CN112206762A - Na-gamma-Al2O3Preparation method of catalyst and application of catalyst in catalytic synthesis of anisole - Google Patents
Na-gamma-Al2O3Preparation method of catalyst and application of catalyst in catalytic synthesis of anisole Download PDFInfo
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- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000007036 catalytic synthesis reaction Methods 0.000 title abstract description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 7
- 238000010926 purge Methods 0.000 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 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012022 methylating agents Substances 0.000 description 4
- 238000007069 methylation reaction Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- -1 aromatic ether compound Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses Na-gamma-Al2O3The preparation method of catalyst and its application in catalytic synthesis of anisole are characterized by that firstly, the gamma-Al is added2O3Calcining at high temperature to activate gamma-Al2O3(ii) a Then the activated gamma-Al is added2O3、CH3OH and Na are stirred and react for 4-4.5 hours at the temperature of 350-400 ℃ in a reaction kettle in a molar ratio of 0.5-1.5: 2.5-3.5: 1-3 to obtain Na-gamma-Al2O3A catalyst. The invention adopts a one-step method to prepare Na-gamma-Al2O3The catalyst has the advantages of simple and rapid synthesis steps, good activity and high catalytic efficiency when used for catalyzing the reaction of dimethyl carbonate and phenol to prepare anisole, high conversion rate of phenol up to more than 80%, basically 100% selectivity of anisole, reusability and regeneration of the catalyst, and good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of anisole synthesis, and relates to Na-gamma-Al2O3A preparation method of the catalyst and application of the catalyst in catalytic synthesis of anisole.
Background
Anisole, also known as anisole and methoxybenzene, is the most basic aromatic ether compound. Anisole is easy to have electrophilic substitution reaction, so that it is widely used for synthesizing compounds containing methoxyl group, and is an intermediate for synthesizing various medicines and organic chemicals; because of its special fragrance, people usually use it as an additive for soaps or detergents; because of its large dielectric constant and high boiling point, it can be used as excellent general-purpose reagent, initiator, solvent, thermostat filler, etc.; in addition, the gasoline can be used as a gasoline additive to replace methyl tert-butyl ether due to the improvement of the octane number of the gasoline. In recent years, the demand of anisole in the market has increased year by year.
At present, the method for industrially producing anisole mainly comprises the steps of reacting phenol with alkali to generate sodium phenate, and reacting the sodium phenate with dimethyl sulfate to synthesize anisole, namely a two-step method.
The equation is as follows:
dimethyl sulfate in the method is a hypertoxic, excessive alkali is needed to be used, a large amount of salt-containing wastewater is generated, the safety risk is high, and the environmental pollution is serious. With the increasing environmental protection importance of China, the traditional high-pollution process is bound to be limited, and the development of the low-cost, green and efficient production process of anisole is bound to be carried out.
Methanol is taken as a methylating agent to react and synthesize anisole under alkaline conditions:
the method for synthesizing anisole from methanol and phenol has the potential advantages of low raw material cost and simple post-treatment, but the methanol has low reaction activity, and is simultaneously subjected to C-methylation and O-methylation reactions in the reaction process of phenol, so that the improvement of the selectivity of anisole is a key point. The process route of methanol as a methylating agent is difficult to industrialize due to its low reactivity and target product selectivity.
