CN116713037A - Solid catalyst for synthesizing tetramethyl ammonium bicarbonate and preparation method and application thereof - Google Patents
Solid catalyst for synthesizing tetramethyl ammonium bicarbonate and preparation method and application thereof Download PDFInfo
- Publication number
- CN116713037A CN116713037A CN202310436224.6A CN202310436224A CN116713037A CN 116713037 A CN116713037 A CN 116713037A CN 202310436224 A CN202310436224 A CN 202310436224A CN 116713037 A CN116713037 A CN 116713037A
- Authority
- CN
- China
- Prior art keywords
- tetramethyl ammonium
- solid catalyst
- ammonium bicarbonate
- ceo
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 39
- VFHDWENBWYCAIB-UHFFFAOYSA-M hydrogen carbonate;tetramethylazanium Chemical compound OC([O-])=O.C[N+](C)(C)C VFHDWENBWYCAIB-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000012695 Ce precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 9
- ZSEHKBVRLFIMPB-UHFFFAOYSA-N cobalt;cyclopenta-1,3-diene Chemical compound [Co].C=1C=C[CH-]C=1 ZSEHKBVRLFIMPB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 150000000703 Cerium Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000352 supercritical drying Methods 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 20
- -1 cyclopentadienyl cobalt dicarbonate Chemical compound 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000002585 base Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- YKLKUNBKAPXTEZ-UHFFFAOYSA-M methyl carbonate;tetramethylazanium Chemical compound COC([O-])=O.C[N+](C)(C)C YKLKUNBKAPXTEZ-UHFFFAOYSA-M 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling 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
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/20—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of quaternary ammonium compounds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention discloses a solid catalyst for synthesizing tetramethyl ammonium bicarbonate, a preparation method and application thereof, wherein the method comprises the following steps: a. mixing cerium salt solution and organic alkali through a hypergravity reactor; mixing and separating solids to obtain a Ce precursor; b. optionally soaking the Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 2-25%, modifying the surface, and then freeze-drying and/or supercritical drying the filtrate to obtain CeO nano particles; c. mixing CeO nano particles with cyclopentadienyl cobalt metal catalyst in solvent, stirring at 40-80 deg.C for 5-12h, separating and drying to obtain CpCo-CeO catalyst with chemical bond structured on surface. The solid catalyst is applied to one-step synthesis of tetramethyl ammonium bicarbonate, has the advantages of high product selectivity and high conversion rate, and can improve the product yield.
Description
Technical Field
The invention relates to a catalyst and an organic synthesis method, in particular to a solid catalyst for synthesizing tetramethyl ammonium bicarbonate, and a preparation method and application thereof.
Background
Tetramethyl ammonium bicarbonate (TMAC) is the starting material for the electrolytic preparation of tetramethyl ammonium hydroxide (TMAH). TMAH is an important organic strong base, mainly used in the electronics industry for preparing cleaning and etching agents, and thus generally requires electronic grade purity. Research on the synthetic process of TMAC is of great importance in reducing the production cost of TMAH industry chain and improving the product grade.
The traditional preparation process of TMAC is: dimethyl carbonate (DMC) and trimethylamine are subjected to methylation reaction to produce tetramethyl ammonium monomethyl carbonate, and then hydrolysis is carried out to obtain TMAC. Trimethylamine is gas at normal temperature, is usually stored and used in the form of aqueous solution or alcohol solution, and the prior literature reports that the methanol solution of trimethylamine is used as a raw material to prepare tetramethyl ammonium bicarbonate through two-step reactions of methylation and hydrolysis. There are also many studies to combine the above two steps into one step, namely, directly using water as a solvent to simultaneously perform methylation and hydrolysis, but DMC can be obviously hydrolyzed under an alkaline reaction system, resulting in lower product yield.
Patent CN113735713a proposes to synthesize TMAC in one step in aqueous solution using an organic amine modified molecular sieve catalyst, but its yield is up to 96%, and the use of molecular sieve can greatly introduce metal ions, which is unfavorable for the application of the product in the field of electronic chemicals.
