CN117563577A - Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method - Google Patents
Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method Download PDFInfo
- Publication number
- CN117563577A CN117563577A CN202311528877.3A CN202311528877A CN117563577A CN 117563577 A CN117563577 A CN 117563577A CN 202311528877 A CN202311528877 A CN 202311528877A CN 117563577 A CN117563577 A CN 117563577A
- Authority
- CN
- China
- Prior art keywords
- carrier
- treatment
- hours
- catalyst
- silicon dioxide
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 230000001276 controlling effect Effects 0.000 claims abstract description 6
- 150000002978 peroxides Chemical class 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 238000007669 thermal treatment Methods 0.000 claims abstract 2
- 238000005303 weighing Methods 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- VVLAIYIMMFWRFW-UHFFFAOYSA-N 2-hydroxyethylazanium;acetate Chemical compound CC(O)=O.NCCO VVLAIYIMMFWRFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000002444 silanisation Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 10
- 229910052772 Samarium Inorganic materials 0.000 description 9
- 229910052792 caesium Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229940017219 methyl propionate Drugs 0.000 description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 5
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 5
- 238000005882 aldol condensation reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for regulating and controlling hydroxyl groups on the surface of a silicon dioxide carrier, which is applied to the preparation of a catalyst for synthesizing methyl methacrylate and mainly comprises the treatment of the carrier and the preparation of the catalyst. Wherein the treatment of the carrier comprises an ion thermal treatment, a pulse program roasting treatment and a peroxide treatment. The carrier treated in different modes can provide the silicon hydroxyl with proper range content for the subsequent loaded active component, reduce the possibility of cluster generation of the active component, further improve the catalytic activity, and the method is simple and easy to implement, does not need to use the traditional organic silanization reagent, and can be suitable for subsequent large-scale industrial application.
Description
Technical Field
The invention relates to a method for systematically regulating and controlling hydroxyl groups on the surface of a silicon carrier, and the treated carrier can be used for preparing a Cs-based catalyst for synthesizing methyl methacrylate by aldol condensation reaction, namely methyl propionate and formaldehyde. The method has higher hydroxyl treatment degree on the surface of the silicon dioxide. The acid-base bifunctional catalyst required by aldol condensation reaction is prepared by adopting the treated carrier, so that the catalytic activity can be effectively improved. The treatment method provided by the invention is simple and easy to operate.
Background
Methyl Methacrylate (MMA) is an important organic chemical raw material and has very wide application. The dominant methods for producing MMA in the industry are Acetone Cyanohydrin (ACH), C1, C4 two-step oxidation, ethylene, coal-based, etc. The coal-based route is that methyl acetate and formaldehyde are used as raw materials, methyl propionate is generated after hydrogenation, and then methyl methacrylate is obtained through gas-phase aldol condensation reaction of the methyl acetate and formaldehyde on a solid catalyst, so that the method is more environment-friendly than the traditional method. However, the existing catalyst, especially the supported solid catalyst, which is commonly used in aldol condensation reaction still has the problems of low activity, serious carbon deposition, short regeneration period and the like.
The activity of supported catalysts generally depends on the particle size and the degree of dispersion of the active components. The use of a suitable carrier not only increases the specific surface area of the catalyst, but also allows the active component to be micronized. Can also improve the toxicity resistance, the heat resistance and the carbon deposition resistance of the catalyst and prolong the service life.
Silica is an important support material due to its high hydrothermal stability, controlled morphology and high surface area. The surface of the catalyst has a large amount of silicon hydroxyl groups, and the type and the amount of the catalyst have different catalytic effects on different reactions. The silica support therefore needs to be modified for different reactions. CN20210355050 discloses a chemical modification method of silica, in which the silicon hydroxyl group on the surface of the silica is substituted by trideceth as a silane coupling agent, so as to improve the dispersibility, compatibility and stability of the silica in a solvent. CN202210147224 uses inorganic acid, alcohol, ammonia and coating agent as raw materials, and adopts a coating mode to modify silicon dioxide. The above-described modification with a hydrophobic silylating agent and other substances can regulate the number of surface hydroxyl groups, but is not suitable for further mass catalyst production because the agent used for modification is generally expensive and the treatment step is complicated.
