CN116272948A - Stable cerium-containing catalyst and preparation method and application thereof - Google Patents
Stable cerium-containing catalyst and preparation method and application thereof Download PDFInfo
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- CN116272948A CN116272948A CN202111559990.9A CN202111559990A CN116272948A CN 116272948 A CN116272948 A CN 116272948A CN 202111559990 A CN202111559990 A CN 202111559990A CN 116272948 A CN116272948 A CN 116272948A
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- cerium
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- aluminum
- magnesium
- containing catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 43
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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 6
- 150000002009 diols Chemical class 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 229940118662 aluminum carbonate Drugs 0.000 claims description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- -1 naHCO 3 Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 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 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 229940083957 1,2-butanediol Drugs 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 1
- 235000000621 Bidens tripartita Nutrition 0.000 description 1
- 240000004082 Bidens tripartita Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 208000006637 fused teeth Diseases 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a stable cerium-containing catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Stirring and mixing soluble salts of magnesium, aluminum and cerium, an alkaline solution and a solvent to obtain a mixed solution; (2) And (3) stirring the mixed solution obtained in the step (1), and then sequentially carrying out crystallization treatment, drying treatment and roasting treatment to obtain the cerium-containing catalyst. The catalyst has the advantages of low production cost, strong alkalinity, high stability, repeated utilization for multiple times, and amplified production, and compared with a homogeneous catalyst, the catalyst has the advantages of easy separation of the catalyst and the product, high product selectivity and the like; the cyclic carbonate is obtained by mixing and stirring carbonate, glycol and cerium-containing catalyst and then heating, and has the advantages of simple synthesis method, mild experimental conditions, no need of solvents, high temperature and high pressure and other harsh conditions, and shorter reaction time.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysis, and particularly relates to a stable cerium-containing catalyst, and a preparation method and application thereof.
Background
Cyclic carbonates are a very important class of chemicals and organic intermediates, and have the characteristics of high boiling point, low odor, low toxicity, biodegradability and the like. Of the cyclic carbonates, glycerol carbonate, ethylene carbonate, propylene carbonate, 1, 2-butylene carbonate and the like are most typical. Ethylene carbonate is often used as a reaction medium for the production of high molecular weight compounds and various chemical processes, an extractant, a plasticizer, a polar solvent for foaming agents, a stabilizer for lubricating oils, and the like; propylene carbonate is useful as a solvent and plasticizer for dielectric polymers for batteries and capacitors, a resin curing accelerator, a pigment dispersant, an aprotic solvent, an intermediate for producing polycarbonates and fine chemicals, and the like; the 1, 2-butylene carbonate has important commercial value, is mainly used for producing plasticizers, surfactants and reactive intermediate materials of polymers, can be used as degreasing solvents, paint removers, wood adhesive resins, foundry sand adhesives and the like, and can be used as battery electrolyte in lithium batteries and the like.
The synthesis of cyclic carbonates by transesterification of diols with carbonates is a green and high-value synthetic conversion route. The diol raw materials used for synthesizing the cyclic carbonate mainly comprise Ethylene Glycol (EG), propylene Glycol (PG), 1, 2-Butanediol (BG) and the like, and the diol has a plurality of important application values, such as manufacturing explosive, plastics, paint and the like, but the main application fields are in the polyester industry. Along with the rapid development of polyester industry in China, the demand of glycol is increased year by year, and the current production process of coal-to-glycol approximately generates 10% of by-product fusel which is rich in substances such as methanol, ethanol, glycol, 1, 2-butanediol and the like, and if the raw materials are fully utilized for producing cyclic carbonate, the method is a very green way.
