CN115634682A - Double-component monoatomic solid base catalyst, preparation and application thereof - Google Patents
Double-component monoatomic solid base catalyst, preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000007787 solid Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 230000002195 synergetic effect Effects 0.000 claims abstract description 57
- 239000002585 base Substances 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 6
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 41
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 16
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 11
- 238000005809 transesterification reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 238000010438 heat treatment Methods 0.000 abstract description 17
- 230000007547 defect Effects 0.000 abstract description 4
- 239000012876 carrier material Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000004873 anchoring Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 22
- 230000008929 regeneration Effects 0.000 description 17
- 238000011069 regeneration method Methods 0.000 description 17
- 239000003513 alkali Substances 0.000 description 10
- 239000011363 dried mixture Substances 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- WNPMJIKMURUYFG-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] WNPMJIKMURUYFG-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 4
- 229940044658 gallium nitrate Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- LSDAFBBAZCPULC-UHFFFAOYSA-N [K].[Sn] Chemical compound [K].[Sn] LSDAFBBAZCPULC-UHFFFAOYSA-N 0.000 description 2
- GWNAJLSPZNJDQW-UHFFFAOYSA-N [Na].[Ge] Chemical compound [Na].[Ge] GWNAJLSPZNJDQW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- GMYSDEOJMBLAKZ-UHFFFAOYSA-N calcium indium Chemical compound [Ca].[In] GMYSDEOJMBLAKZ-UHFFFAOYSA-N 0.000 description 2
- XAMAHSKHODBYNV-UHFFFAOYSA-N cesium germanium Chemical compound [Ge].[Cs] XAMAHSKHODBYNV-UHFFFAOYSA-N 0.000 description 2
- HLAZMVAILNXLKL-UHFFFAOYSA-N germanium potassium Chemical compound [K].[Ge] HLAZMVAILNXLKL-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- AGNPPWAGEICIGZ-UHFFFAOYSA-N strontium tin Chemical compound [Sr].[Sn] AGNPPWAGEICIGZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a bi-component monoatomic solid base catalyst and preparation and application thereof, which consists of an active component and a carrier modified by a synergistic component; wherein, the active component is alkali metal or alkaline earth metal, and the synergistic component is III or IV main group metal; the carrier is one or more of porous carbon materials or oxides. The preparation method is characterized in that two metal component precursors are used as objects and are prepared through two-step dipping and a heat treatment method. The carrier is modified by introducing the synergistic component, and then the basic sites are endowed on the carrier by introducing the active component. The synergistic component metal elements increase the defects and vacancies on the surface of the carrier, promote the dispersion of active component metal atoms and improve the stable anchoring of the active component metal atoms. The high dispersion of the alkaline sites on the carrier material significantly improves the utilization rate of the active sites and the catalytic activity. Meanwhile, the interaction force between the alkaline site and the carrier enables the alkaline site to be firmly anchored on the surface of the carrier, the loss of active sites is reduced, the service life of the catalyst is prolonged, and the catalyst is good in recycling.
Description
Technical Field
The invention relates to the technical field of industrial catalysis, in particular to a double-component monatomic solid base catalyst, and preparation and application thereof.
Background
Dimethyl carbonate (DMC) is widely used in green chemical industry because of its unique physicochemical properties. Because of its advantages of higher octane number, good mixing property, low toxicity and quick biodegradability, it is also used as a substitute for gasoline additives and methyl tert-butyl ether. More importantly, DMC is a promising and environmentally friendly alternative to dimethyl sulfate and phosgene in the methylation and carbonylation reactions, respectively. The conventional DMC synthesis processes are predominantly photochemical, oxidative carbonylation and methine. The photochemical reaction of methanol has now been abandoned due to its toxicity and the formation of harmful by-products. At present, DMC is mainly produced by methanol oxidative carbonylation and nitrite methylation processes. These processes also suffer from low productivity and the formation of carbon monoxide, nitric oxide and hydrogen chloride. Other routes, such as direct synthesis of DMC by catalysis of a transesterification reaction of methanol with ethylene carbonate or propylene carbonate, have also been used to produce DMC. However, the catalytic process generally uses liquid alkali, the catalyst separation cost is high, the amount of waste liquid is large, and the industrial production cost of DMC is increased. The development of an efficient solid base catalyst for the ester exchange synthesis of DMC is emphasized, and compared with the traditional liquid base catalyst in the chemical industry at present, the solid base catalyst has the advantages of easiness in separation from reaction liquid, mild reaction conditions, high activity, easiness in recycling and the like. From the perspective of actual chemical production, the solid base catalyst has low corrosion to equipment, enhances the production continuity, simplifies the production flow, and is expected to become a new environment-friendly catalyst. Although the solid base catalyst has a plurality of advantages, the traditional solid base catalyst has the problems that the basic sites are easy to aggregate and easily run off. The presence of these problems limits the industrial application of solid base catalysts. Therefore, there is a need in the art to develop a high performance solid base catalyst.