In summary, TMAC is synthesized by a one-step process, and the prior art still cannot achieve satisfactory results in terms of product yield, and the invention provides an improved TMAC catalyst and a preparation method thereof, aiming at the defects of the prior art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a solid catalyst for synthesizing tetramethyl ammonium bicarbonate, and a preparation method and application thereof.
Based on a first aspect of the present invention, the present invention proposes a method for preparing a solid catalyst for synthesizing tetramethyl ammonium bicarbonate.
Based on the second aspect of the invention, the invention also provides a solid catalyst for synthesizing tetramethyl ammonium bicarbonate, which is prepared by the method.
Based on the third aspect of the invention, the invention also provides an application of the catalyst in synthesizing tetramethyl ammonium bicarbonate.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
firstly, a preparation method of a solid catalyst for synthesizing tetramethyl ammonium bicarbonate comprises the following steps:
a. mixing cerium salt solution and organic alkali through a hypergravity reactor; mixing and separating solids to obtain a Ce precursor;
b. optionally soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 2-25%, preferably 8-12%, modifying the surface, and then freeze-drying and/or supercritical drying the filtrate to obtain CeO nano particles; when the organic base in the step a does not contain tetramethyl ammonium hydroxide, the surface modification is indispensable; through the surface modification of the tetramethyl ammonium hydroxide, impurities generated by the application of the catalyst in a strong base system can be reduced, and quaternary ammonium base sites are generated to improve the catalytic effect;
c. mixing CeO nano particles with cyclopentadienyl cobalt metal catalyst in solvent, stirring at 40-80 deg.C for 5-12h, separating and drying to obtain CpCo-CeO catalyst with chemical bond structured on surface. The construction of CpCo-chemical bond can regulate and control the surface electron density of Ce, increase the reaction activation energy and improve the selectivity of the product.
In some examples, in step a, the molar ratio of cerium salt to organic base is 1 (1-10);
preferably, the organic base is ammonia and/or tetramethylammonium hydroxide.
Preferably, the cerium salt is one or more of cerium nitrate, cerium sulfate, cerium trichloride, and hydrates thereof.
In some examples, in step a, the hypergravity reactor mixing conditions are: the supergravity level is 150-2000G, preferably 300-800G (1G represents 1 earth surface gravity acceleration, corresponding to 9.8N/kg,100G is 100 times gravity effect), and the residence time is 2-30min, preferably 5-10min.
In some examples, in step b, the surface modification is carried out at a temperature of 40-80 ℃, preferably 60-70 ℃, for a time of 4-8 hours, preferably 5-7 hours.
In some examples, in step b, the lyophilization conditions are: treating at-70deg.C to-30deg.C for 24-72 hr, preferably at-50deg.C to-40deg.C for 36-48 hr; and/or the number of the groups of groups,
the supercritical drying conditions are as follows: by supercritical CO 2 The drying medium is dried under 10-15MPa at 35-45deg.C for 10-20min.
In some examples, the CeO nanoparticles produced in step b have a particle size of 0.1-2nm.
In some examples, in step c, the CeO nanoparticle to cyclopentadienyl cobalt metal catalyst usage ratio is from 0.1 to 10, based on the molar ratio of Ce to Co;
preferably, the cyclopentadienyl cobalt metal catalyst is selected from at least one of cyclopentadienyl cobalt dicarbonate, cyclopentadienyl (dimethyl fumarate) (triethylphosphonite) cobalt (I);
preferably, the solvent in the step c is any one or more of water, acetone, methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane and chloroform.
Next, a solid catalyst for synthesizing tetramethyl ammonium bicarbonate, which is prepared by the method described above.
Again, the use of a solid catalyst for the synthesis of tetramethyl ammonium bicarbonate prepared by the method described above, characterized in that it is used to catalyze the reaction of an aqueous solution of dimethyl carbonate and trimethylamine to prepare tetramethyl ammonium bicarbonate.