At present, the synthesis method of the cyclic carbonate mainly comprises a phosgene method, a carbon dioxide and epoxide ring addition method, direct coupling of carbon dioxide and glycol, a urea alcoholysis method, an ester exchange method and the like. The phosgene method needs to use toxic reagent phosgene, not only causes environmental pollution, but also generates by-product hydrochloric acid, and is forbidden at present; although the ring addition method meets the requirement of green chemistry, the ring addition method needs to react under the severe conditions of high temperature and high pressure, has potential safety hazard, is easy to cause danger, and is unfavorable for industrial production because the raw material source is easy to cause environmental pollution; the coupling method has higher yield, but needs higher reaction pressure, easy reaction explosion, harsh operation condition and lower safety coefficient; the catalyst in the urea alcoholysis method is easy to dissolve in an organic solvent, so that the purity of the product is reduced, and the subsequent separation is difficult. The transesterification method utilizes a heterogeneous catalyst to synthesize the cyclic carbonate by using glycol and carbonate, has simple and mild reaction conditions, easily obtained raw materials, easily separated products and low requirements on equipment, and is the most commonly used synthesis method at present. The catalysts commonly used in the transesterification method at present mainly comprise acid-base homogeneous catalysts (mainly acid alkali metal salts, ionic liquids and the like, including hydrochloric acid, phosphoric acid, concentrated sulfuric acid and the like), heterogeneous acid-base catalysts (molecular sieves, solid catalysts prepared by loading, doping, modifying alkali metal, alkaline earth metal oxides and the like, hydrotalcite and the like) and other lipase catalysts.
CN101108843B discloses a method for synthesizing cyclic carbonate in aqueous system, which uses epoxy compound and carbon dioxide as raw materials, uses bidentate ionic liquid as catalyst and alkali metal salt as promoter in the reaction process, and synthesizes cyclic carbonate under the conditions of reaction pressure of 0.1-10.0MPa, temperature of 313.15-483.15K and time of 0-6 h. The synthesis method has the advantages of low cost, environment friendliness, mild reaction conditions, stable heat, high selectivity, repeated use, high activity and the like, and has a very strong industrial application prospect. But the catalyst of the double-tooth ionic liquid is low in catalytic efficiency of imidazole ring with methyl, and meanwhile, a catalyst promoter is required to be added, so that the catalytic system is complex.
CN105153104a discloses a process for the synthesis of propylene carbonate, said process being carried out as CO 2 And (3) taking propylene oxide as a raw material, loading ionic liquid on bentonite as a catalyst, and synthesizing the propylene carbonate in a high-pressure reaction kettle. The saidThe catalyst provided by the method has high activity and strong selectivity, but still needs to be loaded by a carrier, and is limited to a certain extent in practical application, and even the stability of the catalyst can be reduced.
Therefore, how to find a heterogeneous transesterification catalyst with high activity and high selectivity without solvent and carrier has great value and significance for producing high-quality cyclic carbonates.
Disclosure of Invention
In order to solve the technical problems, the invention provides a stable cerium-containing catalyst, a preparation method and application thereof, wherein the catalyst has the advantages of high stability, high activity, strong reusability and the like; the catalyst can be used for preparing the cyclic carbonate with high selectivity, high yield and easy separation of products by using the carbonate and the diol raw material under a mild condition.
In order to achieve the technical effects, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a stable cerium-containing catalyst, the method comprising the steps of:
(1) Stirring and mixing soluble salts of magnesium, aluminum and cerium, an alkaline solution and a solvent to obtain a mixed solution;
(2) And (3) stirring the mixed solution obtained in the step (1), and then sequentially carrying out crystallization treatment, drying treatment and roasting treatment to obtain the cerium-containing catalyst.
In the invention, the preparation method is simple and easy to operate, low in production cost and capable of realizing amplified production, and the prepared cerium-containing catalyst has the advantages of stronger alkalinity, high stability, high activity and the like.
As a preferred embodiment of the present invention, the molar ratio of the soluble salt of magnesium to the soluble salts of aluminum and cerium in the step (1) is (2-4): 1, and may be, for example, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1 or 4:1, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
In the present invention, the molar ratio of the soluble salts of aluminum and cerium is (1-9): 1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, or 9:1, etc., but not limited to the recited values, other non-recited values within the numerical range are equally applicable.