Disclosure of Invention
The invention aims to improve the defects of the prior art and provide a bi-component monatomic solid base catalyst, a preparation method of the catalyst and the use of the catalyst. Firstly, dispersing the metal of the synergistic component into the carrier before introducing the basic metal sites to obtain the carrier modified by the synergistic component, wherein the carrier material has good specific surface area and abundant pore structures, the synergistic component is fully dispersed on the surface of the carrier, and the introduction of the synergistic component changes the surface structure of the carrier and increases the defects and vacant sites of the carrier. Then, the active component (alkali metal or alkaline earth metal) is introduced into the carrier modified with the synergistic component, and the atoms of the active component are highly dispersed and firmly anchored in the carrier in the form of a single atom under the influence of the atoms of the metal of the synergistic component. The obtained target catalyst shows good catalytic activity and stability in the reaction of synthesizing dimethyl carbonate by ester exchange.
The technical scheme of the invention is as follows: a bi-component monatomic solid base catalyst, characterized in that: consists of active components and a carrier modified by synergistic components; wherein, the active component is alkali metal or alkaline earth metal, and the synergistic component is III or IV main group metal; the carrier is one or more of porous carbon materials or oxides.
Preferably, the active component is lithium, sodium, magnesium, potassium, calcium, rubidium, strontium or cesium; the synergistic component is gallium, germanium, indium or tin; the porous carbon material is one or more of activated carbon, mesoporous carbon or graphene; the oxide is Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 Or CeO 2 One or more of (a).
Preferably, the molar ratio of the active component to the carrier is 0.01-0.15, and the molar ratio of the synergistic component to the carrier is 0.01-0.15.
The invention also provides a method for synthesizing the double-component monatomic solid base catalyst, which comprises the following specific steps:
(1) Weighing a synergistic component precursor, dissolving the synergistic component precursor in a solvent, adding the carrier in proportion, stirring at room temperature, stirring in a water bath, evaporating to dryness, then putting the mixture into an oven for drying, and putting the dried sample into a tubular furnace for pre-activation at low temperature for 2-3 hours in an inert atmosphere at 300-600 ℃ to obtain a synergistic component modified carrier;
(2) Weighing an active component precursor, dissolving the active component precursor in a solvent, adding a carrier modified by the synergistic component according to a proportion, stirring at room temperature, stirring in a water bath, evaporating to dryness, and then putting into a drying oven for drying to obtain a sample to be activated;
(3) And (3) placing the sample to be activated in a tubular furnace, roasting and activating at high temperature under the protection of protective atmosphere, so that the active component precursor is converted into free metal atoms and stably anchored in the carrier modified by the synergistic component, and thus obtaining the double-component monatomic solid base catalyst.
Preferably, the active component precursor is a nitrate, carbonate or acetate corresponding to an alkali metal or an alkaline earth metal, such as: sodium nitrate, magnesium nitrate, potassium nitrate, calcium nitrate, rubidium nitrate, cesium nitrate, potassium carbonate, calcium carbonate, strontium carbonate, and sodium acetate; the precursor of the synergistic component is a metal salt corresponding to metal elements in main groups III or IV, such as: a nitrate salt.
Preferably, the solvent is one or more of organic solvent or inorganic solvent, including ethanol, deionized water and methanol; the protective atmosphere is one of helium, argon or nitrogen.
Preferably, the stirring time in the steps (1) and (2) is 6-8 h, the water bath temperature is 80-90 ℃, the oven temperature is 90-100 ℃, and the drying time is 12-24 h; the temperature of the high-temperature roasting activation in the step (3) is 800-1000 ℃, and the activation time is 3-5 h.
