CN109809970B - Method for producing anisole by catalyzing phenol and methanol - Google Patents
Method for producing anisole by catalyzing phenol and methanol Download PDFInfo
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Abstract
The invention discloses a method for producing anisole by catalyzing phenol and methanol, which adopts a fixed bed reactor, takes carriers such as zinc phosphate, iron phosphate, copper phosphate, chromium phosphate and the like to load modified components such as cerium nitrate, zirconium nitrate, lanthanum nitrate, cobalt nitrate, nickel nitrate and the like and auxiliaries such as potassium fluoride, cesium fluoride, sodium fluoride and the like as catalysts, realizes the high-efficiency synthesis of anisole, has high phenol conversion rate and anisole selectivity, has simple preparation process, low cost, high stability and long service life, and meets the application requirements of industrial catalysts.
Description
Technical Field
The invention belongs to the technical field of preparation of anisole, and particularly relates to a method for producing anisole by catalyzing phenol and methanol.
Background
Anisole, also called as anisyl ether, anisole, methoxybenzene, is an important chemical raw material, and can be used as an additive of soap and detergent due to its special fragrance; as intermediates in the synthesis of fragrances, dyes, enteral insecticides; it can be used as excellent general-purpose reagent, initiator, solvent and thermostat filler, etc. due to its large dielectric constant and high boiling point, and can be used as gasoline additive instead of methyl tert-butyl ether, also can be used as solvent and additive of synthetic resin and fuel in printing industry and paint and pigment industry. In recent years, the demand for anisole in the market has increased dramatically.
The synthetic method of anisole mainly includes a dimethyl sulfate method, a dimethyl carbonate method and a methanol method according to the difference of methylating agents. The dimethyl sulfate method has the advantages of low reaction temperature, good selectivity of target products and low cost, but the used dimethyl sulfate is a highly toxic product, phenol needs to be converted into sodium phenolate in the production process, a large amount of sodium hydroxide needs to be used, a large amount of salt-containing wastewater is generated, the post-treatment is difficult, the environmental pollution of the method is serious, and the process is eliminated; the dimethyl carbonate method and the methanol method adopt green methylating reagents dimethyl carbonate and methanol, do not generate solid waste in the production process, and are two green synthetic routes. However, carbon dioxide and methanol are generated in the reaction process of the dimethyl carbonate method, and the carbon dioxide and the methanol need to be recovered, so that the production process is relatively complex, the equipment investment cost is relatively high, and the anisole cost and the market competitiveness are relatively weak directly; the methanol method has the advantages of low raw material cost, no secondary pollution and simple post-treatment, and is the main research direction of various researchers in recent years.
The process for synthesizing anisole by the methanol method can adopt a batch method and a continuous method, the batch method has the defects of high production labor intensity, high equipment energy consumption and the like and is eliminated, and the continuous method has the advantages of low labor intensity, low energy consumption, simple operation and the like and is the current mainstream process. The catalyst for continuously producing anisole mainly comprises oxides, molecular sieves, phosphates and the like, Oku and the like (Adv Synth Catal, 2005,347(11-13):1553-1557) takes Cs-P-Si ternary oxide as a catalyst, the conversion rate of phenol is 49 percent, and the selectivity of anisole reaches 98 percent at 320 ℃ and 8.2 MPa. Kirichenko et al (Petroleum Chemistry,2008,48(5):389-392) use commercial NaX molecular sieve as catalyst to realize the synthesis of anisole by gas phase alkylation of phenol and methanol, the phenol-alcohol ratio is 1:8 at 320 ℃, the phenol conversion rate is 99.8% at normal pressure, and the anisole selectivity is 90.2%. Zhang et al (Z Phys Chem,2010,224(6):857-864) prepared a series of rare earth phosphate mesoporous materials with the highest conversion rate of phenol of 62.8%, the selectivity of anisole of 96.8% and the by-product of o-cresol only.
Although some breakthroughs are obtained in the research, the catalyst shows higher initial activity, but the catalyst has lower service life as the activity of the catalyst is gradually attenuated along with the reaction, and some catalysts have the problems that better anisole selectivity and higher phenol conversion rate can be obtained only under the condition of higher alcohol-phenol ratio, and the like, so that the energy consumption is increased sharply, the production cost is increased, and the market competitiveness is difficult to achieve; meanwhile, the preparation process of part of catalysts is complex and harsh, which results in higher catalyst cost and limits the realization of industrial application.
Disclosure of Invention
The invention aims to provide an industrial preparation method for producing anisole from phenol and methanol, which has the advantages of simple preparation process, no pollution, high conversion rate and long service life of a catalyst, aiming at the defects or shortcomings in the prior art.