Preferably, the soluble salt of magnesium of step (1) comprises any one or a combination of at least two of magnesium nitrate, magnesium chloride, magnesium carbonate or magnesium sulfate, typical but non-limiting examples of such combinations being: a combination of magnesium nitrate and magnesium chloride, a combination of magnesium chloride and magnesium carbonate, or a combination of magnesium carbonate and magnesium sulfate, etc.
Preferably, the soluble salts of aluminum of step (1) comprise any one or a combination of at least two of aluminum nitrate, aluminum chloride, aluminum carbonate or aluminum sulfate, typical but non-limiting examples of such combinations being: a combination of aluminum nitrate and aluminum chloride, a combination of aluminum chloride and aluminum carbonate, or a combination of aluminum carbonate and aluminum sulfate, etc.
Preferably, the soluble salt of cerium of step (1) comprises any one or a combination of at least two of cerium nitrate, cerium chloride, cerium sulfate or cerium acetate, typical but non-limiting examples of such combinations being: a combination of cerium nitrate and cerium chloride, a combination of cerium chloride and cerium sulfate, or a combination of cerium sulfate and cerium acetate, and the like.
As a preferred embodiment of the present invention, the alkali in the alkaline solution of step (1) comprises NaOH, KOH, naHCO 3 、Na 2 CO 3 Or any one or at least two combinations of aqueous ammonia, typical but non-limiting examples of which are: combination of NaOH and KOH, KOH and NaHCO 3 Or NaHCO (combination of (C)) 3 And ammonia water, etc.
Preferably, the hydroxide ion concentration of the alkaline solution in the step (1) is 2 to 10mol/L, for example, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the solvent of step (1) comprises deionized water.
Preferably, the pH of the mixed solution in step (1) is 9-11, and may be, for example, 9, 9.2, 9.4, 9.6, 9.8, 10, 10.2, 10.4, 10.6, 10.8 or 11, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the method of stirring and mixing the soluble salts of magnesium, aluminum and cerium, the alkaline solution and the solvent in the step (1) comprises: mixing soluble salts of magnesium, aluminum and cerium with a solvent, dispersing for 0.5-2h under ultrasonic stirring, and then dripping an alkaline solution into the soluble salts and the solvent at 20-150 drops/min.
In a preferred embodiment of the present invention, the stirring time in the step (2) is 0.5 to 2 hours, for example, 0.5 hours, 1 hour, 1.5 hours or 2 hours, etc., but the stirring time is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The crystallization treatment in the step (2) is preferably carried out at a temperature of 60 to 180 ℃, for example, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃ or the like, but the crystallization treatment is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
Preferably, the crystallization treatment in step (2) is performed for 8-24 hours, for example, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, etc., but the crystallization treatment is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
As a preferable technical scheme of the invention, the mixed solution obtained after the crystallization treatment in the step (2) is subjected to solid-liquid separation treatment, and the obtained solid is washed to be neutral.
In a preferred embodiment of the present invention, the temperature of the drying treatment in the step (2) is 70 to 120. DegreeC, for example, 70. DegreeC, 80. DegreeC, 90. DegreeC, 100. DegreeC, 110. DegreeC, 120. DegreeC, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the numerical range are applicable.
Preferably, the drying treatment in step (2) is performed for 12-24 hours, for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, etc., but the drying treatment is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The temperature of the baking treatment in the step (2) is preferably 400 to 800 ℃, and may be, for example, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
Preferably, the time of the calcination treatment in step (2) is 2-8h, for example, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In a second aspect, the present invention provides a stable cerium-containing catalyst prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides the use of a cerium-containing catalyst as described in the second aspect for the synthesis of a cyclic carbonate.
As a preferred technical solution of the present invention, the application comprises the following steps: and mixing and stirring the carbonic ester, the glycol and the cerium-containing catalyst, and then performing heating treatment to obtain the cyclic carbonic ester.
In the invention, the synthesis condition of the cyclic carbonate is mild, the process is simple, and the harsh conditions such as organic solvent, high temperature and high pressure are not needed.