The invention also provides application of the double-component single-atom solid base catalyst in the reaction of synthesizing dimethyl carbonate by ester exchange. The method is characterized in that methyl alcohol and ester are catalyzed to generate ester exchange reaction to generate dimethyl carbonate; wherein the ester is ethylene carbonate or propylene carbonate; the mol ratio of the methanol to the ethylene carbonate or the propylene carbonate is 3-10: 1; the dosage of the catalyst is 0.5 to 1 percent of the mass of the ethylene carbonate or the propylene carbonate; the reaction temperature is 60-80 ℃, and the reaction is carried out for 3-10 h under the condition of normal pressure condensation reflux.
The mechanism of the invention is as follows:
the solid base catalyst for the ester exchange reaction provided by the invention is a double-component monatomic solid base catalyst with high dispersion of alkaline sites and loss resistance. Firstly, dispersing the synergistic component metal into a carrier before introducing an alkaline metal site to obtain a synergistic component modified carrier, wherein the carrier material has good specific surface area and rich pore structure, and the synergistic component metal is fully dispersed on the surface of the carrier, so that the surface structure of the carrier is changed, and the dispersibility of the atoms of the later introduced active component is improved; and the introduction of the synergistic component increases the defects and vacant sites of the carrier, is more favorable for the stable anchoring of later introduced active component atoms, and enhances the stability of the alkaline sites. The later introduced active component metal is highly dispersed and firmly anchored in the carrier in the form of a single atom under the influence of the metal atom of the synergistic component. The obtained catalyst shows good catalytic activity and stability in the reaction of synthesizing dimethyl carbonate by ester exchange.
The invention has the beneficial effects that:
the double-component monoatomic solid base catalyst for the transesterification provided by the invention is simple in preparation method and convenient in experimental operation. In addition, the catalyst can be repeatedly used, the use cost of the catalyst is reduced, pollution and energy consumption in the catalyst recovery and regeneration processes are reduced, and the method has important economic value and environmental significance.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and it will be appreciated by those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention and that the present invention is not limited by the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Weighing 0.001mol of gallium nitrate, dissolving the gallium nitrate in deionized water, adding 0.1mol of graphene in a stirring state, stirring at room temperature for 6 hours, evaporating to dryness in a water bath at 80 ℃, drying in a drying oven at 100 ℃ for 12 hours, and then putting in a tubular furnace, introducing argon, heating to 300 ℃, and pre-activating at a constant temperature for 3 hours to obtain the carrier A modified by the synergistic component.
(2) Weighing 0.001mol of potassium nitrate, dissolving the potassium nitrate in deionized water, continuously adding 0.1mol of the carrier A modified by the synergistic component under the stirring state, stirring the mixture for 6 hours at room temperature, evaporating the mixture to dryness in a 80 ℃ water bath, drying the dried mixture in a 100 ℃ drying oven for 12 hours, placing the obtained sample in a tubular furnace, introducing argon, heating the obtained sample to 800 ℃, keeping the temperature constant for 3 hours, and thus obtaining the monatomic solid base catalyst (sample 1-1) with the potassium and gallium bimetal dispersed in graphene. For convenience of comparison, the above single component metal precursors were added separately and comparative samples were prepared using the same preparation method: samples 1-2 were samples to which the synergistic component alone was added, and samples 1-3 were samples to which the active component alone was added.
(3) The resulting catalyst was tested for catalytic transesterification:
0.5mol of methanol, 0.1mol of ethylene carbonate and 0.0528g of catalyst were put into a flask, and stirred for reaction at 70 ℃ for 4 hours under normal pressure, and the supernatant was obtained by centrifugal separation and analyzed by gas chromatography, and the yield of dimethyl carbonate of sample 1-1 was 47.9%, whereas the yields of dimethyl carbonate of sample 1-2 and sample 1-3 were 0.6% and 31.2%, respectively, indicating that the potassium gallium double component monatomic solid base has high catalytic activity. The regeneration catalysis was cycled 4 times and the DMC yield for samples 1-1 was 47.6%, which was a decrease to 13.2% for samples 1-3. This shows that the potassium-gallium double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 2
(1) Weighing 0.001mol of gallium nitrate, dissolving the gallium nitrate in deionized water, adding 0.1mol of activated carbon in a stirring state, stirring at room temperature for 8 hours, evaporating to dryness in a water bath at 85 ℃, drying in a drying oven at 90 ℃ for 12 hours, and then putting in a tubular furnace, introducing argon, heating to 400 ℃, and pre-activating at a constant temperature for 2 hours to obtain the carrier B modified by the synergistic component.
(2) Weighing 0.001mol of sodium nitrate, dissolving in deionized water, continuously adding 0.1mol of carrier B modified by the synergistic component under the stirring state, stirring for 6 hours at room temperature, evaporating to dryness in a water bath at 80 ℃, drying in a drying oven at 90 ℃ for 12 hours, placing the obtained sample in a tubular furnace, introducing argon, heating to 800 ℃, keeping the temperature for 5 hours, and thus obtaining the monatomic solid alkali catalyst (sample 2-1) with sodium and gallium double metals dispersed in active carbon. For convenience of comparison, the above single component metal precursors were added separately to make comparative samples using the same preparation method: the sample 2-2 is a sample to which only the synergistic component is added, and the sample 2-3 is a sample to which only the active component is added.
(3) The resulting catalyst was tested for catalytic transesterification:
0.5mol of methanol, 0.1mol of ethylene carbonate and 0.0528g of catalyst were put into a flask, and stirred at 80 ℃ for reaction for 6 hours under normal pressure, and the supernatant was obtained by centrifugal separation and analyzed by gas chromatography, and the yield of dimethyl carbonate of sample 2-1 was 41.6%, and the yields of dimethyl carbonate of samples 2-2 and 2-3 were 0.7% and 27.5%, respectively, indicating that the sodium gallium double component monatomic solid base had high catalytic activity. The DMC yield of sample 2-1 was 41.2% and that of sample 2-3 was reduced to 10.8% with 4 regenerations. This shows that the sodium gallium double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 3
(1) Weighing 0.007mol of germanium nitrate, dissolving the germanium nitrate in deionized water, adding 0.1mol of activated carbon in a stirring state, stirring the mixture at room temperature for 6 hours, evaporating the mixture to dryness in a water bath at 80 ℃, drying the dried mixture in a drying oven at 100 ℃ for 24 hours, and then putting the dried mixture in a tubular furnace, introducing argon, heating the mixture to 500 ℃, and pre-activating the mixture for 3 hours at constant temperature, thereby obtaining the carrier C modified by the synergistic component.
(2) Weighing 0.007mol of potassium carbonate, dissolving the potassium carbonate in deionized water, continuously adding 0.1mol of carrier C modified by the synergistic component under the stirring state, stirring the mixture at room temperature for 6 hours, evaporating the mixture to dryness in a water bath at 80 ℃, drying the dried mixture in a drying oven at 100 ℃ for 24 hours, placing the obtained sample in a tubular furnace, introducing nitrogen, heating the mixture to 1000 ℃, and keeping the temperature for 3 hours, thereby obtaining the monatomic solid base catalyst (sample 3-1) with the bimetal of potassium and germanium dispersed in the activated carbon. For convenience of comparison, the above single component metal precursors were added separately to make comparative samples using the same preparation method: the sample 3-2 was a sample to which only the synergistic component was added, and the sample 3-3 was a sample to which only the active component was added.
(3) The resulting catalyst was tested for catalytic transesterification:
0.3mol of methanol, 0.1mol of propylene carbonate and 0.0714g of catalyst were put into a flask, and stirred for reaction at 75 ℃ for 4 hours under normal pressure, and after centrifugation to obtain a supernatant and analysis by gas chromatography, the yield of dimethyl carbonate of sample 3-1 was 45.5%, and the yields of dimethyl carbonate of samples 3-2 and 3-3 were 0.5% and 27.3%, respectively, indicating that the potassium germanium double component monatomic solid base has high catalytic activity. The DMC yield of sample 3-1 was 45.6% and the DMC yield of sample 3-3 decreased to 9.7% after 4 regenerations. This shows that the potassium germanium bi-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 4
(1) Weighing 0.007mol of germanium nitrate, dissolving the germanium nitrate in deionized water, adding 0.1mol of graphene in a stirring state, stirring the mixture for 6 hours at room temperature, evaporating the mixture to dryness in a 80 ℃ water bath, drying the dried mixture for 12 hours in a 100 ℃ drying oven, and then putting the dried mixture in a tubular furnace, introducing argon, heating the mixture to 500 ℃, and performing constant-temperature preactivation for 3 hours to obtain the carrier D modified by the synergistic component.