Aiming at the above purpose, the technical scheme adopted by the invention comprises the following steps:
1. adding a carrier into deionized water, adding a modified component, stirring at normal temperature for 4-8 h, aging and drying at 80-100 ℃ for 10-12 h, roasting at 450-600 ℃ for 3-6 h, and cooling to room temperature to prepare a catalyst intermediate; the mass ratio of the carrier to the modified component to the deionized water is (0.01-0.05) to (2-5), the carrier is any one of zinc phosphate, iron phosphate, copper phosphate and chromium phosphate, and the modified component is any one of cerium nitrate, zirconium nitrate, lanthanum nitrate, cobalt nitrate and nickel nitrate.
2. Adding the catalyst intermediate into deionized water, adding an auxiliary agent, stirring at normal temperature for 3-5 h, aging and drying at 90-110 ℃ for 10-12 h, and roasting at 450-600 ℃ for 4-8 h to prepare a catalyst; the mass ratio of the catalyst intermediate to the auxiliary agent to the deionized water is (0.001-0.01) to (2-5), and the auxiliary agent is any one of potassium fluoride, cesium fluoride and sodium fluoride.
3. Granulating and molding the obtained catalyst into cylindrical particles with the diameter of 3-6 mm and the height of 3-6 mm, and filling the cylindrical particles into a fixed bed reactor; after being preheated, phenol and methanol continuously pass through a fixed bed reactor, and are subjected to gas phase reaction to generate anisole under the reaction conditions of the reaction temperature of 280-350 ℃, the reaction pressure of 0.1-3 MPa and the material residence time of 20-40 s.
In the step 1, preferably, the carrier is added into deionized water, the modified component is added, the mixture is stirred at normal temperature for 6 hours, aged and dried at 90 ℃ for 12 hours, roasted at 500-550 ℃ for 4-5 hours, and cooled to room temperature to prepare the catalyst intermediate. The mass ratio of the carrier to the modified component to the deionized water is preferably (0.02-0.04) to (3-4), the carrier is preferably any one of copper phosphate and chromium phosphate, and the modified component is preferably any one of cerium nitrate, zirconium nitrate and nickel nitrate.
In the step 2, preferably, the catalyst intermediate is added into deionized water, and an auxiliary agent is added, the mixture is stirred at normal temperature for 4 hours, aged and dried at 100 ℃ for 12 hours, and roasted at 480-550 ℃ for 5-7 hours to prepare the catalyst. The mass ratio of the catalyst intermediate to the auxiliary agent to the deionized water is preferably 1 (0.004-0.008): 3-4, and the auxiliary agent is preferably any one of potassium fluoride and cesium fluoride.
In the step 3, preferably, the obtained catalyst is granulated and formed into cylindrical particles with the diameter of 4-5 mm and the height of 4-5 mm, and the cylindrical particles are filled into a fixed bed reactor; after being preheated, phenol and methanol continuously pass through a fixed bed reactor, and are subjected to gas phase reaction to generate anisole under the reaction conditions of the reaction temperature of 300-320 ℃, the reaction pressure of 0.5-1.5 MPa and the material residence time of 25-35 s. The molar ratio of the phenol to the methanol is 1 (2-5), and the preferred molar ratio of the phenol to the methanol is 1 (3-4).
The invention has the following beneficial effects:
the invention has the characteristics of simple preparation process and low cost of the catalyst, the catalytic use has the characteristics of high conversion rate, good selectivity and long service life, the conversion rate of phenol can still reach 79.5-88.6 percent and the selectivity of anisole can still reach 98.1-99.3 percent after the reaction is carried out for 200 hours, the reaction is continuously prolonged to 2000 hours, the activity of the catalyst is basically unchanged, and the application requirement of the industrial catalyst is met.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
The phenol conversion and anisole selectivity in the following examples were determined by gas chromatography under the following conditions: the detector is FID, the vaporizing chamber is 240 deg.C, the detector temperature is 240 deg.C, the column temperature is 60 deg.C, the constant temperature is 2min, the temperature is increased to 180 deg.C, the constant temperature is 1min, and the chromatographic column is HP-5.
Example 1
1. Adding 100g of zinc phosphate into 200g of deionized water, adding 1g of cerium nitrate, stirring at normal temperature for 6h, aging and drying at 90 ℃ for 12h, putting into a muffle furnace, roasting at 450 ℃ for 6h, and cooling to room temperature to prepare a catalyst intermediate.
2. Adding 100g of catalyst intermediate into 200g of deionized water, adding 0.1g of sodium fluoride, stirring at normal temperature for 4h, aging and drying at 100 ℃ for 12h, and roasting at 450 ℃ for 8h to prepare the catalyst.