In a preferred embodiment of the present invention, the molar ratio of the carbonate to the diol is (2-10): 1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the mass ratio of the cerium-containing catalyst to glycol is (0.001-0.2): 1, for example, it may be 0.001:1, 0.005:1, 0.01:1, 0.02:1, 0.04:1, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1 or 0.2:1, etc., but not limited to the recited values, other non-recited values within the numerical range are equally applicable.
The temperature of the heat treatment is preferably 80 to 200 ℃, and may be, for example, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, or the like, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The heat-treatment is preferably carried out for a period of 20 to 300 minutes, and may be carried out at 80℃and 100℃and 120℃and 140℃and 160℃and 180℃and 200℃respectively, but the heat-treatment is not limited to the values listed, and other values not listed in the numerical range are applicable.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a heterogeneous catalyst for synthesizing cyclic carbonate, which has the advantages of low production cost, strong alkalinity, high stability, repeated utilization for multiple times, amplified production, easy separation of catalyst and product, high product selectivity and the like compared with the homogeneous catalyst;
(2) The catalyst prepared by the invention has simple process and mild experimental conditions when being applied to synthesizing the cyclic carbonate, and compared with other synthetic routes, the catalyst does not need solvents, high temperature, high pressure and other harsh conditions, and has shorter reaction time; the glycol conversion rate is up to 92% or more, and the cyclic carbonate selectivity and yield are up to 91% or more.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method and application of a cerium-containing catalyst, wherein the preparation method and application comprise the following steps:
(1) 7.68g of Mg (NO 3 ) 2 ·6H 2 O、3.455g Al(NO 3 ) 3 ·9H 2 O、0.65g Ce(NO 3 ) 3 ·6H 2 O and 100ml deionized water are mixed to prepare solution A, dispersed for 1h under ultrasonic stirring, and NaOH and Na are added 2 CO 3 Dissolving in deionized water to prepare solution B with hydroxide ion concentration of 4mol/L, and then dripping the solution B into the solution A at 90 drops/min through a basic burette until the pH value of the mixed solution is 10 to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) for 1h, crystallizing at 120 ℃ for 12h, filtering the obtained slurry, washing the filtered solid with deionized water to be neutral, and drying at 100 DEG CDrying for 18h, grinding the solid after drying, and roasting at 600 ℃ for 5h to obtain Mg 3 Al 0.9 Ce 0.1 An O composite catalyst;
(3) 18.0g of dimethyl carbonate, 3.1g of ethylene glycol and 0.17g of Mg obtained in the step (2) 3 Al 0.9 Ce 0.1 O is added into a reaction kettle, the reaction temperature is 150 ℃, and the reaction is carried out for 100min at 750rpm, thus obtaining the cyclic carbonate.
Example 2
The embodiment provides a preparation method and application of a cerium-containing catalyst, wherein the preparation method and application comprise the following steps:
(1) 5.12g of Mg (NO 3 ) 2 ·6H 2 O、0.375g Al(NO 3 ) 3 ·9H 2 O、3.91g Ce(NO 3 ) 3 ·6H 2 O and 100ml deionized water are mixed to prepare solution A, dispersed for 2h under ultrasonic stirring, and NaOH and NaHCO are added 3 Dissolving in deionized water to prepare a solution B with hydroxide ion concentration of 2mol/L, and then dripping the solution B into the solution A at 150 drops/min through a basic burette until the pH value of the mixed solution is 9 to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) for 2 hours, crystallizing at 180 ℃ for 8 hours to obtain slurry, filtering, washing the filtered solid with deionized water for many times to neutrality, drying at 120 ℃ for 12 hours, grinding the solid after drying, and roasting at 800 ℃ for 2 hours to obtain Mg 2 Al 0.9 Ce 0.1 An O catalyst;
(3) 9.0g of dimethyl carbonate, 3.1g of ethylene glycol and 0.07g of Mg obtained in the step (2) 2 Al 0.9 Ce 0.1 O is added into a reaction kettle, the reaction temperature is 200 ℃, and the reaction is carried out for 20min at 750rpm, thus obtaining the cyclic carbonate.
