CN108484352B - Method for preparing chloromethane by hydrochlorinating methanol - Google Patents
Method for preparing chloromethane by hydrochlorinating methanol Download PDFInfo
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- CN108484352B CN108484352B CN201810308960.2A CN201810308960A CN108484352B CN 108484352 B CN108484352 B CN 108484352B CN 201810308960 A CN201810308960 A CN 201810308960A CN 108484352 B CN108484352 B CN 108484352B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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Abstract
The invention discloses a method for preparing methyl chloride by hydrochlorinating methanol, which comprises the following steps: (1) preparing a catalyst; (2) and (3) carrying out hydrochlorination on the methanol to prepare the methyl chloride. The invention can obviously reduce the selectivity of dimethyl ether in the process of preparing methyl chloride, and simultaneously, the conversion rate of methanol and the yield of methyl chloride are higher.
Description
Technical Field
The invention belongs to the technical field of chloromethane preparation, and particularly relates to a method for preparing chloromethane by hydrochlorinating methanol.
Background
At present, the production technology of methane chloride is quite mature, the production method mainly comprises a methane chlorination method and a methanol hydrochlorination method, and the methanol hydrochlorination method can be divided into 3 technical routes: vapor-liquid phase non-catalytic methods, vapor-liquid phase catalytic methods, and gas-solid phase catalytic methods. Wherein the gas-solid phase catalysis method mainly adopts gamma-Al2O3The method is suitable for large-scale production, and has the advantages of high unit consumption of methanol, high selectivity of methyl chloride and low corrosivity in the reaction process, and the problem of low reactor quality is easily solved. Therefore, the catalytic preparation of methyl chloride by the gas-solid phase method is a widely adopted method in industrial production.
However, in the process of producing methyl chloride by catalytic reaction of methanol and hydrogen chloride, gamma-Al is used as a catalyst2O3Meanwhile, the catalyst is also a catalyst for preparing dimethyl ether by catalyzing methanol, so that a small amount of dimethyl ether is generated under the condition of methanol hydrochlorination reaction. Because the boiling points of dimethyl ether and chloromethane are very close, the separation is difficult, and the two components can not be effectively separated by adopting the conventional rectification separation method. Therefore, in most of the industries, concentrated sulfuric acid is used to separate methyl chloride and dimethyl ether, i.e., dimethyl ether is absorbed by the property of tin salt formed by the reaction between dimethyl ether and sulfuric acid. However, the method has extremely high requirements on the corrosion resistance of equipment and pipelines, and the maintenance cost of the equipment is increased. Meanwhile, the treatment of waste acid has great difficulty and great safety and environmental protection problems.
In some patent documents, a separation method of dissolution, absorption and desorption rectification is adopted to separate and purify dimethyl ether, such as US64588556B, CN104926595A, and the like, and this method is not a method, but a treatment process is added, which increases the equipment operation cost. Patent document US2005159633a1 describes that when η -alumina doped with an alkali metal salt is used as a catalyst in the reaction of methanol with hydrogen chloride, the selectivity to dimethyl ether is significantly reduced. However, according to the experimental verification of the method disclosed in the patent, although the alkali metal salt modified eta-alumina or activated alumina is favorable for the reduction of the formation of dimethyl ether, the reduction is not large, and the conversion rate of methanol is obviously reduced, which obviously has a great influence on the production efficiency and capacity of the device.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a method for preparing methyl chloride by hydrochlorinating methanol, which can obviously reduce the selectivity of dimethyl ether in the process of preparing methyl chloride and simultaneously has higher conversion rate of methanol and yield of methyl chloride.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing methyl chloride by methanol hydrochlorination is characterized by comprising the following steps:
(1) preparing a catalyst: dissolving nitrate or chloride of IIIB group elements in water, wherein the IIIB group elements are one or more than two of La, Ce or Y, soaking active alumina by adopting a wet impregnation method, and drying to finish the preparation of the new catalyst;
(2) preparing methyl chloride through methanol hydrochlorination: filling the prepared catalyst into a long tube reactor, electrically heating to control the reaction temperature to be 200-300 ℃, wherein the ratio of hydrogen chloride to methanol is (1-1.3): (0.5-1), and the material contact time is 3-10 s.
Further, the doped IIIB group elements in the step (1) are nitrates or chlorides of La, Ce and Y, and the soaking carrier is gamma-Al2O3The total load of the activated alumina doped with IIIB group elements is 2-8 wt%.
Further, the reaction temperature in the step (2) is 230-280 ℃.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the preparation method has simple process and low cost, and the conversion rate of methanol and the selectivity of chloromethane can be greatly improved after the prepared catalyst is adopted, so that the preparation method not only has remarkable economic benefit, but also greatly reduces the generation amount of the byproduct dimethyl ether, thereby reducing the waste sulfuric acid generated by absorbing and removing the dimethyl ether in the traditional method, and having obvious environmental protection benefit.