In some examples, the molar ratio of dimethyl carbonate to trimethylamine is 1 (0.5-2);
preferably, the solid catalyst is used in an amount of 1-10% of the mass of dimethyl carbonate;
preferably, the reaction temperature is 100-150 ℃, the reaction pressure is 0-1MPa, and the reaction time is 3-6h.
The solid catalyst provided by the invention is applied to synthesizing tetramethyl ammonium bicarbonate by a one-step method, has the advantages of high product selectivity and high conversion rate, the yield is up to more than 97%, and compared with the prior art, the solid catalyst has obvious advantages, and the possible reaction mechanism is presumed to comprise decomposition and resynthesis reaction processes of DMC, so that the material circulation is realized, and the high product yield is maintained.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
In the present invention, the materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. Cyclopentadienyl cobalt dicarbonate (95%) was purchased from cobalt aladine under the trade designation D166511; cyclopentadienyl (dimethyl fumarate) (triethylphosphonite) cobalt (I) was purchased from Allatin under the designation C405499.
The methods in the examples, unless otherwise specified, are all conventional in the art.
[ example 1 ]
The solid catalyst a was prepared according to the following steps:
a. cerium nitrate hexahydrate solution (0.2 mol/L) and tetramethylammonium hydroxide solution (0.4 mol/L) were mixed according to 1:2, feeding the mixture into a hypergravity reactor according to the volume ratio, and mixing the mixture under the conditions of a hypergravity level of 150G and a residence time of 2 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 2%, modifying and modifying for 4 hours at 40 ℃, filtering, and freeze-drying for 24 hours at-70 ℃ to obtain CeO nano particles with the particle diameter of 2 nm;
c. CeO nano particles with the Ce/Co molar ratio of 0.1 and cyclopentadienyl cobalt dicarbonate are mixed in water, stirred at 40 ℃ for 5 hours, separated and dried, and the CpCo-CeO catalyst with the surface structured with chemical bonds is obtained.
[ example 2 ]
The solid catalyst B was prepared according to the following steps:
a. cerium nitrate hexahydrate solution (1 mol/L) and aqueous ammonia (2 mol/L) were mixed according to a ratio of 1: feeding the mixture into a hypergravity reactor according to the volume ratio of 0.5, and mixing the mixture under the conditions of a hypergravity level of 2000G and a residence time of 30 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 25%, modifying and modifying for 8 hours at 80 ℃, filtering, and freeze-drying for 72 hours at-30 ℃ to obtain CeO nano particles with the particle diameter of 2 nm;
c. CeO nano particles with the Ce/Co molar ratio of 10 and cyclopentadienyl (dimethyl fumarate) (triethyl phosphonite) cobalt (I) are mixed in methanol, stirred at 80 ℃ for 12 hours, separated and dried, and the CpCo-CeO catalyst with chemical bonds constructed on the surface is obtained.
[ example 3 ]
The solid catalyst C was prepared according to the following steps:
a. cerium nitrate hexahydrate (0.5 mol/L) and tetramethylammonium hydroxide solution (5 mol/L) were mixed according to 1:1, feeding the mixture into a hypergravity reactor in a volume ratio, and mixing the mixture under the conditions of a hypergravity level of 1000G and a residence time of 20 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 12%, modifying and modifying for 6 hours at 60 ℃, filtering, and freeze-drying for 48 hours at-50 ℃ to obtain CeO nano particles with the particle size of 0.1 nm;
c. CeO nano particles with the Ce/Co molar ratio of 2 and cyclopentadienyl (dimethyl fumarate) (triethyl phosphonite) cobalt (I) are mixed in ethanol, stirred at 60 ℃ for 8 hours, separated and dried, and then the CpCo-CeO catalyst with chemical bonds constructed on the surface is obtained.