Example 3
The embodiment provides a preparation method and application of a cerium-containing catalyst, wherein the preparation method and application comprise the following steps:
(1) 10.24g of Mg (NO 3 ) 2 ·6H 2 O、3.455g Al(NO 3 ) 3 ·9H 2 O、0.65g Ce(NO 3 ) 3 ·6H 2 Mixing O and 100ml deionized water to prepare a solution A, dispersing for 1h under ultrasonic stirring, dissolving NaOH in the deionized water to prepare a solution B with hydroxide ion concentration of 10mol/L, and then dropwise adding the solution B into the solution A at 20 drops/min through an alkali burette until the pH value of the mixed solution is 11 to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) for 0.5h, crystallizing at 60 ℃ for 24h to obtain slurry, filtering, washing the filtered solid with deionized water for many times to neutrality, drying at 70 ℃ for 24h, grinding the dried solid, and roasting at 400 ℃ for 8h to obtain Mg 4 Al 0.9 Ce 0.1 An O catalyst;
(3) 45.0g of dimethyl carbonate, 3.1g of ethylene glycol and 0.62g of Mg obtained in the step (2) 4 Al 0.9 Ce 0.1 O is added into a reaction kettle, the reaction temperature is 80 ℃, and the reaction is carried out for 300min at 750rpm, thus obtaining the cyclic carbonate.
Example 4
The embodiment provides a preparation method and application of a cerium-containing catalyst, wherein the preparation method and application comprise the following steps:
(1) 7.68g of Mg (NO 3 ) 2 ·6H 2 O、3.376g Al(NO 3 ) 3 ·9H 2 O、0.432g Ce(NO 3 ) 3 ·6H 2 O and 100ml deionized water are mixed to prepare solution A, dispersed for 0.5h under ultrasonic stirring, and NaOH and Na are added 2 CO 3 Dissolving in deionized water to prepare solution B with hydroxide ion concentration of 4mol/L, and then dripping the solution B into the solution A at 90 drops/min through a basic burette until the pH value of the mixed solution is 10.5 to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) for 0.5h, crystallizing at 60 ℃ for 12h to obtain slurry, filtering, washing the filtered solid with deionized water for many times to neutrality, drying at 80 ℃ for 12h, grinding the dried solid, and roasting at 500 ℃ for 5h to obtain Mg 3 Al 0.9 Ce 0.1 An O catalyst;
(3) 18.0g of dimethyl carbonate, 3.1g of ethylene glycol and 0.17g of Mg prepared in the step (2) 3 Al 0.9 Ce 0.1 O is added into a reaction kettle, the reaction temperature is 150 ℃, and the reaction is carried out for 40min at 750rpm, thus obtaining the cyclic carbonate.
Example 5
The difference between this example and example 4 is that the reaction time in step (3) was 30min, and the other conditions were the same as in example 4.
Example 6
The difference between this example and example 4 is that the reaction temperature in step (3) is 120℃and the other conditions are the same as in example 4.
Example 7
The difference between this example and example 6 is that the catalyst after the synthesis of the cyclic carbonate in step (3) of example 6 was separated, washed and dried, and then the catalyst was continuously recycled for the catalytic synthesis of the cyclic carbonate in step (3), and the catalyst was repeatedly recycled 5 times, and the other conditions were the same as in example 6.
Example 8
This example differs from example 5 only in that step (1)' 3.376g Al (NO 3 ) 3 ·9H 2 O、0.432g Ce(NO 3 ) 3 ·6H 2 O "is replaced with" 1.875g Al (NO) 3 ) 3 ·9H 2 O、2.171g Ce(NO 3 ) 3 ·6H 2 O ", other conditions were the same as in example 4.
Example 9
This example differs from example 8 only in that step (3) "3.1g of ethylene glycol" was replaced with "3.1g of 1.2-propanediol", except that the same conditions were used in example 8.
Example 10
This example differs from example 8 only in that step (3) "3.1g of ethylene glycol" was replaced with "3.1g of 1.2-butanediol", and the reaction temperature of step (3) was 160℃under the same conditions as in example 8.
Example 11
The difference between this example and example 4 is that the temperature of the baking treatment in step (2) was 300℃and the other conditions were the same as in example 4.
Example 12
The difference between this example and example 4 is that the temperature of the baking treatment in step (2) was 900℃and the other conditions were the same as in example 4.
Comparative example 1
The comparative example provides a preparation method and application of a cerium-containing catalyst, wherein the preparation method and application comprise the following steps:
(1) 2.171g Ce (NO) 3 ) 3 ·6H 2 Mixing O and 100ml deionized water, dispersing for 0.5h under ultrasonic stirring, dissolving NaOH in the deionized water to prepare solution B with hydroxide ion concentration of 4mol/L, and then dropwise adding the solution B into the solution A at 90 drops/min through a basic burette until the pH value of the mixed solution is 10.5 to obtain a mixed solution;
(2) Stirring the mixed solution obtained in the step (1) for 0.5h, crystallizing at 60 ℃ for 12h to obtain slurry, filtering, washing the filtered solid with deionized water for many times to neutrality, drying at 80 ℃ for 12h, grinding the dried solid, and roasting at 500 ℃ for 5h to obtain CeO 2 A catalyst;
(3) 18.0g of dimethyl carbonate, 3.1g of ethylene glycol and 0.17g of CeO prepared in the step (2) are mixed 2 The catalyst was added to a reaction vessel at a reaction temperature of 120℃and at 750rpm for 40min to give a cyclic carbonate.
Comparative example 2
The present comparative example differs from comparative example 1 only in that "2.171g Ce (NO 3 ) 3 ·6H 2 O "is replaced with" 1.875g Al (NO) 3 ) 3 ·9H 2 O ", other conditions were the same as in comparative example 1.
Comparative example 3
The present comparative example differs from comparative example 1 only in that "2.171g Ce (NO 3 ) 3 ·6H 2 O "is replaced by" 7.68g Mg (NO) 3 ) 2 ·6H 2 O ", other conditions were the same as in comparative example 1.
Comparative example 4
The present comparative example differs from comparative example 1 only in that "2.171g Ce (NO 3 ) 3 ·6H 2 O "is replaced by" 7.68g Mg (NO) 3 ) 2 ·6H 2 O and 1.875g Al (NO) 3 ) 3 ·9H 2 O ", other conditions were the same as in comparative example 1.
Comparative example 5
The present comparative example differs from comparative example 1 only in that "2.171g Ce (NO 3 ) 3 ·6H 2 O "is replaced by" 7.68g Mg (NO) 3 ) 2 ·6H 2 O and 2.171g Ce (NO) 3 ) 3 ·6H 2 O ", other conditions were the same as in comparative example 1.
The cyclic carbonate solutions obtained in step (3) of examples 1 to 12 and comparative examples 1 to 5 were centrifuged at 3000rpm for 3min, and an appropriate amount of the supernatant was added to an internal standard (biphenyl) and quantitatively analyzed by a gas chromatography internal standard method. The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the cerium-containing catalyst prepared by the invention is applied to the synthesis of cyclic carbonate, the glycol conversion rate is more than or equal to 92%, the product cyclic carbonate selectivity is more than or equal to 91%, and the cyclic carbonate yield is more than 91%; the cerium-containing catalyst prepared in the example 7 still has good catalytic effect when being recycled for 5 times, and the yield of the cyclic carbonate is still more than or equal to 90%; examples 8, 9 and 10 show that the prepared cerium-containing catalyst can achieve quite high selectivity and yield of the corresponding cyclic carbonate product, whether ethylene glycol is used for preparing ethylene carbonate or 1, 2-propylene glycol is used for preparing propylene carbonate, and 1, 2-butanediol is used for preparing butylene carbonate; example 11 roasting treatment temperature is too low, resulting in incomplete reaction, and soluble salts of magnesium, aluminum and cerium are not completely decomposed into metal oxide form, resulting in deterioration of catalytic effect; example 12 calcination treatment temperature was too high, resulting in catalyst sintering, resulting in reduced surface area, reduced pore volume, reduced active site dispersibility, reduced contact area with reactants, and poor catalytic performance.
