, washing with deionized water until the pH value is neutral, and drying the catalyst precursor for 12 hours at the temperature of 100 ℃. And (3) placing the dried catalyst precursor into a muffle furnace, and roasting for 3 hours at 550 ℃ to obtain reddish brown solid oxide, namely the iron-cerium composite oxide catalyst with 10% of cerium oxide by mass. The yield of 2, 3-butanedione was tested to be 91.04%.
Example 3
86.34g of ferric trichloride and 18.92g of cerium nitrate hexahydrate are weighed and dissolved in deionized water, and stirred to be completely dissolved into an iron-cerium salt solution; weighing 41.5g of sodium carbonate, dissolving in deionized water, and heating and stirring properly until the sodium carbonate is completely dissolved to form a precipitant solution; at room temperature, simultaneously dropwise adding an iron cerium salt solution and a precipitator solution, maintaining the pH value between 8 and 9, and completing dropwise adding for about 2 hours; after the coprecipitation dropwise addition is completed, the temperature of the catalyst system is raised to 75 ℃, and the catalyst system is aged for 1 hour; and (3) after the aging is finished, filtering the prepared catalyst precursor, collecting a solid filter cake, washing with deionized water until the pH value is neutral, and drying the catalyst precursor for 12 hours at the temperature of 100 ℃. And (3) placing the dried catalyst precursor into a muffle furnace, and roasting for 3 hours at 550 ℃ to obtain reddish brown solid oxide, namely the iron-cerium composite oxide catalyst with the cerium oxide mass ratio of 15%. The yield of 2, 3-butanedione was 95.68%.
Example 4
81.26g of ferric trichloride and 25.23g of cerium nitrate hexahydrate are weighed and dissolved in deionized water, and stirred to be completely dissolved into an iron-cerium salt solution; weighing 40.5g of sodium carbonate, dissolving in deionized water, and heating and stirring properly until the sodium carbonate is completely dissolved to form a precipitant solution; at room temperature, simultaneously dropwise adding an iron cerium salt solution and a precipitator solution, maintaining the pH value between 8 and 9, and completing dropwise adding for about 2 hours; after the coprecipitation dropwise addition is completed, the temperature of the catalyst system is raised to 75 ℃, and the catalyst system is aged for 1 hour; and (3) after the aging is finished, filtering the prepared catalyst precursor, collecting a solid filter cake, washing with deionized water until the pH value is neutral, and drying the catalyst precursor for 12 hours at the temperature of 100 ℃. And (3) placing the dried catalyst precursor into a muffle furnace, and roasting for 3 hours at 550 ℃ to obtain reddish brown solid oxide, namely the iron-cerium composite oxide catalyst with the cerium oxide mass accounting for 20%. The yield of 2, 3-butanedione was 94.34%.
Example 5
With the catalyst prepared in example 3, the activity of the catalyst was tested at different feed molar ratios, the other reaction conditions were unchanged, and the results are shown in table 1.
TABLE 1 Activity of the catalysts at different raw material molar ratios
Example 6
The catalyst prepared in example 3 was tested for activity at different reaction temperatures, with the other reaction conditions unchanged, and the results are shown in table 2.
TABLE 2 Activity of the catalysts at different reaction temperatures
Example 7
With the catalyst prepared in example 3, the activity of the catalyst was tested at different feed liquid space velocities, and the other reaction test conditions were unchanged, with the results shown in table 3.
TABLE 3 Activity of the catalysts at different feed space velocities
| Acetoin liquid space velocity (g/mL. Cat.h) | Acetoin conversion (%) | Acetoin yield (%) |
| 0.1 | 100 | 90.39 |
| 0.2 | 100 | 93.52 |
| 0.3 | 100 | 95.68 |
| 0.4 | 99.3 | 92.18 |
Example 8
Catalytic reaction was carried out with the catalyst prepared in example 3, and when the reaction yield was reduced, the feed was stopped, cooled to 100 ℃, and air was switched to nitrogen; when the temperature of the preheater and the reaction furnace is reduced to 100 ℃, starting to feed an absolute ethyl alcohol cleaning pipeline and a reactor, cleaning until the ethyl alcohol is colorless or light yellow, closing a feed pump, and continuously purging the pipeline for 30min by using nitrogen;
switching the air path to air, and starting programmed heating passivation: raising the temperature to 300 ℃ at 100 ℃ for 200min and keeping for 60min; raising the temperature to 450 ℃ at 300 ℃ for 150min and keeping for 60min; heating to 550deg.C for 100min, and roasting at 550deg.C for 3 hr;
and after the roasting is finished, the temperature is reduced to the reaction temperature, the air speed is adjusted to the air speed of the reaction condition, the preheater is set to the required condition, and the feeding is started.
The reaction is carried out for about 23 days, the reaction liquid is taken, the gas phase detection is carried out, the acetoin content of the reaction liquid exceeds 1%, the yield is reduced to about 93%, the reaction is stopped, and the catalyst is regenerated. As shown in Table 4, the activity of the regenerated catalyst is basically recovered, the yield after three operations can also reach more than 95%, the operation duration is slightly reduced, and the catalyst can be estimated to be recycled for 15-20 times.
