CN109678713B - Method for preparing diphenyl carbonate by ester exchange - Google Patents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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Abstract
The invention relates to a method for preparing diphenyl carbonate by transesterification of dimethyl carbonate and phenol, which mainly solves the problem of low activity of heterogeneous catalysts in the prior art. The catalyst is a titanium oxide system with a high proportion of exposed (001) crystal face modified by a composite oxide. The technical scheme of the invention effectively improves the activity and selectivity of the catalyst, better solves the problem of low activity of the catalyst in the reaction of synthesizing the diphenyl carbonate by the ester exchange of phenol and dimethyl carbonate, and can be used in the industrial production of the diphenyl carbonate.
Description
Technical Field
The invention relates to a method for preparing diphenyl carbonate by phenol ester exchange.
Background
Diphenyl carbonate (DPC) is a raw material for preparing polycarbonate by a non-phosgene method, and the conventional preparation method is a phosgene method, which is restricted by policy due to potential harm of the highly toxic phosgene to the environment and safety production. The process for synthesizing diphenyl carbonate by the ester exchange reaction of phenol (PhOH) and dimethyl carbonate (DMC) under the action of a catalyst avoids using a highly toxic raw material phosgene, and a main byproduct methanol can be recycled for synthesizing a starting raw material dimethyl carbonate, so that the method is a green process route with the most industrial prospect.
At present, the ester exchange of dimethyl carbonate and phenol to synthesize diphenyl carbonate uses homogeneous catalyst. Niu et al [ H.Niu et al, J.mol.Catal.A 235(2005)240]Using Cp2TiCl2As catalyst, conversion of phenol under optimized conditionsThe yield was 46.8%, and the selectivity to diphenyl carbonate was 54.9%. Lee et al [ H.Lee et al, Catal. Today87(2003)139]Using Bu2SnO as a catalyst, CF3SO3H is used as an auxiliary agent, and under the optimized conditions, the conversion rate of the dimethyl carbonate is 58.5 percent, and the yield of the diphenyl carbonate is 18.3 percent. Many processes using homogeneous titanium catalysts have also achieved good results [ d.andre et al, US 20100010252; p.cao et al, j.mol.catal. (China)24(2010) 492; gao, chi.j.catal.22 (2001)405]. Homogeneous catalysts have the problem of difficult separation from the product and are not easy to reuse, so that heterogeneous catalysts are the main direction for future development, and documents report different oxides such as lead, zinc, tin, titanium and the like. Wherein the TiO is2As an effective ingredient, has received wide attention. Puxin, etc. uses titanium dioxide as catalyst, the conversion rate of phenol can reach 33.7%, and the ester exchange selectivity is good. Yi Longping (Natural gas chemical industry, 2616, 41, 60)]Titanium dioxide is dispersed on carbon to catalyze phenol and dimethyl carbonate to carry out ester exchange to synthesize diphenyl carbonate, the conversion rate of phenol is 39.6 percent, and the selectivity of diphenyl carbonate reaches 75.6 percent.
Disclosure of Invention
The invention aims to solve the problem of low reaction activity of a catalyst in diphenyl carbonate synthesis in the prior art, and develops a method for preparing diphenyl carbonate by phenol ester exchange.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for preparing diphenyl carbonate by the ester exchange reaction of dimethyl carbonate and phenol comprises the following steps: adopts a composite oxide modified (001) crystal face titanium oxide catalytic system.
Dimethyl carbonate and phenol are used as raw materials, the reaction temperature is 120-190 ℃, and the molar ratio of the dimethyl carbonate to the phenol is 0.5-5: 1, the reaction time is 5-50 h, and the weight ratio of the catalyst to the phenol is 0.01-0.5: 1. the reaction is divided into two steps, the temperature of the first step is 140-180 ℃, and the molar ratio of dimethyl carbonate to phenol is 1-3: 1, dropwise adding dimethyl carbonate for 2-6 h, reacting at the temperature of 140-180 ℃ for the second step of reaction for 5-20 h, wherein the weight ratio of the catalyst to phenol is 0.05-0.5: 1; the catalyst for the two-step reaction is the same, and the weight ratio of the catalyst to the phenol is 0.01-0.5: 1.
in the above technical solution, preferably, the exposure ratio of the (001) crystal plane of the titanium oxide in the titanium oxide catalyst system is 20 to 90%, and particularly preferably, the exposure ratio is 30 to 70%.
Wherein the exposure ratio is the ratio of the (001) crystal plane area to the crystal plane area of the single crystal particle.
In the above scheme, preferably, the composite oxide in the titanium oxide catalyst system is an alkaline earth or alkali metal oxide. Particularly preferably, the composite oxide in the titanium oxide catalytic system is one or more of manganese oxide, iron oxide, copper oxide and zinc oxide.
In the above aspect, the molar ratio of the composite oxide to the titanium oxide in the titanium oxide catalyst system is preferably 0.001 to 0.5, and particularly preferably 0.005 to 0.3.
In the above technical scheme, preferably, the molar ratio of dimethyl carbonate to phenol is 0.5-5: 1, particularly preferably 1 to 3: 1.
In the technical scheme, the reaction temperature in the first step is preferably 120-190 ℃, particularly preferably 140-185 ℃, and the reaction time is 5-50 h.
In the technical scheme, the reaction temperature in the second step is preferably 140-180 ℃, and the reaction time is 5-20 h.
The preparation method of the catalyst comprises the following steps:
1) putting titanium and a composite oxide precursor into a hydrothermal kettle;
2) adding a solvent;
3) adding acid and fluoride;
4) sealing the hydrothermal kettle, performing hydrothermal reaction, cooling and filtering;
5) washing with alkali liquor, drying and roasting to obtain the catalyst for reaction.
In the above scheme, preferably, the titanium precursor may be selected from one or more of titanium chloride, titanium fluoride, titanium sulfate, and titanate;
in the above scheme, preferably, the precursor of the composite oxide is one or more of chloride, nitrate and sulfate of manganese, iron, copper, zinc and tin; particularly preferably one or more of copper, zinc chloride and nitrate.
In the above scheme, preferably, the solvent is one or more of water, alcohol, ether and ester;
in the above scheme, preferably, the acid is one or more of sulfuric acid, hydrochloric acid, nitric acid and hydrofluoric acid;
in the above scheme, preferably, the fluoride is one or more of hydrofluoric acid, sodium fluoride and potassium fluoride;
in the above aspect, preferably, when the titanium precursor is tetrabutyl titanate and the fluorine precursor is hydrofluoric acid, the molar ratio of titanium to fluorine is 1:0.2 to 1.
In the scheme, the hydrothermal reaction temperature is preferably 100-200 ℃, and the reaction time is 6-72 hours;
in the above scheme, preferably, the alkali source is sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, triethylamine
Or one or more of triethanolamine;
in the scheme, the roasting temperature is preferably 100-400 ℃, and particularly preferably 120-300 ℃.
The method adopts a titanium oxide composite catalytic system with exposed (001) crystal face, is a good heterogeneous catalyst, and under a certain exposure ratio, titanium oxide and composite oxide act synergistically, so that high reaction activity and selectivity are maintained, and the titanium oxide can be quickly separated from the system after reaction. At the reaction temperature of 180 ℃ in the first step, the molar ratio of dimethyl carbonate to phenol is 2, the dropping time of dimethyl carbonate is 4 hours, the reaction temperature of 180 ℃ in the second step is 10 hours, and the weight ratio of the catalyst to phenol is 0.2: under the condition of 1, the conversion rate of phenol is 59.5 percent, the selectivity of diphenyl carbonate is 85.3 percent, the selectivity of methyl phenyl carbonate is 14.7 percent, the catalyst is repeatedly used for 10 times, the activity is not obviously reduced, and better technical effects are obtained.
The invention is further illustrated by the following examples. It is to be noted that the following examples are only for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention.
Detailed Description
[ example 1 ]
Putting 50ml of tetrabutyl titanate and 1.12g of zinc nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, adding 10ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 160 ℃ for 24h, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M NaOH, drying at 110 ℃ for standing overnight, and roasting in a muffle furnace at 200 ℃ for 4h to obtain a sample, which is marked as T1, wherein the exposure ratio of the crystal face of titanium oxide (001) is 65%.
[ example 2 ]
Putting 50ml of tetrabutyl titanate and 2.24g of zinc nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, adding 12ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 160 ℃ for 24 hours, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M NaOH, drying at 110 ℃ for standing overnight, and roasting in a muffle furnace at 200 ℃ for 4 hours to obtain a sample, which is marked as T2, wherein the exposure ratio of the crystal face of titanium oxide (001) is 70%.
[ example 3 ]
Putting 50ml of tetrabutyl titanate and 4.47g of zinc nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, adding 12ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 160 ℃ for 24 hours, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M NaOH, drying at 110 ℃ for standing overnight, and roasting in a muffle furnace at 200 ℃ for 4 hours to obtain a sample, which is marked as T3, wherein the exposure ratio of the crystal face of titanium oxide (001) is 70%.
[ example 4 ]
Putting 50ml of tetrabutyl titanate and 5.63g of copper nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, adding 12ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 170 ℃ for 24h, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M sodium carbonate, drying at 110 ℃ for standing overnight, and roasting in a muffle furnace at 200 ℃ for 3h to obtain a sample, which is recorded as a sample T4, wherein the exposure ratio of the crystal face of titanium oxide (001) is 70%.
[ example 5 ]
Putting 50ml of tetrabutyl titanate and 5.7g of ferric nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, adding 14ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 170 ℃ for 24h, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M sodium carbonate, drying at 110 ℃ for standing overnight, and roasting in a muffle furnace at 200 ℃ for 3h to obtain a sample, which is recorded as a sample T5, wherein the exposure ratio of the crystal face of titanium oxide (001) is 75%.
[ example 6 ]
Putting 50ml of tetrabutyl titanate and 2.7g of manganese nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, adding 14ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 170 ℃ for 24h, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M sodium carbonate, drying at 110 ℃ for standing overnight, and roasting in a muffle furnace at 200 ℃ for 3h to obtain a sample, which is recorded as a sample T6, wherein the exposure ratio of the crystal face of titanium oxide (001) is 75%.
[ example 7 ]
50ml of titanium fluoride and 4.47g of zinc nitrate are put into a dry hydrothermal kettle, 10ml of saturated NaF aqueous solution is added, the reaction kettle is sealed and is kept overnight for 24 hours at 160 ℃, the mixture is cooled to room temperature and then is centrifugally separated, the mixture is washed for 5 times by 0.1M NaOH, and a sample is obtained after 110-hour overnight drying, and the sample is recorded as a sample T7, wherein the exposure ratio of the crystal face of titanium oxide (001) is 70%.
Comparative example 1
And (2) putting 50ml of tetrabutyl titanate into a dry hydrothermal kettle, adding 10ml of aqueous solution, sealing the reaction kettle, standing overnight at 160 ℃ for 24 hours, cooling to room temperature, performing centrifugal separation, washing with 0.1M NaOH for 5 times, and drying at 110 ℃ overnight to obtain a sample, which is recorded as a sample T8, wherein the exposure ratio of the crystal face of titanium oxide (001) is 8%.
Comparative example 2
And (2) putting 50ml of tetrabutyl titanate into a dry hydrothermal kettle, adding 25ml of HF aqueous solution, sealing the reaction kettle, standing overnight at 160 ℃ for 24 hours, cooling to room temperature, performing centrifugal separation, washing with 0.1M NaOH for 5 times, and drying at 110 ℃ overnight to obtain a sample, which is recorded as a sample T9, wherein the exposure ratio of the crystal face of titanium oxide (001) is 95%.
Comparative example 3
And (2) putting 50ml of tetrabutyl titanate and 2.24g of zinc nitrate into a dry hydrothermal kettle, adding 50ml of deionized water, sealing the reaction kettle, standing overnight for 24 hours at 160 ℃, cooling to room temperature, performing centrifugal separation, washing for 5 times by using 0.1M NaOH, drying at 110 ℃ for one night, and roasting at 200 ℃ in a muffle furnace for 4 hours to obtain a sample, namely T10, wherein the exposure ratio of the crystal face of titanium oxide (001) is 8%.
[ example 8 ]
Adding catalyst T15.0 g into a three-neck flask connected with a gas guide tube, a temperature control thermocouple, a constant pressure dropping funnel and a rectifying column, introducing nitrogen, adding phenol 50.0g, heating to 175 ℃, then starting to drop 95.7g of DMC, wherein the dropping time is 4h, the dropping speed is 25g/h, and simultaneously distilling off azeotrope of DMC and methanol through the rectifying column. After the dropwise addition, the reaction was continued at 175 ℃ for 10 hours, while the disproportionation product DMC was distilled off through a rectifying column, and after the reaction was completed, the conversion of phenol was 59.5%, the selectivity for diphenyl carbonate was 85.3%, and the selectivity for methyl phenyl carbonate was 14.7% by chromatography.
[ example 9 ]
The catalysts prepared in examples 1 to 7 and comparative examples 1 to 3 were used in the reaction of dimethyl carbonate and phenol under the same conditions as in example 8, and the reaction results were as shown in table 1:
TABLE 1
[ example 19 ]
After the reaction, the catalyst T2 was separated, washed with ethanol, dried in an oven at 120 ℃ for 12 hours, and then reacted again, and the reaction was repeated 10 times, and the results obtained are shown in table 2.
TABLE 2
Claims (6)
1. A method for preparing diphenyl carbonate by the ester exchange reaction of dimethyl carbonate and phenol is characterized in that a (001) crystal face titanium oxide catalytic system modified by composite oxide is adopted; the (001) crystal face exposure ratio of titanium oxide in the titanium oxide catalytic system is 20-90%;
the preparation method of the titanium oxide catalyst system comprises the following steps:
1) putting titanium and a composite oxide precursor into a hydrothermal kettle;
2) adding a solvent;
3) adding acid and fluoride;
4) sealing the hydrothermal kettle, performing hydrothermal reaction, cooling and filtering;
5) washing with alkali liquor, drying and roasting to obtain the catalyst for reaction.
2. The method according to claim 1, wherein the reaction temperature is 120-190 ℃, and the molar ratio of dimethyl carbonate to phenol is 0.5-5: 1, the reaction time is 5-50 h, and the weight ratio of the catalyst to the phenol is 0.01-0.5: 1.
3. the method according to claim 1, wherein the reaction is carried out in two steps, the temperature of the first step is 140-180 ℃, and the molar ratio of dimethyl carbonate to phenol is 1-3: 1, dropwise adding dimethyl carbonate for 2-6 h, reacting at the temperature of 140-180 ℃ for the second step of reaction for 5-20 h, wherein the weight ratio of the catalyst to phenol is 0.05-0.5: 1; the catalyst for the two-step reaction is the same, and the weight ratio of the catalyst to the phenol is 0.01-0.5: 1.
4. the method of claim 1, wherein the composite oxide in the titanium oxide catalyst system is one or more oxides of manganese, iron, copper, zinc, and tin.
5. The method of claim 1, wherein the molar ratio of the complex oxide to the titanium oxide in the titanium oxide catalyst system is 0.001 to 0.5.
6. The preparation method according to claim 1, wherein the titanium precursor is selected from one or more of titanium chloride, titanium fluoride, titanium sulfate and titanate; the precursor of the composite oxide component is one or more of chloride, nitrate and sulfate of manganese, iron, copper, zinc and tin; the solvent is one or more of water, alcohol, ether and ester; the acid is one or more of sulfuric acid, hydrochloric acid, nitric acid and hydrofluoric acid; the fluoride is one or more of hydrofluoric acid, sodium fluoride and potassium fluoride; the hydrothermal reaction temperature is 100-200 ℃, and the hydrothermal reaction time is 6-72 h; the alkali source is one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, triethylamine or triethanolamine; the roasting temperature is 100-400 ℃.
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| CN111170972A (en) * | 2019-12-28 | 2020-05-19 | 安徽中羰碳一工业技术有限责任公司 | Method for synthesizing benzofuranone by one-step method |
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| CN102050740A (en) * | 2009-08-18 | 2011-05-11 | 中国科学院成都有机化学有限公司 | Method for interesterification synthesis of diphenyl carbonate by dimethyl carbonate |
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| CN106345475A (en) * | 2016-09-24 | 2017-01-25 | 上海大学 | Preparation method of titanium dioxide specific crystal face carrying ferric oxide denitration catalyst |
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| CN101128572A (en) * | 2005-02-21 | 2008-02-20 | 株式会社日本触媒 | Method for producing fatty acid alkyl esters and/or glycerin |
| CN102050740A (en) * | 2009-08-18 | 2011-05-11 | 中国科学院成都有机化学有限公司 | Method for interesterification synthesis of diphenyl carbonate by dimethyl carbonate |
| CN105032406A (en) * | 2015-07-09 | 2015-11-11 | 河海大学 | Preparation method and application for palladium-modified titanium dioxide with three-dimensional flower-like structure exposure [001] crystal face |
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