Detailed Description
The invention relates to a method for preparing methyl chloride by hydrochlorinating methanol, which comprises the following steps:
(1) preparing a catalyst: dissolving nitrate or chloride of IIIB group element in water, the IIIB group element is one or more of La, Ce or Y, and soaking gamma-Al by wet dipping method2O3And drying the activated alumina to complete the preparation of the new catalyst, wherein the total load of the doped IIIB group elements is 2-8 wt%.
(2) Preparing methyl chloride through methanol hydrochlorination: filling the prepared catalyst into a 800ml long tube reactor, wherein the specification of the long tube reactor is that the inner diameter of the tube is 26mm, the length of the tube is 1200mm, the reaction temperature is controlled by electric heating to be 200-300 ℃, preferably 230-280 ℃, and the ratio of hydrogen chloride to methanol is (1-1.3): (0.5-1), and the material contact time is 3-10 s.
The preparation method has simple process and low cost, the prepared catalyst is obtained by doping and modifying the industrial catalyst active alumina used in the traditional methyl chloride production by III-B group elements, the activity is high after modification, and the conversion rate of methanol and the selectivity of methyl chloride can be greatly improved after the catalyst is adopted, so that the preparation method not only has remarkable economic benefit, but also greatly reduces the generation amount of byproduct dimethyl ether, thereby reducing the waste sulfuric acid generated by absorbing and removing dimethyl ether in the traditional method, and having obvious environmental protection benefit.
Example 1
Adding La (NO)3)3·6H2Dissolving O in water to prepare an aqueous solution, and soaking hollow activated alumina with the particle size of 4-5 mm in the aqueous solution to obtain La (NO)3)3·6H2O solution concentration according to La minusCalculated and designed with the loading capacity of 3wt percent, and finally dried and loaded with alumina particles at 120 ℃ to obtain 3 percent of La-Al2O3. 800ml of 3% La-Al2O3Filling the mixture into a long tube reactor, electrically heating the reaction tube under the protection of nitrogen to raise the temperature to 230 ℃ in the middle of a bed layer, keeping the temperature for 1h, introducing methanol and hydrogen chloride gas, wherein the molar ratio of hydrogen chloride to methanol is 1.1:1, the passing time of the materials in a catalyst bed layer is 7s, the conversion rate of methanol is 99.6 percent, the selectivity of methyl chloride is 99.7 percent and the selectivity of dimethyl ether is 0.07 percent after the reaction is stable.
Example 2
Adding La (NO)3)3·6H2O and YCl3Dissolving the mixture in water to prepare an aqueous solution, and soaking hollow activated alumina with the particle size of 4-5 mm in the aqueous solution to obtain La (NO)3)3·6H2O and YCl3The solution concentration is calculated and designed according to the La load of 3 wt% and the Y load of 2 wt%, and finally the loaded alumina particles are dried at 120 ℃ to obtain 3% La-2% Y-Al2O3. 800ml of 3% La-2% Y-Al2O3Filling the mixture into a long tube reactor, electrically heating the reaction tube under the protection of nitrogen to raise the temperature to 230 ℃ in the middle of a bed layer, keeping the temperature for 1h, introducing methanol and hydrogen chloride gas, wherein the molar ratio of hydrogen chloride to methanol is 1.2:1, the passing time of the materials in a catalyst bed layer is 5s, the conversion rate of methanol is 99.8 percent, the selectivity of methyl chloride is 99.8 percent and the selectivity of dimethyl ether is 0.03 percent after the reaction is stable.
Example 3
Adding Ce (NO)3)3·6H2O and Y (NO)3)3·6H2Dissolving O in water to prepare an aqueous solution, and soaking hollow activated alumina with the particle size of 4-5 mm in the aqueous solution to obtain Ce (NO)3)3·6H2O and Y (NO)3)3·6H2The concentration of O solution is calculated and designed according to 5 wt% of Ce load and 1 wt% of Y load, and finally the loaded alumina particles are dried at 120 ℃ to obtain 5% Ce-1% Y-Al2O3. 800ml of 5% Ce-1% Y-Al2O3Filling the mixture into a long tube reactor, electrically heating the reaction tube to 280 ℃ in the middle of a bed layer under the protection of nitrogen, keeping the temperature for 1h, and introducing methanol and chlorineThe molar ratio of hydrogen chloride to methanol is 1.3:1, the passing time of materials in a catalyst bed layer is 3s, the conversion rate of methanol is 98.2 percent after the reaction is stable, the selectivity of methyl chloride is 99.1 percent, and the selectivity of dimethyl ether is 0.09 percent.