[ example 4 ]
The solid catalyst D was prepared according to the following steps:
a. cerium nitrate hexahydrate solution (0.8 mol/L) and aqueous ammonia (0.8 mol/L) were mixed according to 1:2, feeding the mixture into a hypergravity reactor according to the volume ratio, and mixing the mixture under the conditions of a hypergravity level of 300G and a residence time of 10 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 8%, modifying and modifying for 5 hours at 50 ℃, filtering, and freeze-drying for 36 hours at-40 ℃ to obtain CeO nano particles with the particle size of 0.5 nm;
c. CeO nano particles with the Ce/Co molar ratio of 2 and cyclopentadienyl (dimethyl fumarate) (triethyl phosphonite) cobalt (I) are mixed in acetone, stirred at 50 ℃ for 6 hours, separated and dried, and then the CpCo-CeO catalyst with chemical bonds constructed on the surface is obtained.
[ example 5 ]
The solid catalyst E was prepared according to the following steps:
a. cerium nitrate hexahydrate (0.8 mol/L) and tetramethylammonium hydroxide (1.6 mol/L) were mixed according to a ratio of 1:3, feeding the mixture into a hypergravity reactor according to the volume ratio, and mixing the mixture under the conditions of a hypergravity level of 1500G and a residence time of 25 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 20%, modifying and modifying for 7 hours at the temperature of 70 ℃, and freeze-drying for 30 hours at the temperature of minus 60 ℃ after filtering to obtain CeO nano particles with the particle size of 0.4 nm;
c. CeO nano particles with Ce/Co molar ratio of 8 and cyclopentadienyl cobalt dicarbonate are mixed in water, stirred at 70 ℃ for 6 hours, separated and dried, and the CpCo-CeO catalyst with chemical bonds constructed on the surface is obtained.
[ example 6 ]
The solid catalyst F was prepared according to the following steps:
a. cerium nitrate hexahydrate solution (0.3 mol/L) and tetramethylammonium hydroxide solution (0.3 mol/L) were mixed according to 1:3, feeding the mixture into a hypergravity reactor according to the volume ratio, and mixing the mixture under the conditions of a hypergravity level of 500G and a residence time of 5 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. soaking a Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 18%, modifying and modifying for 7 hours at 50 ℃, filtering, and freeze-drying for 60 hours at-50 ℃ to obtain CeO nano particles with the particle size of 1 nm;
c. CeO nano particles with the Ce/Co molar ratio of 5 and cyclopentadienyl cobalt dicarbonate are mixed in ethanol, stirred for 10 hours at 70 ℃, separated and dried, and the CpCo-CeO catalyst with the surface structured with chemical bonds is obtained.
[ example 7 ]
The solid catalyst G was prepared according to the following steps:
a. cerium nitrate hexahydrate solution (0.6 mol/L) and tetramethylammonium hydroxide solution (1.2 mol/L) were mixed according to 1:4, feeding the mixture into a hypergravity reactor according to the volume ratio, and mixing the mixture under the conditions of a hypergravity level of 1700G and a residence time of 15 min; centrifugally separating the solid after mixing to obtain a Ce precursor;
b. freeze-drying the Ce precursor for 70 hours at the temperature of minus 60 ℃ to obtain CeO nano particles with the particle size of 1.2 nm;
c. CeO nano particles with Ce/Co molar ratio of 3 and cyclopentadienyl cobalt dicarbonate are mixed in methanol, stirred at 70 ℃ for 7 hours, separated and dried, and the CpCo-CeO catalyst with chemical bonds constructed on the surface is obtained.
Comparative example 1
Ce precursor was prepared as in step a of example 2 and directly denoted as solid catalyst H.
Comparative example 2
A solid catalyst was prepared in substantially the same manner as in example 2, except that step c was not carried out, and the CeO nanoparticles obtained in step b were directly designated as solid catalyst I.
[ comparative example 3 ]
A solid catalyst J was prepared in substantially the same manner as in example 2, except that the modification in step b was not carried out, and the Ce precursor obtained in step a was directly mixed with cyclopentadienyl (dimethyl fumarate) (triethylphosphonite) cobalt (I) to carry out the reaction in step c.