Disclosure of Invention
Based on the problems, the invention aims to provide a method for systematically regulating and controlling hydroxyl groups on the surface of a silicon carrier, and a catalyst prepared by using a modified silicon dioxide carrier is used for synthesizing methyl methacrylate by a one-step method of methyl propionate and formaldehyde.
A silica carrier surface hydroxyl regulation method for synthesizing a methyl methacrylate Cs-based catalyst comprises the following steps:
a) Preparing a modified silica carrier;
b) Weighing salt of active components Sm and Cs with certain mass, placing in a blue cap bottle, and adding deionized water to prepare a salt solution;
c) Adding the carrier obtained in the step a) into the salt solution containing the active component prepared in the step b), standing and soaking for 5-24h, and drying in an oven at 50-100 ℃ for 3-6h;
d) Placing the Sm and Cs precursor catalyst obtained in the step c) in a muffle furnace, roasting for 3-12h at 500 ℃ according to a certain heating program, and naturally cooling to room temperature to obtain the catalyst.
Wherein the carrier in the method is porous silica spheres, the particle size of the particles is 2-5mm, and the pore diameter of the most integrable is 2-10nm;
the loading of the active component is calculated by taking the mass of the carrier as a reference and the mass of the oxide of the active component, wherein the preferable loading of Cs is 1-10%, and the preferable loading of Sm active component is 3-5%;
the main sources of active components Cs and Sm salt in the method are one or a combination of more of cesium nitrate, cesium carbonate, cesium acetate, cesium hydroxide, samarium nitrate, samarium chloride and samarium sulfate;
compared with the prior art for preparing the catalyst, the invention has the beneficial effects that:
before preparing the catalyst, firstly modifying the silicon dioxide carrier, systematically regulating and controlling the silicon hydroxyl content on the surface of the carrier, wherein the silicon hydroxyl content on the surface of the modified carrier reaches the optimal amount required by the preparation of the catalyst in the next step, and continuously adding Sm and Cs as acid-base active components to be loaded on the modified silicon carrier, so that the catalyst has better activity. By adopting the mode for regulation and control, a proper amount of silicon hydroxyl groups can be provided, the possibility of clusters of active components is reduced, the catalytic activity is improved, and the method is simple, has short steps and is suitable for large-scale preparation of subsequent catalysts.
The specific embodiment is as follows:
the following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by a person of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are within the scope of the invention.
Determination of the silicon hydroxyl group: the content of silicon hydroxyl is determined by titration, and the specific steps are as follows: 2g of the sample was weighed into a 200mL beaker, 25mL of absolute ethanol was added, and 75mL of 20% NaCl solution was added. Shaking uniformly, adding prepared HCl to adjust the pH to 4, slowly adding NaOH solution to adjust the pH to 9, and recording the amounts of the NaOH solutions added to different samples after a certain period of time. Finally, according to the following formula: n= (C V N) A ) The content of surface silicon hydroxyl groups was calculated by S x m and the results of the measurements performed in the different examples are shown in table 1.
Catalytic performance test: in a fixed bed microreactor, 3g were introducedThe catalyst was charged into the reactor with a methyl propionate/formaldehyde molar ratio of 1/1, methyl propionate/methanol 1/2, and a feed space velocity of 0.6h -1 The reaction temperature was 360℃and the evaluation results are shown in Table 2.
Example 1
And (3) taking a proper amount of ethanolamine acetate in a beaker, then placing the beaker in an oil bath at a set temperature for stirring, then weighing a silica carrier with the mass of 10g, adding the silica carrier into the ethanolamine acetate, stirring at a required temperature for 1h, wherein the beaker is in an open state in the whole process, and the temperature of the oil bath is kept at 100 ℃. After the treatment is finished, centrifugally collecting a solid product, drying the solid product at 120 ℃ for 6 hours, calcining the solid product at 500 ℃ for 4 hours, and tabletting to obtain a treated carrier;
example 2
And (3) taking a proper amount of ethanolamine acetate in a beaker, then placing the beaker in an oil bath at a set temperature for stirring, then weighing a silica carrier with the mass of 10g, adding the silica carrier into the ethanolamine acetate, stirring at a required temperature for 3 hours, wherein the beaker is in an open state in the whole process, and the temperature of the oil bath is kept at 120 ℃. After the treatment is finished, centrifugally collecting a solid product, drying the solid product at 120 ℃ for 6 hours, calcining the solid product at 500 ℃ for 4 hours, and tabletting to obtain a treated carrier;
example 3
10g of silica carrier is weighed and put into a crucible, and then the crucible is put into a reaction chamber for pulse roasting treatment. In the process, two-step program roasting is selected, the first step is to regulate the frequency of the pulse signal by a controller, heat the pulse signal to 500 ℃ for 3 hours at a frequency of 200 Hz and each time the duration is 100 milliseconds, and then increase the frequency of the pulse signal to keep the pulse signal at 800 ℃ for 5 hours. After the pulse roasting treatment is finished, the silicon dioxide carrier is naturally cooled in a sealing way, so that the carrier subjected to the pulse roasting treatment is obtained;
example 4
10g of silicon dioxide carrier is weighed and put into a three-necked flask, 30mL of peroxide with mass fraction of 5% and ammonia water are added, the mixture is stirred for 5 hours at the constant temperature of 100 ℃ in an oil bath after being mixed, the condensation reflux and the outlet for releasing decomposed gas are ensured in the treatment process, and the obtained carrier is dried for 3 hours at the constant temperature in a drying box at 50 ℃.