Dimethyl carbonate is taken as a methylating agent to generate anisole under the action of an alkaline catalyst:
dimethyl carbonate is used as an environment-friendly methylating agent, when the dimethyl carbonate is used for synthesizing anisole with phenol, alkali is not needed, carbon dioxide and methanol with equimolar amount are generated, and no pollutant is generated in the reaction process. Compared with methanol as a methylation reagent, the dimethyl carbonate has obvious relative advantages, is environment-friendly, pollution-free, high in selectivity and high in conversion rate, and the product is easy to separate and can be recycled, so that the dimethyl carbonate becomes the most effective process route at present, but the dimethyl carbonate needs to be carried out under the condition of a high-temperature high-pressure catalyst when participating in the methylation reaction. Ouk and the like, and anisole is synthesized under normal pressure using a solid/liquid phase transfer catalyst. The reaction was carried out using tetrabutylammonium bromide (TBAB) as the phase transfer catalyst, 0.75 equivalents of K2CO3The reaction is carried out at 93 ℃ for 5 hours under normal pressure, the yield of anisole reaches 99 percent, but the dosage of dimethyl carbonate is larger (30 equivalents). And the Antonac and the like use TBD as a catalyst, the temperature is controlled at 170 ℃, and microwave irradiation is carried out for 10 minutes, so that the complete conversion of phenol is realized, and the selectivity of anisole reaches 100%. However, DBU and TBD are expensive, high in cost and not easy to realize industrialization. In conclusion, the green process for synthesizing anisole by catalyzing phenol and dimethyl carbonate does not realize industrial production, is always limited by high equipment investment and high raw material cost, and the preparation and selection of a proper supported catalyst is a problem to be solved urgently by scientific researchers.
Disclosure of Invention
The invention aims to provide Na-gamma-Al aiming at the problems of longer process route, environmental pollution, low catalytic activity of a catalyst, unstable catalytic activity and the like in the synthesis of anisole2O3A preparation method of a catalyst, which aims to solve the problems in the prior art.
Na-gamma-Al used in the invention2O3The preparation method of the catalyst comprises the following steps:
1. mixing gamma-Al2O3Calcining at 500-550 ℃ for 5-6 hours to activate gamma-Al2O3。
2. gamma-Al in molar ratio2O3：CH3OH: na is 0.5-1.5: 2.5-3.5: 1-3, and the activated gamma-Al in the step 1 is subjected to anhydrous and oxygen-free sealing conditions2O3、CH3OH and Na are stirred and react for 4-4.5 hours at the temperature of 350-400 ℃ to obtain Na-gamma-Al2O3A catalyst.
In the step 1, the stirring speed is preferably 600 to 650 rpm.
In the above step 2, γ -Al is preferable2O3：CH3OH: the molar ratio of Na is 0.8-1: 3-3.3: 1.5-2.
Na-gamma-Al of the invention2O3The method for synthesizing anisole by the catalysis of the catalyst comprises the following steps: mixing dimethyl carbonate, phenol and Na-gamma-Al2O3Adding the catalyst into a high-pressure reaction kettle, and reacting for 1-6 hours at 170-220 ℃ under a closed condition to obtain anisole.
In the method for catalytically synthesizing anisole, the mass ratio of dimethyl carbonate to phenol is preferably 2: 1-4: 1, and Na-gamma-Al is preferably selected2O3The adding amount of the catalyst is 2-9% of the total mass of the dimethyl carbonate and the phenol.
In the method for catalytically synthesizing anisole, the reaction is preferably carried out for 1 to 3 hours at 180 to 200 ℃ under a sealed condition.
The invention has the following beneficial effects:
1. the invention changes the traditional method of using gamma-Al2O3The traditional preparation method of the super-strong base is that the carrier is treated by alkali hydroxide, then alkali simple substance is added at the melting point temperature of the alkali hydroxide for further treatment, the whole preparation process needs two steps and is not easy to realize the continuity of operation, and the industrialization is difficult to realize; the invention adopts a one-step method to prepare Na-gamma-Al2O3Catalyst, i.e. mixing of gamma-Al2O3、CH3OH and Na are added according to a certain molar ratio, and the metal sodium reacts with methanol to generate sodium methoxide and then reacts with gamma-Al2O3Combined with Na-gamma-Al2O3A catalyst.
2. Compared with the common catalyst, the catalyst has super-strong alkalinity, can provide reaction conditions for dimethyl carbonate and phenol, the conversion rate of the phenol can reach more than 80 percent, and the selectivity of anisole can basically reach 100 percent; compared with the same type of catalyst, the catalyst has the advantages of simple and rapid synthesis steps, good activity, high catalytic efficiency, no environmental pollution, no corrosion to equipment, repeated use and regeneration, and good industrial application prospect.