[ comparative example 4 ]
A solid catalyst K was prepared in substantially the same manner as in example 2, except that the lyophilization conditions in step b were modified to the following drying conditions: drying at 60℃under 50kPa for 4h.
Comparative example 5
Cyclopentadienyl (dimethyl fumarate) (triethylphosphonite) cobalt (I) was directly designated as solid catalyst L.
[ application examples 1 to 7, comparative application examples 1 to 6 ]
Different solid catalysts are respectively adopted to synthesize TMAC through a one-step reaction:
and adding dimethyl carbonate and a catalyst into a reaction kettle, wherein the dosage of the catalyst is 2wt% of that of the dimethyl carbonate, heating to 120 ℃, adding an aqueous solution of trimethylamine (the mass ratio of water to trimethylamine is 7:3), the molar ratio of the trimethylamine to the dimethyl carbonate is 1:1, and sampling and testing after 5 hours of timing reaction.
The reaction results are shown in Table 1:
table 1, application examples 1 to 7, comparative application examples 1 to 6, results of the performance test
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. The preparation method of the solid catalyst for synthesizing the tetramethyl ammonium bicarbonate is characterized by comprising the following steps of:
a. mixing cerium salt solution and organic alkali through a hypergravity reactor; mixing and separating solids to obtain a Ce precursor;
b. optionally soaking the Ce precursor in a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 2-25%, preferably 8-12%, modifying the surface, and then freeze-drying and/or supercritical drying the filtrate to obtain CeO nano particles; when the organic base in the step a does not contain tetramethyl ammonium hydroxide, the surface modification is indispensable;
c. mixing CeO nano particles with cyclopentadienyl cobalt metal catalyst in solvent, stirring at 40-80 deg.C for 5-12h, separating and drying to obtain CpCo-CeO catalyst with chemical bond structured on surface.
2. The method for preparing a solid catalyst for synthesizing tetramethyl ammonium bicarbonate according to claim 1, wherein in the step a, the molar ratio of cerium salt to organic base is 1 (1-10);
preferably, the organic base is ammonia and/or tetramethylammonium hydroxide.
3. The method for preparing a solid catalyst for synthesizing tetramethyl ammonium bicarbonate according to claim 2, wherein in the step a, the mixing condition of the hypergravity reactor is as follows: the supergravity level is 150-2000G, preferably 300-800G, and the residence time is 2-30min, preferably 5-10min.
4. A process for the preparation of a solid catalyst for the synthesis of tetramethyl ammonium bicarbonate according to any one of claims 1 to 3, wherein in step b the surface modification is carried out at a temperature of 40-80 ℃, preferably 60-70 ℃, for a time of 4-8h, preferably 5-7h.
5. The method for preparing a solid catalyst for synthesizing tetramethyl ammonium bicarbonate according to claim 4, wherein in the step b, the freeze-drying condition is as follows: treating at-70deg.C to-30deg.C for 24-72 hr, preferably at-50deg.C to-40deg.C for 36-48 hr; and/or the number of the groups of groups,
the supercritical drying conditions are as follows: by supercritical CO 2 The drying medium is dried under 10-15MPa at 35-45deg.C for 10-20min.
6. The method for preparing solid catalyst for synthesizing tetramethyl ammonium bicarbonate according to claim 5, wherein the particle size of the CeO nanoparticles prepared in the step b is 0.1-2nm.
7. A process for the preparation of a solid catalyst for the synthesis of tetramethyl ammonium bicarbonate according to any one of claims 1 to 3, wherein in step c the ratio of CeO nanoparticles to cyclopentadienyl cobalt metal catalyst is comprised between 0.1 and 10, calculated as molar ratio Ce to Co;
preferably, the cyclopentadienyl cobalt metal catalyst is selected from at least one of cyclopentadienyl cobalt dicarbonate, cyclopentadienyl (dimethyl fumarate) (triethylphosphonite) cobalt (I);
preferably, the solvent in the step c is any one or more of water, acetone, methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane and chloroform.