Obtaining a carrier after peroxide treatment;
example 5
Weighing 10g of silica carrier, performing the ion heat treatment of the example 1, and performing the pulse roasting treatment of the example 3 to obtain a twice-treated silica carrier;
example 6
(1) Accurately weighing 0.21g of samarium nitrate and 0.21g of cesium nitrate, and adding a certain amount of deionized water for full dissolution to obtain an aqueous solution containing samarium and cesium;
(2) The silica carrier obtained in the example (1) is added into the solution and then is kept stand for 12 hours, then is dried at 120 ℃ for 12 hours, and is put into a muffle furnace for roasting for 4 hours at 500 ℃, and is cooled to obtain the catalyst.
Example 7
(1) Accurately weighing 0.40g of samarium nitrate and 0.42g of cesium nitrate, and adding a certain amount of deionized water for full dissolution to obtain an aqueous solution containing samarium and cesium;
(2) The silica carrier obtained in the example (2) is added into the solution and then is kept stand for 12 hours, then is dried for 12 hours at 120 ℃, is put into a muffle furnace for roasting for 4 hours at 500 ℃, and is cooled to obtain the catalyst.
Example 8
(1) Accurately weighing 0.35g of samarium sulfate and 0.42g of cesium nitrate, and adding a certain amount of deionized water for full dissolution to obtain an aqueous solution containing samarium and cesium;
(2) The silica carrier obtained in the example (3) is added into the solution and then is kept stand for 12 hours, then is dried for 12 hours at 120 ℃, is put into a muffle furnace for roasting for 4 hours at 500 ℃, and is cooled to obtain the catalyst.
Example 9
(1) Accurately weighing 0.19g of samarium nitrate and 0.42g of cesium nitrate, and adding a certain amount of deionized water for full dissolution to obtain an aqueous solution containing samarium and cesium;
(2) The silica carrier obtained in the example (4) is added into the solution and then is kept stand for 12 hours, then is dried for 12 hours at 120 ℃, is put into a muffle furnace for roasting for 4 hours at 500 ℃, and is cooled to obtain the catalyst.
Example 10
(1) Accurately weighing 0.28g of samarium nitrate and 0.42g of cesium carbonate, and adding a certain amount of deionized water for full dissolution to obtain an aqueous solution containing samarium and cesium;
(2) The silica carrier obtained in the example (5) is added into the solution and then is kept stand for 12 hours, then is dried for 12 hours at 120 ℃, is put into a muffle furnace for roasting for 4 hours at 500 ℃, and is cooled to obtain the catalyst.
Comparative example
(1) Directly weighing untreated 10g of silica carrier;
(2) The catalyst was prepared in the same manner as in example 6, and the carrier was selected from the untreated silica carrier in the above (1).