3. Granulating the obtained catalyst, forming into cylindrical particles with diameter of 4mm and height of 4mm, and filling into a fixed bed reactor, wherein the filling amount of the catalyst is 30mL, the inner diameter of the reaction tube is 28mm, and the material is 316L stainless steel; after being preheated, phenol and methanol continuously pass through a fixed bed reactor according to the molar ratio of 1:3, and carry out gas phase reaction to generate anisole under the reaction conditions of the reaction temperature of 300 ℃, the reaction pressure of normal pressure and the material retention time of 30 s. The results of the reaction for 200h are shown in Table 1.
Example 2
1. Adding 100g of iron phosphate into 300g of deionized water, adding 2g of zirconium nitrate, stirring at normal temperature for 6h, aging and drying at 90 ℃ for 12h, putting into a muffle furnace, roasting at 500 ℃ for 4h, and cooling to room temperature to obtain a catalyst intermediate.
2. Adding 100g of catalyst intermediate into 300g of deionized water, adding 0.4g of cesium fluoride, stirring at normal temperature for 4h, aging and drying at 100 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the catalyst.
3. This step was the same as step 3 of example 1, and the results of the reaction for 200h are shown in Table 1.
Example 3
1. Adding 100g of copper phosphate into 500g of deionized water, adding 5g of lanthanum nitrate, stirring at normal temperature for 6h, aging and drying at 90 ℃ for 12h, putting into a muffle furnace, roasting at 600 ℃ for 3h, and cooling to room temperature to obtain a catalyst intermediate.
2. Adding 100g of catalyst intermediate into 500g of deionized water, adding 1g of potassium fluoride, stirring at normal temperature for 4h, aging and drying at 100 ℃ for 12h, and roasting at 600 ℃ for 4h to prepare the catalyst.
3. This step was the same as step 3 of example 1, and the results of the reaction for 200h are shown in Table 1.
Example 4
1. Adding 100g of chromium phosphate into 500g of deionized water, adding 4g of zirconium nitrate, stirring at normal temperature for 6h, aging and drying at 90 ℃ for 12h, putting into a muffle furnace, roasting at 550 ℃ for 4h, and cooling to room temperature to obtain a catalyst intermediate.
2. Adding 100g of catalyst intermediate into 400g of deionized water, adding 0.8g of potassium fluoride, stirring at normal temperature for 4h, aging and drying at 100 ℃ for 12h, and roasting at 550 ℃ for 4h to prepare the catalyst.
3. This step was the same as step 3 of example 1, and the results of the reaction for 200h are shown in Table 1.
Example 5
1. Adding 100g of copper phosphate into 400g of deionized water, adding 4g of nickel nitrate, stirring at normal temperature for 6h, aging and drying at 90 ℃ for 12h, putting into a muffle furnace, roasting at 500 ℃ for 7h, and cooling to room temperature to obtain a catalyst intermediate.
2. Adding 100g of catalyst intermediate into 400g of deionized water, adding 0.4g of potassium fluoride, stirring at normal temperature for 4h, aging and drying at 100 ℃ for 12h, and roasting at 480 ℃ for 6h to prepare the catalyst.
3. This step was the same as step 3 of example 1, and the results of the reaction for 200h are shown in Table 1.
Example 6
1. Adding 100g of chromium phosphate into 300g of deionized water, adding 4g of cerium nitrate, stirring at normal temperature for 8h, aging and drying at 90 ℃ for 12h, putting into a muffle furnace, roasting at 550 ℃ for 5h, and cooling to room temperature to obtain a catalyst intermediate.
2. Adding 100g of the catalyst intermediate into 300g of deionized water, adding 0.6g of cesium fluoride, stirring at normal temperature for 4h, aging and drying at 100 ℃ for 12h, and roasting at 500 ℃ for 5h to obtain the catalyst.