Drawings
FIG. 1 shows the activated γ -Al of example 12O3(left) and prepared Na-gamma-Al2O3SEM image of catalyst (right).
FIG. 2 shows Na-. gamma. -Al prepared in example 12O3XRD pattern of the catalyst.
Detailed Description
The invention is described in detail below with reference to the figures and examples, but the scope of protection of the invention is not limited to these examples.
Example 1
1. Taking gamma-Al2O310.2417g (0.1mol) were charged into a muffle furnaceCalcining at 550 ℃ for 6 hours to activate gamma-Al2O3Taking out the gamma-Al when the temperature of the muffle furnace is reduced to room temperature2O3。
2. Will N2Introducing the mixture into a high-pressure reaction kettle, purging for 10 minutes, and adding activated gamma-Al2O3Continuously purging to obtain CH3OH 13mL (0.33mol) was charged into the autoclave, and sodium metal 4.6956g (0.2mol) was added to wait for CH3After the reaction of OH and metallic sodium is finished, 5g of CaO is added to absorb moisture and improve the alkalinity of the catalyst; removing N2Blowing and closing the high-pressure reaction kettle cover, stirring and reacting for 4 hours at the temperature of 350 ℃ at 650 rpm to obtain gray powder Na-gamma-Al2O3A catalyst.
As can be seen from FIG. 1, the activated gamma-Al2O3The surface appearance is irregular small particles, the pore size is uniform, the surface structure is regular, and the prepared Na-gamma-Al2O3The catalyst has more ideal surface structure, rich surface pore structure, high crystallization degree and wider pore diameter range; in fig. 2, the diffraction peaks at 2 θ of 36.86 °, 45.29 °, and 67.27 ° are typical γ -Al2O3Diffraction peak, wider base line and unobvious peak pattern, which indicates gamma-Al2O3The crystallization is incomplete and the product is in a microcrystalline state. Meanwhile, comparing a standard PDF card library by Jade 6 data processing software to obtain a diffraction peak NaAlCO at the 2 theta (32.89 degrees)3(OH)2A characteristic peak of (dawsonite) whose crystal system is an orthorhombic hexagonal system and whose crystal grain size is
The diffraction peak at 7.45 ° 2 θ is C2H2AlNaO6·3H2Characteristic peak of O, grain size of
Example 2
1. Taking gamma-Al2O310.2417g (0.1mol) were added to a muffle furnace and calcined at 500 ℃ for 6 hours to activate gamma-Al2O3Temperature of furnace waiting for muffleCooling to room temperature and taking out the gamma-Al2O3。
2. Will N2Introducing the mixture into a high-pressure reaction kettle, purging for 10 minutes, and adding activated gamma-Al2O3Continuously purging to obtain CH3OH 13mL (0.32mol) was charged into the autoclave, and sodium metal 4.1425g (0.18mol) was added to wait for CH3After the reaction of OH and metallic sodium is finished, 5g of CaO is added to absorb moisture and improve the alkalinity of the catalyst; removing N2Blowing and closing the high-pressure reaction kettle cover, stirring and reacting for 4 hours at the temperature of 400 ℃ at 650 rpm to obtain gray powder Na-gamma-Al2O3A catalyst.
Example 3
1. Taking gamma-Al2O310.2417g (0.1mol) were put into a muffle furnace and calcined at 550 ℃ for 5 hours to activate gamma-Al2O3Taking out the gamma-Al when the temperature of the muffle furnace is reduced to room temperature2O3。
2. Will N2Introducing the mixture into a high-pressure reaction kettle, purging for 10 minutes, and adding activated gamma-Al2O3Continuously purging to obtain CH3OH 12mL (0.3mol) was charged into the autoclave, and sodium metal 3.4536g (0.15mol) was added to wait for CH3After the reaction of OH and metallic sodium is finished, 5g of CaO is added to absorb moisture and improve the alkalinity of the catalyst; removing N2Blowing and closing the high-pressure reaction kettle cover, stirring and reacting for 4.5 hours at the temperature of 400 ℃ at 600 revolutions per minute to obtain powdered Na-gamma-Al2O3A catalyst.