TABLE 4 comparison of catalyst run lengths and yields
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The catalytic synthesis method of 2, 3-butanedione is characterized by comprising the following steps:
pressing, crushing and sieving the iron-cerium composite oxide catalyst by a tablet press, filling the iron-cerium composite oxide catalyst into a miniature fixed bed reactor, heating, introducing acetoin and air for reaction to obtain a butanedione crude product, and purifying the butanedione crude product to obtain 2, 3-butanedione;
the mass ratio of cerium oxide in the iron-cerium composite oxide catalyst is 5-20%.
2. The catalytic synthesis process according to claim 1, wherein the temperature is increased to 180-250℃and the acetoin space velocity is 0.1-0.4. 0.4g/mL.cat.h, acetoin and O in air 2 The molar ratio of (2) is 1:2.5-5.
3. The catalytic synthesis process according to claim 1, further comprising a catalyst regeneration process:
stopping feeding when the reaction yield is reduced, cooling to 100 ℃, and simultaneously switching air to nitrogen; when the temperature of the preheater and the reaction furnace is reduced to 100 ℃, starting to feed an absolute ethyl alcohol cleaning pipeline and a reactor, cleaning until the ethyl alcohol is colorless or light yellow, closing a feed pump, and continuously purging the pipeline for 30min by using nitrogen;
switching the air path to air, and performing programmed temperature rising calcination by the reaction furnace;
and after the roasting is finished, the temperature is reduced to the reaction temperature, the air speed is adjusted to the air speed of the reaction condition, the preheater is set to the required condition, and the feeding is started.
4. The catalytic synthesis process according to claim 3, wherein the temperature-programmed calcination is specifically:
raising the temperature from 100 ℃ to 300 ℃ for 200min and keeping for 60min; then the temperature of the reaction furnace is increased from 300 ℃ to 450 ℃ for 150min and kept for 60min; the temperature of the reaction furnace is increased from 450 ℃ to 550 ℃ for 100min, and the reaction furnace is baked for 3h at 550 ℃.
5. The catalytic synthesis process according to claim 1, wherein the process for preparing the iron-cerium composite oxide catalyst comprises the steps of:
s1, dissolving ferric salt and cerium salt in water to form an iron-cerium salt solution; dissolving a precipitant in water to form a precipitant aqueous solution;
s2, simultaneously dropwise adding an iron-cerium salt solution and a precipitant aqueous solution, and heating and aging the mixed solution after the dropwise adding is completed;
s3, filtering the aged mixed solution, collecting a solid filter cake, washing and drying to obtain a catalyst precursor;
and S4, roasting the catalyst precursor to obtain the reddish brown catalyst.
6. The catalytic synthesis process according to claim 5, wherein the precipitant comprises sodium hydroxide, sodium carbonate, sodium bicarbonate, aqueous ammonia, the iron salt comprises one or more of ferric trichloride, ferric acetate, ferric sulfate, and ferric nitrate, the cerium salt comprises one or more of cerium chloride, cerium nitrate, cerium sulfate, and cerium acetate, and the molar ratio of iron element to cerium element in the iron salt and cerium salt is 8.6-41:1.
7. The catalytic synthesis process according to claim 5, wherein in step S2, the dropping temperature is room temperature, and the pH of the mixed solution is controlled to be 8 to 9; the aging temperature is 65-80 ℃ and the aging time is 1-2h.
8. The catalytic synthesis process according to claim 5, wherein the washing in step S3 is carried out with deionized water to a neutral pH, a drying temperature of 80-110 ℃ and a drying time of 12-24h.
9. The catalytic synthesis process according to claim 5, wherein in step S4, the calcination temperature is 450-550 ℃, the calcination time is 3-5h, and the calcination atmosphere is air.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686992A (en) * | 2005-03-24 | 2005-10-26 | 大连来克精化有限公司 | Method for preparing butanedione through oxidating acetylmethylcarbinol |
| CN105541588A (en) * | 2016-02-25 | 2016-05-04 | 济南悟通化学科技有限公司 | Synthesis method of butanedione |
| CA3024051A1 (en) * | 2017-11-14 | 2019-05-14 | China Petroleum And Chemical Corporation | Cu-based catalyst, its preparation process and use thereof |
| WO2022142709A1 (en) * | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Supported composite oxide catalyst and preparation and use thereof |
| WO2022142708A1 (en) * | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Composite oxide catalyst, preparation method therefor, and use thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686992A (en) * | 2005-03-24 | 2005-10-26 | 大连来克精化有限公司 | Method for preparing butanedione through oxidating acetylmethylcarbinol |
| CN105541588A (en) * | 2016-02-25 | 2016-05-04 | 济南悟通化学科技有限公司 | Synthesis method of butanedione |
| CA3024051A1 (en) * | 2017-11-14 | 2019-05-14 | China Petroleum And Chemical Corporation | Cu-based catalyst, its preparation process and use thereof |
| WO2022142709A1 (en) * | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Supported composite oxide catalyst and preparation and use thereof |
| WO2022142708A1 (en) * | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Composite oxide catalyst, preparation method therefor, and use thereof |
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