(2) Weighing 0.007mol of sodium nitrate, dissolving the sodium nitrate in deionized water, continuously adding 0.1mol of the carrier D modified by the synergistic component under the stirring state, stirring the mixture at room temperature for 8 hours, evaporating the mixture to dryness in a 90 ℃ water bath, drying the dried mixture in a 100 ℃ drying oven for 12 hours, placing the obtained sample in a tubular furnace, introducing argon, heating the obtained sample to 900 ℃, keeping the temperature for 3 hours, and thus obtaining the monatomic solid base catalyst (sample 4-1) with sodium and germanium bimetal dispersed in graphene. For convenience of comparison, the above single component metal precursors were added separately and comparative samples were prepared using the same preparation method: the sample 4-2 was a sample to which only the synergistic component was added, and the sample 4-3 was a sample to which only the active component was added.
(3) The resulting catalyst was tested for catalytic transesterification:
0.3mol of methanol, 0.1mol of propylene carbonate and 0.102g0.0714g of catalyst are added into a flask, and the mixture is stirred for reaction for 4 hours at 60 ℃ under normal pressure, and after centrifugation to obtain a supernatant, the supernatant is analyzed by gas chromatography, and the yield of the dimethyl carbonate of the sample 4-1 is 34.8%, while the yields of the dimethyl carbonate of the samples 4-2 and 4-3 are respectively 0.6% and 20.5%, which shows that the sodium germanium bi-component monatomic solid base has higher catalytic activity. The DMC yield of sample 4-1 was 35.2% and the DMC yield of sample 4-3 was reduced to 9.6% with 4 regenerations. This shows that the sodium germanium double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 5
(1) 0.008mol of indium nitrate is weighed and dissolved in ethanol, and 0.1mol of CeO is added under the stirring state 2 Stirring at room temperature for 7h, evaporating to dryness in a 80 ℃ water bath, drying in a 90 ℃ oven for 24h, putting in a tubular furnace, introducing argon, heating to 600 ℃, and pre-activating at constant temperature for 3h to obtain the carrier E modified by the synergistic component.
(2) Weighing 0.008mol of calcium nitrate, dissolving the calcium nitrate in ethanol, continuously adding 0.1mol of carrier E modified by synergistic components under the stirring state, stirring for 6 hours at room temperature, evaporating to dryness in a 80 ℃ water bath, drying in a 100 ℃ drying oven for 12 hours, placing the obtained sample in a tubular furnace, introducing argon, heating to 1000 ℃, keeping the temperature for 3 hours, and thus obtaining the calcium and indium bimetal which are dispersed in CeO 2 The monatomic solid base catalyst of (sample 5-1). For convenience of comparison, the above single component metal precursors were added separately to make comparative samples using the same preparation method: the sample 5-2 is a sample to which only the synergistic component was added, and the sample 5-3 is a sample to which only the active component was added.
(3) The resulting catalyst was tested for catalytic transesterification:
0.8mol of methanol, 0.1mol of ethylene carbonate and 0.0616g of catalyst were put into a flask, and stirred for reaction at 70 ℃ for 10 hours under normal pressure, and after centrifugation to obtain a supernatant and analysis by gas chromatography, the yield of dimethyl carbonate of sample 5-1 was 36.2%, and the yields of dimethyl carbonate of samples 5-2 and 5-3 were 0.4% and 22.2%, respectively, indicating that the calcium-indium double component monatomic solid base has high catalytic activity. The DMC yield of sample 5-1 was 36.1% and that of sample 5-3 was reduced to 7.9% with 4 regenerations. This shows that the calcium indium double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 6
(1) Weighing 0.008mol of tin nitrate, dissolving the tin nitrate in ethanol, adding 0.1mol of graphene in a stirring state, stirring at room temperature for 6 hours, evaporating to dryness in a 80 ℃ water bath, drying in a 100 ℃ drying oven for 12 hours, putting in a tubular furnace, introducing argon, heating to 400 ℃, keeping the temperature, and pre-activating for 3 hours to obtain the carrier F modified by the synergistic component.