Example 4
Adding LaCl3、Ce(NO3)3·6H2O and Y (NO)3)3·6H2Dissolving O in water to prepare an aqueous solution, soaking hollow activated alumina with the particle size of 4-5 mm in the aqueous solution, and adding LaCl3、Ce(NO3)3·6H2O and Y (NO)3)3·6H2The concentration of O solution is calculated and designed according to the respective loading amounts of La, Y and Ce of 2 wt%, 5 wt% and 1 wt%, and finally the loaded alumina particles are dried at 120 ℃ to obtain 2% La-5% Y-1% Ce-Al2O3. 800ml of 2% La-5% Y-1% Ce-Al2O3Filling the mixture into a long tube reactor, electrically heating the reaction tube under the protection of nitrogen to raise the temperature to 250 ℃ in the middle of a bed layer, keeping the temperature for 1h, introducing methanol and hydrogen chloride gas, wherein the molar ratio of hydrogen chloride to methanol is 1.05:1, the passing time of the materials in a catalyst bed layer is 10s, the conversion rate of methanol is 99.5 percent, the selectivity of methyl chloride is 99.5 percent and the selectivity of dimethyl ether is 0.02 percent after the reaction is stable.
Comparative example 1
Filling 800ml of hollow activated alumina with particles of 4-5 mm into a long tube reactor, electrically heating the reaction tube to the middle temperature of a bed layer of 230 ℃ under the protection of nitrogen, keeping the temperature for 1h, introducing methanol and hydrogen chloride gas, wherein the molar ratio of the hydrogen chloride to the methanol is 1.2:1, the passing time of materials in a catalyst bed layer is 5s, the conversion rate of the methanol is 97.8 percent, the selectivity of methyl chloride is 98.5 percent, and the selectivity of dimethyl ether is 0.89 percent after the reaction is stable. Comparative example 2
800ml of hollow activated alumina 4-5 mm particles doped with CsCl 5% Cs-Al2O3Filling the mixture into a long tube reactor, electrically heating the reaction tube to 230 ℃ in the middle of a bed layer under the protection of nitrogen, keeping the temperature for 1h, introducing methanol and hydrogen chloride gas, wherein the molar ratio of the hydrogen chloride to the methanol is 1.2:1, the passing time of the materials in a catalyst bed layer is 5s, and carrying out reverse reactionAfter the reaction, the conversion rate of methanol is 81.5%, the selectivity of chloromethane is 98.7% and the selectivity of dimethyl ether is 0.72%.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made based on the present invention to solve the same technical problems and achieve the same technical effects are within the scope of the present invention.
Claims (3)
1. A method for preparing methyl chloride by methanol hydrochlorination is characterized by comprising the following steps:
(1) preparing a catalyst: dissolving nitrate or chloride of IIIB group elements in water, wherein the IIIB group elements are one or more than two of La, Ce or Y, soaking active alumina by adopting a wet impregnation method, and drying to finish the preparation of the new catalyst;
(2) preparing methyl chloride through methanol hydrochlorination: filling the prepared catalyst into a long tube reactor, electrically heating to control the reaction temperature to be 200-300 ℃, wherein the ratio of hydrogen chloride to methanol is (1-1.3): (0.5-1), and the material contact time is 3-10 s.
2. The process for the preparation of methyl chloride by hydrochlorination of methanol according to claim 1, characterized in that: the doped IIIB group elements in the step (1) are nitrates or chlorides of La, Ce and Y, and the soaking carrier is gamma-Al2O3The total load of the activated alumina doped with IIIB group elements is 2-8 wt%.
3. The process for the preparation of methyl chloride by hydrochlorination of methanol according to claim 1, characterized in that: the reaction temperature in the step (2) is 230-280 ℃.
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| DD237065A3 (en) * | 1980-04-30 | 1986-07-02 | Buna Chem Werke Veb | METHOD FOR PRODUCING LOWER ALKYL CHLORIDE |
| DD237058A3 (en) * | 1980-04-30 | 1986-07-02 | Buna Chem Werke Veb | METHOD FOR PRODUCING CATALYSTS BASED ON ACTIVE CARBON |
| JPS5944098B2 (en) * | 1981-08-03 | 1984-10-26 | 韓国科学技術院 | Method for producing methyl chloride |
| JP2003501255A (en) * | 1999-06-15 | 2003-01-14 | イネオス・クロール・リミテッド | Use of alkali metal treated eta-alumina as a catalyst for the treatment of methanol hydrochloride. |
| CN100998949A (en) * | 2006-01-10 | 2007-07-18 | 李群生 | Catalyst for preparing chloroethylene from acetylene hydrochlorination and its preparation method |
| CN101574657B (en) * | 2009-06-18 | 2011-06-29 | 河北科技大学 | Catalyst for preparing chloromethane and ammonia gas and preparation method thereof |
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