3. This step was the same as step 3 of example 1, and the results of the reaction for 200h are shown in Table 1.
TABLE 1 results of the reaction
| Sample (I) | Conversion of phenol | Anisole selectivity | O-methyl phenol | Others |
| Example 1 | 79.5％ | 98.8％ | 1.0％ | 0.2％ |
| Example 2 | 81.3％ | 98.6％ | 1.1％ | 0.3％ |
| Example 3 | 83.4％ | 99.3％ | 0.6％ | 0.1％ |
| Example 4 | 88.6％ | 98.1％ | 1.6％ | 0.3％ |
| Example 5 | 85.7％ | 98.4％ | 1.4％ | 0.2％ |
| Example 6 | 86.1％ | 99.0％ | 0.8％ | 0.2％ |
Claims (8)
1. A method for producing anisole by catalyzing phenol and methanol is characterized by comprising the following steps:
(1) adding a carrier into deionized water, adding a modified component, stirring at normal temperature for 4-8 h, aging and drying at 80-100 ℃ for 10-12 h, roasting at 450-600 ℃ for 3-6 h, and cooling to room temperature to prepare a catalyst intermediate; the mass ratio of the carrier to the modified component to the deionized water is (0.01-0.05) to (2-5), the carrier is any one of zinc phosphate, iron phosphate, copper phosphate and chromium phosphate, and the modified component is any one of cerium nitrate, zirconium nitrate, lanthanum nitrate and nickel nitrate;
(2) adding the catalyst intermediate into deionized water, adding an auxiliary agent, stirring at normal temperature for 3-5 h, aging and drying at 90-110 ℃ for 10-12 h, and roasting at 450-600 ℃ for 4-8 h to prepare a catalyst; wherein the mass ratio of the catalyst intermediate to the auxiliary agent to the deionized water is 1 (0.001-0.01) to 2-5, and the auxiliary agent is any one of potassium fluoride, cesium fluoride and sodium fluoride;
(3) granulating and molding the obtained catalyst into cylindrical particles with the diameter of 3-6 mm and the height of 3-6 mm, and filling the cylindrical particles into a fixed bed reactor; after being preheated, phenol and methanol continuously pass through a fixed bed reactor, and are subjected to gas phase reaction to generate anisole under the reaction conditions of the reaction temperature of 280-350 ℃, the reaction pressure of 0.1-3 MPa and the material residence time of 20-40 s.
2. The method for producing anisole by catalyzing phenol with methanol as recited in claim 1, wherein: in the step (1), adding the carrier into deionized water, adding the modified component, stirring at normal temperature for 6 hours, aging and drying at 90 ℃ for 12 hours, roasting at 500-550 ℃ for 4-5 hours, and cooling to room temperature to prepare the catalyst intermediate.
3. The method for catalyzing phenol and methanol to produce anisole according to claim 1 or 2, characterized in that: in the step (1), the mass ratio of the carrier to the modified component to the deionized water is 1 (0.02-0.04) to (3-4), the carrier is any one of copper phosphate and chromium phosphate, and the modified component is any one of cerium nitrate, zirconium nitrate and nickel nitrate.
4. The method for catalyzing phenol and methanol to produce anisole according to claim 1, wherein: in the step (2), adding the catalyst intermediate into deionized water, adding an auxiliary agent, stirring at normal temperature for 4 hours, aging and drying at 100 ℃ for 12 hours, and roasting at 480-550 ℃ for 5-7 hours to prepare the catalyst.
5. The method for catalyzing phenol and methanol to produce anisole according to claim 1 or 4, wherein: in the step (2), the mass ratio of the catalyst intermediate to the auxiliary agent to the deionized water is 1 (0.004-0.008) to (3-4), and the auxiliary agent is any one of cesium fluoride and potassium fluoride.
6. The method for catalyzing phenol and methanol to produce anisole according to claim 1, wherein: in the step (3), the obtained catalyst is granulated and formed into cylindrical particles with the diameter of 4-5 mm and the height of 4-5 mm, and the cylindrical particles are filled into a fixed bed reactor; after being preheated, phenol and methanol continuously pass through a fixed bed reactor, and are subjected to gas phase reaction to generate anisole under the reaction conditions of the reaction temperature of 300-320 ℃, the reaction pressure of 0.5-1.5 MPa and the material residence time of 25-35 s.
7. The method for catalyzing phenol and methanol to produce anisole according to claim 1 or 6, wherein: in the step (3), the molar ratio of phenol to methanol is 1 (2-5).
8. The method for catalyzing phenol and methanol to produce anisole of claim 7 wherein: in the step (3), the molar ratio of phenol to methanol is 1 (3-4).
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| CN111187148B (en) * | 2020-02-24 | 2022-08-09 | 上海大学 | Method for simultaneously preparing o-hydroxy phenetole and 1, 3-benzodioxole-2-one |
| CN111298843B (en) * | 2020-04-03 | 2023-12-08 | 陕西煤业化工技术研究院有限责任公司 | Catalyst for catalyzing reaction of pyrogallol and dimethyl carbonate to synthesize 1,2, 3-trimethoxybenzene as well as preparation method and application thereof |
| CN113233963A (en) * | 2021-05-27 | 2021-08-10 | 宝鸡文理学院 | Method for preparing anisole from phenol and methanol |
| CN114736105B (en) * | 2022-04-19 | 2024-04-12 | 邵阳学院 | Method for synthesizing anisole by catalyzing calcium-aluminum composite oxide |
| CN115448820B (en) * | 2022-10-13 | 2023-12-05 | 南京工业大学 | Mild method for preparing aryl methyl ether from phenol and methanol |
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| CN1157283A (en) * | 1995-12-28 | 1997-08-20 | 株式会社日本触媒 | Process for production of alkyl ether of phenol and catalyst used therein |
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