TABLE 1 hydroxyl content of silicon support surface in different examples
| Examples | Carrier silicon hydroxyl content (number/nm) 2 ) |
| Comparative example | 1.01 |
| 1 | 1.02 |
| 2 | 0.99 |
| 3 | 0.94 |
| 4 | 1.13 |
| 5 | 0.96 |
TABLE 2 evaluation results of catalyst Activity
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (2)
1. The method for regulating and controlling the hydroxyl groups on the surface of the silicon dioxide carrier is applied to the preparation of a catalyst for synthesizing methyl methacrylate, and is characterized by comprising the following steps of:
(a) Ion thermal treatment: and (3) placing a proper amount of ethanolamine acetate in a beaker, placing the beaker in an oil bath at a set temperature for stirring, weighing a certain mass of silicon dioxide carrier, adding the silicon dioxide carrier into the oil bath, and stirring for 1-3 hours while keeping the temperature of the oil bath at 120 ℃. After the treatment is finished, centrifugally collecting a solid product, drying the solid product at 120 ℃ for 6 hours, calcining the solid product at 500 ℃ for 4 hours, and tabletting to obtain a treated carrier;
(b) Pulse program roasting treatment: weighing a certain mass of silicon dioxide carrier, placing the silicon dioxide carrier in a crucible, selecting a pulse program for roasting, firstly, regulating and controlling the frequency of a pulse signal through a controller, heating at a certain frequency and keeping the temperature at 500 ℃ for 3 hours, then adding a frequency signal to keep the temperature at 800 ℃ for 5 hours, naturally cooling to room temperature after finishing, and finally obtaining the carrier after the pulse program roasting treatment;
(c) Peroxide treatment: putting a certain mass of silica carrier into a three-necked flask, adding 30mL of peroxide with mass fraction of 5% and ammonia water, mixing at constant temperature of 100 ℃ in an oil bath, stirring for 5h, ensuring condensation reflux and an outlet for releasing decomposed gas in the treatment process, and drying the obtained carrier at constant temperature in a drying oven at 50 ℃ for 3h. Obtaining the carrier after peroxide treatment.
2. The method according to claim 1, wherein the silica carrier surface is precisely controlled by the above (a), (b) and (c).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311528877.3A CN117563577A (en) | 2023-11-16 | 2023-11-16 | Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311528877.3A CN117563577A (en) | 2023-11-16 | 2023-11-16 | Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117563577A true CN117563577A (en) | 2024-02-20 |
Family
ID=89861899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311528877.3A Pending CN117563577A (en) | 2023-11-16 | 2023-11-16 | Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117563577A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2009014261A (en) * | 2009-12-21 | 2011-06-21 | Ct Investig Y Estudios Del Ipn | Method for the synthesis of zeolites by the amorphization-crystal lization of fly ashes. |
| WO2017185927A1 (en) * | 2016-04-27 | 2017-11-02 | 武汉凯迪工程技术研究总院有限公司 | Multi-level channel-type cobalt-based fischer-tropsch synthetic catalyst with core-shell structure and preparation method therefor |
| US20200164346A1 (en) * | 2018-11-22 | 2020-05-28 | National Engineering Research Center Of Chemical Fertilizer Catalyst, Fuzhou University | Ruthenium-based catalyst for hydrogen production from ammonia decomposition, preparation method therefor and application thereof |
| CN111344059A (en) * | 2017-09-13 | 2020-06-26 | 卢塞特英国国际有限公司 | Catalyst for producing ethylenically unsaturated carboxylic acid or carboxylic acid ester and production method |
| CN112774658A (en) * | 2021-02-02 | 2021-05-11 | 中国科学院过程工程研究所 | Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof |
| CN114334627A (en) * | 2020-09-29 | 2022-04-12 | 长鑫存储技术有限公司 | Oxide layer forming method and semiconductor structure |
| CN115155627A (en) * | 2022-07-26 | 2022-10-11 | 中化泉州能源科技有限责任公司 | Multi-component composite catalyst for preparing 1, 3-propylene glycol by hydrogenating methyl 3-hydroxypropionate and preparation method thereof |
| CN116621701A (en) * | 2022-02-14 | 2023-08-22 | 中国石油化工股份有限公司 | Solid base catalyst, preparation method thereof and synthesis method of methyl methacrylate |
-
2023
- 2023-11-16 CN CN202311528877.3A patent/CN117563577A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2009014261A (en) * | 2009-12-21 | 2011-06-21 | Ct Investig Y Estudios Del Ipn | Method for the synthesis of zeolites by the amorphization-crystal lization of fly ashes. |