The catalysts prepared in comparative examples 1-3 only contain a single metal oxide, the catalyst prepared in comparative example 4 is Mg-Al oxide and the catalyst prepared in comparative example 5 is Mg-Ce oxide, and the selectivity and yield of the cyclic carbonate are low when the catalyst is applied to the synthesis of the cyclic carbonate, so that the selectivity and yield of the catalytic synthesis of the cyclic carbonate are good only when the catalyst contains three metals of magnesium, aluminum and cerium.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A method for preparing a stable cerium-containing catalyst, comprising the steps of:
(1) Stirring and mixing soluble salts of magnesium, aluminum and cerium, an alkaline solution and a solvent to obtain a mixed solution;
(2) And (3) stirring the mixed solution obtained in the step (1), and then sequentially carrying out crystallization treatment, drying treatment and roasting treatment to obtain the cerium-containing catalyst.
2. The method according to claim 1, wherein the molar ratio of the soluble salt of magnesium to the soluble salts of aluminum and cerium in step (1) is (2-4): 1;
preferably, the soluble salt of magnesium of step (1) comprises any one or a combination of at least two of magnesium nitrate, magnesium chloride, magnesium carbonate or magnesium sulfate;
preferably, the soluble salt of aluminum of step (1) comprises any one or a combination of at least two of aluminum nitrate, aluminum chloride, aluminum carbonate or aluminum sulfate;
preferably, the soluble salt of cerium of step (1) comprises any one or a combination of at least two of cerium nitrate, cerium chloride, cerium sulfate or cerium acetate.
3. The process according to claim 1 or 2, wherein the base in the alkaline solution of step (1) comprises NaOH, KOH, naHCO 3 、Na 2 CO 3 Or any one or a combination of at least two of ammonia water;
preferably, the hydroxide ion concentration of the alkaline solution in the step (1) is 2-10mol/L;
preferably, the solvent of step (1) comprises deionized water;
preferably, the pH value of the mixed solution in the step (1) is 9-11;
preferably, the method of stirring and mixing the soluble salts of magnesium, aluminum and cerium, the alkaline solution and the solvent in the step (1) comprises: mixing soluble salts of magnesium, aluminum and cerium with a solvent, dispersing for 0.5-2h under ultrasonic stirring, and then dripping an alkaline solution into the soluble salts and the solvent at 20-150 drops/min.
4. A method according to any one of claims 1 to 3, wherein the stirring time in step (2) is 0.5 to 2 hours;
preferably, the temperature of the crystallization treatment in the step (2) is 60-180 ℃;
preferably, the crystallization treatment in the step (2) is performed for 8-24 hours.
5. The process according to any one of claims 1 to 4, wherein the crystallization treatment in step (2) is followed by solid-liquid separation treatment of the resulting mixed solution, and the resulting solid is washed to neutrality.
6. The method according to any one of claims 1 to 5, wherein the temperature of the drying treatment in step (2) is 70 to 120 ℃;
preferably, the drying treatment in the step (2) is carried out for 12-24 hours;
preferably, the temperature of the roasting treatment in the step (2) is 400-800 ℃;
preferably, the roasting treatment in the step (2) is carried out for 2-8 hours.
7. A stabilized cerium-containing catalyst prepared by the method of any one of claims 1 to 6.
8. The use of a cerium-containing catalyst according to claim 7, wherein the cerium-containing catalyst is used for the synthesis of cyclic carbonates.
9. The application according to claim 8, characterized in that the application comprises the steps of: and mixing and stirring the carbonic ester, the glycol and the cerium-containing catalyst, and then performing heating treatment to obtain the cyclic carbonic ester.
10. Use according to claim 9, characterized in that the carbonate to diol molar ratio is (2-10): 1;
preferably, the mass ratio of the cerium-containing catalyst to glycol is (0.001-0.2): 1;
preferably, the temperature of the heating treatment is 80-200 ℃;
preferably, the heat-preserving time of the heating treatment is 20-300min.
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