(2) Weighing 0.008mol of potassium acetate, dissolving the potassium acetate in ethanol, continuously adding 0.1mol of carrier F modified by the synergistic component under the stirring state, stirring at room temperature for 6h, evaporating to dryness in a water bath at 80 ℃, drying in a drying oven at 100 ℃ for 12h, placing the obtained sample in a tubular furnace, introducing helium, heating to 850 ℃, and keeping the temperature for 3h to obtain the monatomic solid base catalyst (sample 6-1) with the potassium and tin bimetal dispersed in graphene. For convenience of comparison, the above single component metal precursors were added separately and comparative samples were prepared using the same preparation method: the sample 6-2 was a sample to which only the synergistic component was added, and the sample 6-3 was a sample to which only the active component was added.
(3) The resulting catalyst was tested for catalytic transesterification:
0.8mol of methanol, 0.1mol of ethylene carbonate and 0.0704g of catalyst are added into a flask, and the mixture is stirred and reacted for 4 hours at 65 ℃ under normal pressure, and after centrifugal separation, supernatant liquid is obtained and analyzed by gas chromatography, the yield of dimethyl carbonate of the sample 6-1 is 46.8 percent, and the yields of dimethyl carbonate of the sample 6-2 and the sample 6-3 are respectively 0.5 percent and 31.3 percent, which shows that the potassium-tin bi-component monatomic solid base has higher catalytic activity. The DMC yield of sample 6-1 was 46.2% and the DMC yield of sample 6-3 was reduced to 11.7% with 4 regenerations. This shows that the potassium tin double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 7
(1) Weighing 0.015mol of tin nitrate, dissolving the tin nitrate in ethanol, adding 0.1mol of activated carbon in a stirring state, stirring the mixture at room temperature for 6 hours, evaporating the mixture to dryness in a water bath at 80 ℃, drying the dried mixture in a drying oven at 100 ℃ for 12 hours, and then putting the dried mixture in a tubular furnace, introducing argon, heating the mixture to 500 ℃, and pre-activating the mixture at constant temperature for 3 hours to obtain the carrier G modified by the synergistic component.
(2) Weighing 0.015mol of strontium nitrate, dissolving the strontium nitrate in ethanol, continuously adding 0.1mol of carrier G modified by the synergistic component under the stirring state, stirring for 6 hours at room temperature, evaporating to dryness in a water bath at 80 ℃, drying in a drying oven at 100 ℃ for 12 hours, placing the obtained sample in a tubular furnace, introducing argon, heating to 950 ℃, and keeping the temperature for 3 hours, thereby obtaining the monatomic solid base catalyst (sample 7-1) with the bimetallic strontium and tin dispersed in the graphene. For convenience of comparison, the above single component metal precursors were added separately and comparative samples were prepared using the same preparation method: sample 7-2 is a sample to which only the synergistic component was added, and sample 7-3 is a sample to which only the active component was added.
(3) The resulting catalyst was tested for catalytic transesterification:
1mol of methanol, 0.1mol of propylene carbonate and 0.0918g of catalyst were put into a flask, and the mixture was stirred at 70 ℃ for reaction for 8 hours under normal pressure, and the supernatant was obtained by centrifugal separation and analyzed by gas chromatography, and the yield of dimethyl carbonate was 37.8% for sample 7-1 and 0.4% and 25.4% for samples 7-2 and 7-3, respectively, indicating that the strontium-tin bi-component monatomic solid base had high catalytic activity. The DMC yield of sample 7-1 was 38.3% and that of sample 7-3 was reduced to 8.9% with 4 regenerations. This shows that the strontium-tin double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
Example 8
(1) 0.015mol of germanium nitrate is weighed and dissolved in ethanol, and 0.1mol of ZrO is added under the stirring state 2 Stirring at room temperature for 6h, evaporating to dryness in 80 deg.C water bath, oven drying at 100 deg.C for 12h, placing in a tubular furnace, introducing argon, heating to 500 deg.C, and pre-activating at constant temperature for 3h to obtain the final productSynergistic component modified carrier H.
(2) Weighing 0.015mol of cesium nitrate to dissolve in ethanol, continuously adding 0.1mol of carrier H modified by a synergistic component under a stirring state, stirring at room temperature for 8 hours, evaporating to dryness in a 85 ℃ water bath, drying in a 100 ℃ oven for 24 hours, placing the obtained sample in a tubular furnace, introducing argon, heating to 900 ℃, keeping the temperature for 3 hours, and thus obtaining a monatomic solid base catalyst (sample 8-1) with cesium and germanium bimetal dispersed in graphene. For convenience of comparison, the above single component metal precursors were added separately and comparative samples were prepared using the same preparation method: the sample 8-2 was a sample to which only the synergistic component was added, and the sample 8-3 was a sample to which only the active component was added.