| WO2017185927A1 (en) * | 2016-04-27 | 2017-11-02 | 武汉凯迪工程技术研究总院有限公司 | Multi-level channel-type cobalt-based fischer-tropsch synthetic catalyst with core-shell structure and preparation method therefor |
| CN111344059A (en) * | 2017-09-13 | 2020-06-26 | 卢塞特英国国际有限公司 | Catalyst for producing ethylenically unsaturated carboxylic acid or carboxylic acid ester and production method |
| US20200164346A1 (en) * | 2018-11-22 | 2020-05-28 | National Engineering Research Center Of Chemical Fertilizer Catalyst, Fuzhou University | Ruthenium-based catalyst for hydrogen production from ammonia decomposition, preparation method therefor and application thereof |
| CN114334627A (en) * | 2020-09-29 | 2022-04-12 | 长鑫存储技术有限公司 | Oxide layer forming method and semiconductor structure |
| CN112774658A (en) * | 2021-02-02 | 2021-05-11 | 中国科学院过程工程研究所 | Acid-base bifunctional catalyst for synthesizing methyl acrylate from methyl acetate and formaldehyde and preparation method thereof |
| CN116621701A (en) * | 2022-02-14 | 2023-08-22 | 中国石油化工股份有限公司 | Solid base catalyst, preparation method thereof and synthesis method of methyl methacrylate |
| CN115155627A (en) * | 2022-07-26 | 2022-10-11 | 中化泉州能源科技有限责任公司 | Multi-component composite catalyst for preparing 1, 3-propylene glycol by hydrogenating methyl 3-hydroxypropionate and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李斌;齐翔;解铭;王光远;张乐;王博;申利红;: "气相催化丙酸与甲醛缩合反应制甲基丙烯酸", 工业催化, no. 09, 15 September 2018 (2018-09-15) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108465466B (en) | Cerium dioxide-coated Pd spherical catalyst and preparation method thereof | |
| CN107824172B (en) | Preparation method of nano alumina carrier with surface rich in defect sites | |
| CN109453766B (en) | Ag-loaded TiO with atomic-level dispersion2Preparation method of mesoporous nanobelt photocatalyst | |
| CN111715200B (en) | Alumina carrier with core-shell structure and preparation and application thereof | |
| CN109746029B (en) | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation | |
| CN110813300B (en) | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite | |
| CN107486197A (en) | Preparation method of low-carbon alkane dehydrogenation microspherical catalyst | |
| CN117563577A (en) | Preparation method of catalyst for synthesizing methyl methacrylate by using silica carrier surface hydroxyl regulation method | |
| CN113877560B (en) | Synthesis method of methyl acrylate and solid base catalyst thereof | |
| CN109748294A (en) | The method of spherical mesoporous molecular screen material and preparation method thereof and catalyst and its preparation method and application and preparing propylene by dehydrogenating propane | |
| CN109746028B (en) | Propane dehydrogenation catalyst, preparation method thereof and method for preparing propylene by propane dehydrogenation | |
| CN110614118A (en) | Isobutane dehydrogenation catalyst with three-hole sepiolite spherical mesoporous composite material as carrier and preparation method and application thereof | |
| RU2765118C1 (en) | Method for obtaining a spherical aluminum oxide carrier | |
| JP6529375B2 (en) | Metal catalyst, production method thereof and regeneration method thereof | |
| RU2329100C2 (en) | Method of obtaining oxide catalysts on a substrate | |
| CN113117699A (en) | Sulfate radical modified iridium-based methane combustion catalyst, and preparation and application thereof | |
| CN104549357B (en) | Precious metal hydrogenation catalyst, preparation method and application thereof | |
| KR20170091969A (en) | Method for manufacturing zinc-doped alumina dehydrogenation catalyst | |
| CN105642301A (en) | Preparation method of copper bismuth catalyst for synthesis of 1, 4-butynediol | |
| CN114570412B (en) | Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application | |
| CN113441166B (en) | Nitrogen-phosphorus co-doped carbon-based cobalt catalyst, preparation method thereof and synthetic method of saturated aliphatic primary amine | |
| CN115814824A (en) | P-coordinated Co-Rh bimetallic catalyst, synthesis method and application | |
| RU2806328C2 (en) | Method of producing catalyst for synthesis of unsaturated carboxylic acid | |
| CN115672387B (en) | Methane anaerobic aromatization catalyst and preparation method and application thereof | |
| CN116371416B (en) | Nickel-niobium/attapulgite-based ordered mesoporous catalyst and preparation method and application thereof |
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 |