Example 4
Dimethyl carbonate and phenol are added into a high-pressure reaction kettle according to different mol ratios, and Na-gamma-Al prepared in the example 1 with different mass contents of the total mass of the dimethyl carbonate and the phenol is added2O3And (3) the catalyst is reacted at different temperatures for different times under a closed condition, and the conversion rate of the phenol and the ratio of the anisole in the product are measured by a gas-mass spectrometer. Specific reaction conditions and reaction results are shown in table 1.
TABLE 1
| Reaction temperature/. degree.C | Reaction time/h | Reactant proportioning | Amount of catalyst/% | Conversion rate/% | Yield/%) |
| 170 | 2 | 2 | 5 | 81.86 | 80.99 |
| 180 | 1 | 3 | 7 | 81.26 | 80.38 |
| 180 | 1 | 3 | 3 | 98.75 | 96.55 |
| 180 | 3 | 3 | 7 | 83.17 | 81.22 |
| 180 | 1 | 4 | 5 | 80.58 | 80.06 |
| 180 | 3 | 3 | 3 | 96.63 | 95.46 |
| 190 | 2 | 3 | 7 | 84.58 | 81.75 |
| 190 | 2 | 2 | 5 | 86.29 | 85.59 |
| 190 | 3 | 3 | 5 | 84.09 | 81.12 |
| 190 | 2 | 3 | 3 | 81.35 | 80.89 |
As can be seen from Table 1, when the catalyst of the invention is used for catalyzing dimethyl carbonate to react with phenol to synthesize anisole, the conversion rate of the phenol can reach more than 80%, and the yield of the anisole is further improved.
Claims (7)
1. Na-gamma-Al2O3A process for the preparation of a catalyst, characterized in that said process consists of the following steps:
(1) mixing gamma-Al2O3Calcining at 500-550 ℃ for 5-6 hours to activate gamma-Al2O3；
(2) gamma-Al in molar ratio2O3：CH3OH: na is 0.5-1.5: 2.5-3.5: 1-3, and the activated gamma-Al obtained in the step (1) is subjected to anhydrous, oxygen-free and sealed conditions2O3、CH3OH and Na are stirred and react for 4-4.5 hours at the temperature of 350-400 ℃ to obtain Na-gamma-Al2O3A catalyst.
2. Na- γ -Al according to claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: in the step (2), the stirring speed is 600-650 rpm.
3. Na- γ -Al according to claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: in the step (2), gamma-Al2O3：CH3OH: the molar ratio of Na is 0.8-1: 3-3.3: 1.5-2.
4. A method of using the method of claim 1Na-gamma-Al prepared by the method2O3The method for synthesizing anisole by the catalysis of the catalyst is characterized in that: mixing dimethyl carbonate, phenol and Na-gamma-Al2O3Adding the catalyst into a high-pressure reaction kettle, and reacting for 1-6 hours at 170-220 ℃ under a closed condition to obtain anisole.
5. Na- γ -Al according to claim 42O3The method for synthesizing anisole by the catalysis of the catalyst is characterized in that: the mass ratio of the dimethyl carbonate to the phenol is 2: 1-4: 1.
6. Na- γ -Al according to claim 42O3The method for synthesizing anisole by the catalysis of the catalyst is characterized in that: the Na-gamma-Al2O3The adding amount of the catalyst is 2-9% of the total mass of the dimethyl carbonate and the phenol.
7. Na- γ -Al according to claim 42O3The method for synthesizing anisole by the catalysis of the catalyst is characterized in that: reacting for 1-3 hours at 180-200 ℃ under a sealed condition.
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| CN114736105A (en) * | 2022-04-19 | 2022-07-12 | 邵阳学院 | Method for catalytic synthesis of anisole from calcium-aluminum composite oxide |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114736105B (en) * | 2022-04-19 | 2024-04-12 | 邵阳学院 | Method for synthesizing anisole by catalyzing calcium-aluminum composite oxide |
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