8. A solid catalyst for synthesizing tetramethyl ammonium bicarbonate produced by the method of any one of claims 1-7.
9. Use of a solid catalyst for synthesizing tetramethyl ammonium bicarbonate prepared by the method of any one of claims 1 to 7, wherein the solid catalyst is used for catalyzing the reaction of an aqueous solution of dimethyl carbonate and trimethylamine to prepare tetramethyl ammonium bicarbonate.
10. The use according to claim 9, wherein the molar ratio of dimethyl carbonate to trimethylamine is 1 (0.5-2);
preferably, the solid catalyst is used in an amount of 1-10% of the mass of dimethyl carbonate;
preferably, the reaction temperature is 100-150 ℃, the reaction pressure is 0-1MPa, and the reaction time is 3-6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310436224.6A CN116713037A (en) | 2023-04-23 | 2023-04-23 | Solid catalyst for synthesizing tetramethyl ammonium bicarbonate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310436224.6A CN116713037A (en) | 2023-04-23 | 2023-04-23 | Solid catalyst for synthesizing tetramethyl ammonium bicarbonate and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116713037A true CN116713037A (en) | 2023-09-08 |
Family
ID=87872219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310436224.6A Pending CN116713037A (en) | 2023-04-23 | 2023-04-23 | Solid catalyst for synthesizing tetramethyl ammonium bicarbonate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116713037A (en) |
-
2023
- 2023-04-23 CN CN202310436224.6A patent/CN116713037A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5767039A (en) | Process for manufacturing methanol and process for manufacturing catalyst for methanol synthesis | |
| CN105197956B (en) | The preparation method of the HTSs of TS 1 | |
| CN108380216B (en) | Preparation method and application of cobalt-based catalyst for catalyzing carbon dioxide to prepare ethanol | |
| CN111573691B (en) | Flower-shaped mordenite and preparation method and application thereof | |
| CN112007655A (en) | Catalyst for inhibiting generation of C1 byproduct in Fischer-Tropsch synthesis process and preparation method thereof | |
| CN103922931B (en) | A kind of method of a step catalytically synthesizing glycol ether acetate | |
| CN107176898A (en) | A kind of method that aldehyde ketone is prepared as catalyst efficient catalytic molecular oxygen oxidation alcohol using houghite | |
| CN116713037A (en) | Solid catalyst for synthesizing tetramethyl ammonium bicarbonate and preparation method and application thereof | |
| CN115414942B (en) | Catalyst for synthesizing N, N-bis (3-aminopropyl) methylamine and preparation method and application thereof | |
| CN114249637B (en) | Method for preparing dimethyl ether by dehydrating methanol | |
| CN107262148B (en) | Strip-shaped crystal grain titanium-silicon molecular sieve and synthesis method and application thereof | |
| CN109721066B (en) | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method | |
| CN105111044A (en) | Method for synthesizing isopentenol from butenol | |
| CN115430418A (en) | Catalyst, preparation method thereof and method for preparing acetic acid by using catalyst | |
| CN108996516B (en) | Preparation method of large-particle-size titanium silicalite molecular sieve catalyst and method for preparing cyclohexanone oxime by using same | |
| CN108928836B (en) | Synthesis method of nano SAPO-34 molecular sieve | |
| KR100851725B1 (en) | Method for producing a palladium-containing hydrogenation catalyst | |
| CN115215307B (en) | Synthesis method of hydroxylamine solution | |
| CN114471580B (en) | Synthesis and application method of supported nickel-gallium catalyst | |
| CN114904563B (en) | ZSM-5 supported noble metal catalyst, preparation method and application | |
| CN114621108B (en) | Method for preparing glycine from glyoxylic acid | |
| CN114534734B (en) | Solid base catalyst for synthesizing 3, 5-dimethylphenol by acetone gas phase method, and preparation method and application thereof | |
| CN114573000B (en) | Granular TNU-9 molecular sieve and preparation method thereof | |
| JPH0219098B2 (en) | ||
| CN114950543A (en) | Preparation method and application of titanium silicalite molecular sieve catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |