WO2024063425A1 - Procédé de production de chlorure de méthyle à efficacité énergétique améliorée à l'aide d'une réaction en plusieurs étapes - Google Patents

Procédé de production de chlorure de méthyle à efficacité énergétique améliorée à l'aide d'une réaction en plusieurs étapes Download PDF

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WO2024063425A1
WO2024063425A1 PCT/KR2023/013632 KR2023013632W WO2024063425A1 WO 2024063425 A1 WO2024063425 A1 WO 2024063425A1 KR 2023013632 W KR2023013632 W KR 2023013632W WO 2024063425 A1 WO2024063425 A1 WO 2024063425A1
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reaction
methane
methyl chloride
methanol
energy efficiency
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Korean (ko)
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채호정
김영민
박명준
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/06—Preparation of halogenated hydrocarbons by addition of halogens combined with replacement of hydrogen atoms by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
    • C07C19/03—Chloromethanes

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  • the present invention relates to a method for producing methyl chloride by a multi-step reaction with improved energy efficiency, and more specifically, in the process of producing methyl chloride through methane chlorination, chloride, a by-product generated in the methane chlorination reaction, which is the primary reaction,
  • This relates to a method for producing methyl chloride through a multi-step reaction that can improve process energy efficiency by converting hydrogen into methyl chloride by adding methanol as a secondary reaction without separately separating and recovering hydrogen.
  • Korean Patent Publication KR 10-1979-0001615 B1 (published on November 23, 1979) relates to a process for chlorinating methane and adopts a step of recycling unreacted products, and hydrogen chloride (HCl), a by-product of the chlorination reaction.
  • a process for separating and recovering is presented.
  • Korean Patent KR 10-2087960 (announced on March 12, 2020) proposes to combine hydrogen chloride, a by-product of the chlorination reaction, with methanol and By converting it into methyl chloride through reaction, a method is proposed to efficiently treat harmful hydrogen chloride generated as a by-product of the chlorination reaction and at the same time improve the overall production amount of methyl chloride.
  • the prior art separates methyl chloride and hydrogen chloride from the methane chlorination reaction product and then reacts the separated hydrogen chloride with methanol.
  • Methods for the separation include absorption separation using the solubility of hydrogen chloride in water, or deep cold separation by compressing, cooling, and liquefying the gas and then separating it by distillation using the difference in boiling point.
  • absorption separation using the solubility of hydrogen chloride in water
  • deep cold separation by compressing, cooling, and liquefying the gas and then separating it by distillation using the difference in boiling point.
  • Patent Document 1 Korean Patent Gazette KR 10-1979-0001615 B1 (1797.11.23. Announcement date)
  • Patent Document 2 Korean Patent Publication KR 10-2087960 B1 (2020.03.12. Announcement date)
  • Non-patent Document 1 Appl. Catal., 11(1984), 35
  • the present invention was created to solve the above problems.
  • methyl chloride is produced through a methane chlorination reaction, and as a secondary reaction, hydrogen chloride produced as a by-product in the methane chlorination reaction is reacted with methanol to produce chloride.
  • chlorinated methane such as methyl chloride is separated from the primary reaction product of the methane chlorination reaction, and methanol is produced without separating hydrogen chloride from the mixture of unreacted methane and hydrogen chloride remaining.
  • the purpose is to provide a method for producing methyl chloride that can improve process energy efficiency by reacting methanol with hydrogen chloride by contacting it with or directly contacting the product mixture after the reaction with methanol.
  • the present invention includes the following steps: 1) conducting a chlorination reaction of methane and chlorine gas to obtain a first reaction product containing methyl chloride, unreacted methane, and hydrogen chloride; 2) separating chlorinated methane (XCM) from the first reaction product; 3) reacting methanol with the first reaction product from which chlorinated methane (XCM) containing unreacted methane and hydrogen chloride was separated in step 2) to produce a second reaction product containing unreacted methane and methyl chloride step; 4) separating unreacted methane from the second reaction product and returning it to step 1); 5) separating methyl chloride from the second reaction product from which the unreacted methane was separated in step 4) and the chlorinated methane (XCM) separated in step 2); energy efficiency, comprising: A method for producing methyl chloride by this improved multi-step reaction is provided.
  • methane and chlorine gas in step 1), can be chlorinated under oxygen-free conditions in the presence of a sulfated metal oxide catalyst or a crystalline carbon material catalyst, at a temperature of 200 to 500 ° C., methane to chlorine It may be carried out at a gas molar ratio of 10:1 to 1:5 and a gas time space velocity (GHSV) of the reactants of 500 to 10000 cc/g/h.
  • GHSV gas time space velocity
  • step 3) may be a gas phase reaction of the hydrogen chloride and methanol in the presence of a metal oxide catalyst including an alumina catalyst, and the reaction conditions include a temperature of 250 to 450° C., hydrogen chloride to methanol. It may be characterized as being carried out at a molar ratio of 3:1 to 1:3 and a gas time space velocity (GHSV) of the reactants of 500 to 10000 cc/g/h.
  • GHSV gas time space velocity
  • step 4 a step of removing water in advance may be further included.
  • the present invention is another example of a method for producing methyl chloride through a multi-step reaction with improved energy efficiency, comprising: a) reacting methane and chlorine gas to obtain a first reaction product containing methyl chloride, unreacted methane, and hydrogen chloride; ; b) adding methanol to the first reaction product to obtain a second reaction product in which methyl chloride is additionally produced by the reaction of hydrogen chloride and methanol; c) separating unreacted methane from the second reaction product and returning it to step a); d) separating methyl chloride from the second reaction product from which the unreacted methane was separated; providing a method for producing methyl chloride by a multi-step reaction with improved energy efficiency, comprising:
  • methane and chlorine gas in step a), can be chlorinated under oxygen-free conditions in the presence of a sulfated metal oxide catalyst or a crystalline carbon material catalyst, and the reaction conditions include a temperature of 200 to 500 ° C. It can be carried out at a molar ratio of methane to chlorine gas of 10:1 to 1:5 and a gas hourly space velocity (GHSV) of the reactants of 500 to 10000 cc/g/h.
  • GHSV gas hourly space velocity
  • step b) may be a gas phase reaction of hydrogen chloride and methanol in the presence of a metal oxide catalyst including an alumina catalyst, and the reaction conditions include a temperature of 250 to 450 ° C. and a ratio of hydrogen chloride to methanol. It may be characterized as being carried out at a molar ratio of 3:1 to 1:3 and a gas time space velocity (GHSV) of the reactants of 500 to 10000 cc/g/h.
  • GHSV gas time space velocity
  • step c) of the present invention a step of previously removing water may be further included.
  • the present invention is a method for producing methyl chloride through a multi-step reaction in which methyl chloride is produced through a methane chlorination reaction as a first reaction, and methyl chloride is produced by reacting hydrogen chloride produced as a by-product in the methane chlorination reaction with methanol as a secondary reaction.
  • chlorinated methane such as methyl chloride is separated and the remaining unreacted methane and hydrogen chloride are contacted with methanol without being separated, or the product mixture after the reaction is directly contacted with methanol to form methanol and hydrogen chloride.
  • unreacted methane, methyl chloride, etc. contained in the reaction product of the methane chlorination reaction can act as an inert gas for the reaction and serve as a buffer for the reaction heat, allowing the methanol hydrochlorination reaction to proceed stably. There is a possible effect.
  • Figure 1 shows a process of performing a methanol hydrochlorination reaction by contacting methanol without separating hydrogen chloride from the mixture of unreacted methane and hydrogen chloride remaining after separating the chlorinated methane after methane chlorination according to an embodiment of the present invention.
  • This is a schematic diagram.
  • Figure 2 is a schematic diagram of a process for performing a methanol hydrochlorination reaction by directly contacting the product mixture with methanol after the reaction according to an embodiment of the present invention.
  • Figure 3 is a schematic diagram of the process used for computer simulation in Example 1 of the present invention
  • Figure 4 is a schematic diagram of the process used for computer simulation in Example 2
  • Figure 5 is a schematic diagram of the process used for computer simulation in Comparative Example 1. This is a schematic diagram of the process used.
  • the present invention is a multi-step reaction comprising producing methyl chloride through a methane chlorination reaction as a first reaction and producing methyl chloride by reacting hydrogen chloride, a by-product generated from the methane chlorination, with methanol as a secondary reaction.
  • hydrogen chloride is selectively mixed with methanol. It relates to a method for producing methyl chloride through a multi-step reaction that can improve process energy efficiency by reacting to produce methyl chloride and leaving behind only unreacted methane.
  • the method for producing methyl chloride by a multi-step reaction with improved energy efficiency includes the following steps.
  • step 3 reacting methanol with the first reaction product from which chlorinated methane (XCM) containing unreacted methane and hydrogen chloride was separated in step 2) to produce a second reaction product containing unreacted methane and methyl chloride step;
  • XCM chlorinated methane
  • step 1) methane and chlorine gas are chlorinated without a catalyst or in the presence of a catalyst to produce a first reaction product containing methyl chloride and hydrogen chloride.
  • the reactants, methane and chlorine gas are It is continuously introduced into the first reactor and a chlorination reaction occurs within the first reactor.
  • the first reaction product according to the chlorination reaction includes unreacted methane, unreacted chlorine, and chlorinated methane.
  • the chlorinated methane (XCM) includes the target product, methyl chloride (CH 3 Cl, MCM), and other chlorides of methane, such as methylene chloride (CH 2 Cl 2 ), chloroform (CHCl 3 ), and tetrachloromethane (CCl 4 ). You can.
  • the reaction conditions for the chlorination reaction are preferably 200 to 500°C, and more preferably 300 to 400°C. Additionally, the molar ratio of methane to chlorine gas is preferably 10:1 to 1:5, and more preferably 5:1 to 1:1. In addition, the gas hourly space velocity (GHSV) of the reactants is preferably 500 to 10,000 cc/g/h, and more preferably 1,000 to 5,000 cc/g/h.
  • GHSV gas hourly space velocity
  • step 1) can simplify the process by performing the reaction under oxygen-free conditions.
  • the first reactor in step 1) is not particularly limited in form or type, and is illustratively a fluidized bed reactor capable of continuously introducing reactants or transferring products to another place, or a circulating fluidized bed reactor such as a riser.
  • a fluidized bed reactor capable of continuously introducing reactants or transferring products to another place
  • a circulating fluidized bed reactor such as a riser.
  • the use of other types of reactors such as fixed bed reactors is not limited.
  • the chlorination reaction may be carried out without a catalyst or in the presence of a catalyst
  • the catalyst used during the catalytic reaction is not particularly limited, but may be at least one of a zeolite-based catalyst, a metal oxide catalyst, and a crystalline carbon material catalyst, most preferably. may be a crystalline carbon material catalyst.
  • the zeolite-based catalyst may be at least one selected from the group consisting of H-MOR, H-ZSM-5, Na-L, Na-X, and Na-Y, and the metal oxide catalyst may be a sulfated metal oxide catalyst. there is. Additionally, the sulfated metal oxide catalyst may be at least one selected from the group consisting of a sulfated zirconia catalyst and a sulfated tin oxide catalyst.
  • the sulfated zirconia catalyst preferably includes the following steps: i) mixing an amine reactant and a zirconium precursor containing an oxygen element, and then dissolving the mixture in a solvent to form a mixed solution; ii) heating and stirring the mixed solution formed in step a) to form a gel-shaped product; iii) calcination of the gel-shaped product formed in step ii) to form zirconia (ZrO 2 ); iv) preparing sulfated zirconia (SO 4 2- /ZrO 2 ) by impregnating the zirconia formed in step iii) in a solution containing a sulfur oxidizing agent and then heating to evaporate the solvent; and v) calcining the sulfated zirconia prepared in step iv) at 500 to 800° C. in an air atmosphere.
  • the amine reactant used in the method for producing the sulfated zirconia catalyst is preferably selected from aspartic acid, glutamic acid, glycine, taurine, sarcosine, iminodiacetate, alanine, phenylalanine, isoleucine, histidine, lysine, arginine and water-soluble salts thereof.
  • the zirconium precursor containing the oxygen element is preferably ZrOC1 2 ⁇ 8H 2 O (zirconyl chloride octahydrate) and ZrO(NO 3 ) 2 ⁇ xH 2 O (zirconium (IV) oxynitric acid hydrate, Zirconium ( IV) oxynitrate hydrate).
  • the content of sulfate ions (SO 4 2- ) in the sulfated zirconia catalyst may preferably be 10.0 wt% or more.
  • the total acid density of the sulfated zirconia catalyst by the ammonia elevated temperature desorption method (NH 3 -TPD) may preferably be 8 mmolNH 3 /g or more, and the acid density of the super strong acid point (acid point with an acid point desorption temperature of more than 400 ° C.) The ratio may be more than 80% of the total acid density.
  • the sulfated tin oxide (SO 4 2- /SnO 2 ) catalyst is preferably i) dissolved in a tin precursor in a solvent, and then dissolved in aqueous ammonia until the pH of the solution reaches 7.5 or higher.
  • the tin precursor used in the method for producing the sulfated tin oxide catalyst is preferably at least one selected from SnCl 2 , SnCl 2 ⁇ 2H 2 O, CH 3 (CH 2 )3SnCl 3 , SnCl 4 ⁇ 5H 2 O, and SnCl 4 It could be more than that.
  • the content of sulfate ions (SO 4 2- ) in the sulfated tin oxide catalyst may preferably be 5.0 wt% or more.
  • the total acid density of the sulfurized tin oxide catalyst by the ammonia elevated temperature desorption method may preferably be 3.0 mmolNH 3 /g or more, and the super strong acid point (acid point with an acid point desorption temperature of more than 400 °C) may be preferably 3.0 mmolNH 3 /g or more.
  • the acid density ratio may be more than 50% of the total acid density.
  • the crystalline carbon material catalyst may be at least one selected from the group consisting of graphene, carbon nanotubes, and graphite.
  • the crystalline carbon material catalyst may be in the form of a transition metal supported or not supported, and the transition metal is preferably ruthenium (Ru), platinum (Pt), rhodium (Rh), cobalt (Co), and nickel (Ni). and palladium (Pd).
  • the crystalline carbon material catalyst supported with a transition metal preferably includes the steps of i) supporting a transition metal on a crystalline carbon material catalyst; ii) drying the result of step i); and iii) baking the result of step ii) above. In step ii), the result of step i) is dried.
  • drying may be preferably performed at 60 to 150°C, and more preferably at 80 to 120°C.
  • step iii) the result of step ii) is fired.
  • the firing may be preferably performed at 200 to 700°C, and more preferably at 300 to 500°C.
  • Step 2) above is a step of separating chlorinated methane, unreacted methane, and hydrogen chloride from the first reaction product.
  • the first reaction product produced in step 1) is introduced into the third separator, and chlorinated methane is separated from the first reaction product in the third separator.
  • chlorinated methane XCM
  • XCM chlorinated methane
  • chlorinated methane XCM
  • XCM chlorinated methane
  • the first reaction product after the chlorinated methane (XCM) is separated as described above includes at least unreacted methane and hydrogen chloride, and the first reaction product after the methyl chloride is separated is the next step without performing a separate additional separation process. used in the reaction.
  • step 3 methanol is added to the first reaction product from which unreacted methane and chlorinated methane (XCM) containing hydrogen chloride were separated in step 2), and methyl chloride is additionally produced by the reaction of hydrogen chloride and methanol. get results.
  • XCM unreacted methane and chlorinated methane
  • the second reaction product according to the reaction in step 3) includes methyl chloride and unreacted methane, and may also include dimethyl ether (CH 3 OCH 3 ) and water (H 2 O) as reaction by-products.
  • the temperature is preferably 250 to 450°C, and more preferably 300 to 400°C.
  • the molar ratio of hydrogen chloride to methanol is preferably 3:1 to 1:3, and more preferably 1.5:1 to 1:1.5.
  • the gas hourly space velocity (GHSV) of the reactants is preferably 500 to 10,000 cc/g/h, and more preferably 1,000 to 5,000 cc/g/h.
  • the reaction in step 3) can be carried out as a catalytic or non-catalytic reaction, and in the case of a catalytic reaction, there is no particular limitation on the catalyst used as long as the methanol conversion rate can be induced to 90% or more, but preferably a metal Oxide catalysts can be used, and the metal oxide catalyst may contain only one metal or may be in a complex form containing two or more different metals.
  • the metal oxide catalyst preferably includes an alumina catalyst, and the alumina catalyst is most preferably a mesoporous alumina catalyst.
  • the BET specific surface area of the metal oxide catalyst may be preferably 200 m2/g or more, more preferably 300 m2/g or more, and most preferably It may be 330 to 350 m2/g.
  • the average pore size of the mesoporous alumina catalyst may preferably be 3.0 nm to 30.0 nm, and more preferably 3.0 nm to 10.0 nm.
  • the second reactor in step 3) is not particularly limited in form or type, and may be, for example, a fluidized bed reactor capable of continuously introducing reactants or transferring products to another location, or a circulating fluidized bed reactor such as a riser. , the use of other types of reactors such as fixed bed reactors is not limited.
  • step 4 unreacted methane is separated from the second reaction product in step 3) and returned to step 1).
  • the second reaction product produced in step 3) is first introduced into a water separator to remove water, and then introduced into the first separator, and the second reaction product produced in step 3) is first introduced into the water separator. 2 It can be in the form of separation of the components of the reaction product.
  • dimethyl ether may also be produced as a reaction by-product in the second reaction product, and by-products such as dimethyl ether may be separately separated and recovered before flowing into the first separator.
  • Chlorinated methane (XCM) from which unreacted methane has been removed is discharged from the bottom of the first separator. At this time, the chlorinated methane (XCM) separated to the bottom is mainly discharged to the bottom because the second reactor produces only methyl chloride through the reaction of hydrogen chloride and methanol.
  • step 5 the XCM discharged from the bottom of the first separator in step 4) is introduced into a second separator to separate and recover methyl chloride.
  • a second separator There is no particular limitation as to the separation process method for the components in the second separator as long as a method known to those skilled in the art is used, but distillation, which separates the components according to differences in boiling points, is preferable.
  • Methyl chloride is separated and stored separately, and there is no particular limitation as long as the separation process method known to those skilled in the art is used.
  • FIG. 2 Another embodiment according to the invention is shown in Figure 2.
  • the method for producing reactive methyl chloride according to FIG. 2 relates to a method for producing methyl chloride through a multi-step reaction that can improve process energy efficiency by reacting hydrogen chloride with methanol in the product mixture after the reaction without a separate process of separating and recovering it.
  • the method for producing methyl chloride by a multi-step reaction with improved energy efficiency includes the following steps.
  • step 2 of first separating chlorinated methane (XCM) from the product after the reaction in the method of FIG. 1, and methanol is added directly to the product after the reaction.
  • a reaction is performed to produce methyl chloride by contacting with . That is, it corresponds to steps 3), 4), and 5) in the manufacturing method of FIG. 1 and steps b), c), and d) in the manufacturing method of FIG. 2.
  • step b) differs in that chlorinated methane is present in addition to hydrogen chloride and unreacted methane.
  • chlorinated methane also does not react with methanol and acts like an inert substance, so the reaction between hydrogen chloride and methanol It was confirmed that it had no effect.
  • steps b), c), and d please refer to the description of steps 3), 4), and 5) of FIG. 1 above.
  • the methyl chloride production method according to the present invention has higher energy efficiency compared to the conventional methyl chloride production method.
  • the reactant injection volume of the CH 4 chlorination reactor is CH 4 1283.4 kg/h (80 kmol/h) and Cl 2 7090.6 kg/h (100 kmol/h), including Recycled CH 4 3249 kg/h (202.5 kmol/h).
  • the CH 4 /Cl 2 molar ratio at the reactor inlet was set to 2.825. At this time, the CH 4 conversion rate was 20.37% and the Cl 2 conversion rate was 100%.
  • the external methanol input as a reactant in the methanol hydrochlorination reactor was 3204.1 kg/h (100 kmol/h), and the conversion rate of methanol and HCl after reaction was 97.65% and 96.47%.
  • unreacted methane, chlorinated methane, etc. present in the reactant did not appear to react with methanol at all as there was no change in the number of moles before and after the reaction in the reactor.
  • the final reactant selectivity was 79.25% for MCM, 13.69% for DCM, and 7.05% for TCM, respectively.
  • the amount of MCM produced per hour was 6109.9 kg/h, the energy input per hour for this was 10,662,678 kJ/h, and the energy input per unit MCM was 10,662,678 kJ/h.
  • the amount was 1745 kJ/kg-MCM.
  • the reactant injection volume of the CH 4 chlorination reactor is CH 4 1283.4 kg/h (80 kmol/h) and Cl 2 7090.6 kg/h (100 kmol/h), including Recycled CH 4 3246 kg/h (202.4 kmol/h).
  • the CH 4 /Cl 2 molar ratio at the reactor inlet was set to 2.824. At this time, the CH 4 conversion rate was 20.39% and the Cl 2 conversion rate was 100%.
  • the external methanol input as a reactant in the methanol hydrochlorination reactor was 3204.1 kg/h (100 kmol/h), and the conversion rate of methanol and HCl after reaction was 97.41% and 95.97%.
  • the unreacted methane present in the reactant appeared to have not reacted with methanol at all as there was no change in the number of moles before and after the reaction in the reactor.
  • the final reactant selectivity was 79.21% for MCM, 13.72% for DCM, and 7.07% for TCM, respectively.
  • the amount of MCM produced per hour was 6089.3 kg/h, the energy input per hour for this was 10,762,492 kJ/h, and the energy input per unit of MCM was 10,762,492 kJ/h.
  • the amount was 1,767 kJ/kg-MCM.
  • Example 2 In order to compare the effect of the present invention, HCl recovered in Example 2 was separated from unreacted methane in advance, the separated hydrogen chloride was reacted with methanol, HCl was dissolved in water to make an aqueous HCl solution, and water was recovered from this aqueous HCl solution to form HCl. After separation, the obtained HCl was reacted with methanol again to obtain methyl chloride.
  • the process was configured as shown in Figure 5, and process simulation was performed using Honeywell's UniSim Design Suite R480.
  • the reactant injection volume of the CH 4 chlorination reactor is CH 4 1283.4 kg/h (80 kmol/h) and Cl 2 7090.6 kg/h (100 kmol/h), including Recycled CH 4 3249 kg/h (202.5 kmol/h).
  • the CH 4 /Cl 2 molar ratio at the reactor inlet was set to 2.825. At this time, the CH 4 conversion rate was 20.44% and the Cl 2 conversion rate was 100%.
  • the external methanol input as a reactant in the methanol hydrochlorination reactor was 3204.1 kg/h (100 kmol/h), and the conversion rate of methanol and HCl after reaction was 97.52% and 96.68%.
  • the final reactant selectivity was 79.04% for MCM, 13.78% for DCM, and 7.18% for TCM, respectively.
  • the amount of MCM produced per hour was 6047.6 kg/h, the energy input per hour for this was 22,458,991 kJ/h, and the energy input per unit of MCM was 22,458,991 kJ/h.
  • the amount was 3,714 kJ/kg-MCM.
  • Table 1 shows a comparison of the final product concentration and hourly production of MCM in Examples 1 and 2 and Comparative Example 1, and the energy input into the process for this.
  • the present invention is a method for producing methyl chloride through a multi-step reaction in which methyl chloride is produced through a methane chlorination reaction as a first reaction, and methyl chloride is produced by reacting hydrogen chloride produced as a by-product in the methane chlorination reaction with methanol as a secondary reaction.
  • the production yield of methyl chloride is improved by directly performing methanol hydrochlorination without performing a separate hydrogen chloride separation process, and the process energy efficiency is improved because the separate process for removing hydrogen chloride can be omitted.
  • It can be widely used in the industrial field of producing methyl chloride from methane.

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Abstract

La présente invention concerne un procédé de production de chlorure de méthyle avec une efficacité énergétique améliorée à l'aide d'une réaction en plusieurs étapes, dans la production de chlorure de méthyle par chloration de méthane, du méthane chloré tel que du chlorure de méthyle est séparé des produits d'une réaction de chloration de méthane en tant que réaction primaire, et le mélange restant de méthane n'ayant pas réagi et de chlorure d'hydrogène est mis en contact avec du méthanol sans séparation du chlorure d'hydrogène, ou le mélange de produits après la réaction est directement ajouté et mis à réagir avec du méthanol, ce qui permet d'obtenir une conversion en chlorure de méthyle, ce qui permet d'obtenir une amélioration de l'efficacité énergétique de traitement.
PCT/KR2023/013632 2022-09-22 2023-09-12 Procédé de production de chlorure de méthyle à efficacité énergétique améliorée à l'aide d'une réaction en plusieurs étapes WO2024063425A1 (fr)

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CN110922292A (zh) * 2019-08-07 2020-03-27 北京诺维新材科技有限公司 一种氯甲烷的制备方法
CN112225637A (zh) * 2020-10-12 2021-01-15 中国科学技术大学 一步法制备一氯甲烷的方法

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