(3) The resulting catalyst was tested for catalytic transesterification:
1mol of methanol, 0.1mol of propylene carbonate and 0.0918g of catalyst were put into a flask, and the reaction was carried out under normal pressure and stirring at 80 ℃ for 4 hours, and the supernatant was obtained by centrifugal separation and analyzed by gas chromatography, and the yield of dimethyl carbonate of sample 8-1 was 39.5%, whereas the yields of dimethyl carbonate of samples 8-2 and 8-3 were 0.6% and 27.1%, respectively, indicating that the cesium germanium bi-component monatomic solid base had high catalytic activity. The DMC yield of sample 8-1 was 39.7% and that of sample 8-3 was reduced to 9.6% with 4 regenerations. The result shows that the cesium-germanium double-component monatomic solid alkali has higher regeneration performance and the alkaline site is not easy to lose.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A two-component monatomic solid base catalyst, characterized in that: consists of active components and a carrier modified by synergistic components; wherein the active component is alkali metal or alkaline earth metal, and the synergistic component is metal of main group III or IV; the carrier is one or more of porous carbon materials or oxides.
2. The bi-component monatomic solid base catalyst of claim 1 wherein: the active component is lithium, sodium, magnesium, potassium, calcium, rubidium, strontium or cesium; the synergistic component is gallium, germanium, indium or tin;
the porous carbon material is one or more of active carbon, mesoporous carbon or graphene; the oxide is Al 2 O 3 、SiO 2 、TiO 2 、ZrO 2 Or CeO 2 One or more of (a).
3. The two-component monatomic solid base catalyst of claim 1 wherein: the molar ratio of the active component to the carrier is 0.01-0.15, and the molar ratio of the synergistic component to the carrier is 0.01-0.15.
4. A method for synthesizing the bi-component monatomic solid base catalyst of claim 1, comprising the steps of:
(1) Weighing a precursor of the synergistic component, dissolving the precursor in a solvent, adding the carrier in proportion, stirring in a water bath, drying by distillation, then putting the dried sample into an oven for drying, and putting the dried sample into a tubular furnace for low-temperature pre-activation for 2-3 hours at 300-600 ℃ in an inert atmosphere to obtain a carrier modified by the synergistic component;
(2) Weighing an active component precursor, dissolving the active component precursor in a solvent, adding a carrier modified by the synergistic component according to a proportion, stirring in a water bath, evaporating to dryness, and then putting into a drying oven for drying to obtain a sample to be activated;
(3) And (3) placing the sample to be activated in a tubular furnace, roasting and activating at high temperature under the protection of protective atmosphere, so that the precursor of the active component is converted into free metal atoms and stably anchored in the carrier modified by the synergistic component, and thus the bi-component monatomic solid base catalyst is obtained.
5. The method of claim 4, wherein: the active component precursor is nitrate, carbonate or acetate corresponding to alkali metal or alkaline earth metal;
the precursor of the synergistic component is nitrate corresponding to metal elements in main groups III or IV.
6. The method of claim 4, wherein: the solvent is ethanol, deionized water or methanol; the protective atmosphere is one of helium, argon or nitrogen.
7. The method of claim 4, wherein: the stirring time in the steps (1) and (2) is 6-8 h, the water bath temperature is 80-90 ℃, the oven temperature is 90-100 ℃, and the drying time is 12-24 h; the temperature of the high-temperature roasting activation in the step (3) is 800-1000 ℃, and the activation time is 3-5 h.
8. Use of the two-component monoatomic solid base catalyst according to claim 1 in a reaction for synthesizing dimethyl carbonate through transesterification.
9. The use of claim 8, wherein methanol is catalyzed to transesterify with an ester to produce dimethyl carbonate; wherein the ester is ethylene carbonate or propylene carbonate; the mol ratio of the methanol to the ethylene carbonate or the propylene carbonate is 3-10: 1; the dosage of the catalyst is 0.5 to 1 percent of the mass of the ethylene carbonate or the propylene carbonate; the reaction temperature is 60-80 ℃, and the reaction is carried out for 3-10 h under the condition of normal pressure condensation reflux.
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