CN110483568B - Green synthesis method of methyl-chloride - Google Patents
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- CN110483568B CN110483568B CN201910730112.5A CN201910730112A CN110483568B CN 110483568 B CN110483568 B CN 110483568B CN 201910730112 A CN201910730112 A CN 201910730112A CN 110483568 B CN110483568 B CN 110483568B
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229940050176 methyl chloride Drugs 0.000 title claims abstract description 52
- 238000001308 synthesis method Methods 0.000 title claims abstract description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011593 sulfur Substances 0.000 claims abstract description 43
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims abstract description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 16
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005660 chlorination reaction Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 239000013078 crystal Substances 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical class ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 5
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- XJFIKRXIJXAJGH-UHFFFAOYSA-N 5-chloro-1,3-dihydroimidazo[4,5-b]pyridin-2-one Chemical group ClC1=CC=C2NC(=O)NC2=N1 XJFIKRXIJXAJGH-UHFFFAOYSA-N 0.000 description 2
- 239000005945 Chlorpyrifos-methyl Substances 0.000 description 2
- 239000005924 Pirimiphos-methyl Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- QHOQHJPRIBSPCY-UHFFFAOYSA-N pirimiphos-methyl Chemical group CCN(CC)C1=NC(C)=CC(OP(=S)(OC)OC)=N1 QHOQHJPRIBSPCY-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010062016 Immunosuppression Diseases 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005845 Tolclofos-methyl Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NBAUXRCSDWYKRP-UHFFFAOYSA-N dimethyl phosphorochloridothioate Chemical compound COP(Cl)(=O)SC NBAUXRCSDWYKRP-UHFFFAOYSA-N 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 231100000753 hepatic injury Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001506 immunosuppresive effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- OBZIQQJJIKNWNO-UHFFFAOYSA-N tolclofos-methyl Chemical compound COP(=S)(OC)OC1=C(Cl)C=C(C)C=C1Cl OBZIQQJJIKNWNO-UHFFFAOYSA-N 0.000 description 1
- XWSLYQXUTWUIKM-UHFFFAOYSA-N trimethoxy(sulfanylidene)-$l^{5}-phosphane Chemical compound COP(=S)(OC)OC XWSLYQXUTWUIKM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a green synthesis method of methyl-chloride, which comprises the following steps: s1, in a reaction system for preparing methyl-chloride by taking methyl sulfide and chlorine as raw materials, utilizing the characteristic that disulfide dichloride can chlorinate the methyl sulfide, and continuously reacting disulfide dichloride generated in the reaction process with the methyl sulfide to convert the disulfide dichloride into the methyl-chloride and sulfur by controlling the introduction amount of the chlorine; s2, after the reaction is finished, adding a catalyst A and a catalyst B into the reaction system to separate out sulfur in the system in loose crystals, separating to obtain sulfur and a methyl-chloride crude product, and carrying out reduced pressure rectification to obtain the high-purity methyl-chloride. The method can prepare high-purity methyl-chloride, improve the yield, and obtain crystal sulfur with excellent properties which can be reused; effectively avoids a large amount of salt-containing wastewater and elastic sulfur waste residues, also avoids pollution caused by waste gas, is green and environment-friendly, and has remarkable social and environmental benefits.
Description
Technical Field
The invention belongs to the technical field of preparation of pesticide intermediates, and particularly relates to a green synthesis method of methyl-chloride.
Background
O, O-dimethyl thiophosphoryl chloride (methyl chloride for short, the same below) is a special intermediate for synthesizing thiophosphate pesticides. The methyl-chloride can be used for preparing nearly twenty high-efficiency and medium-low-toxicity organophosphorus pesticides, such as pirimiphos-methyl, chlorpyrifos-methyl, fenitrothion, tolclofos-methyl and the like. Wherein the chlorpyrifos-methyl, the pirimiphos-methyl and the like are high-efficiency low-toxicity organophosphorus varieties recommended by the Food and Agriculture Organization (FAO) of the United nations. The demand for methyl-chloride in the pesticide market has seen an increasing trend year after year in recent years.
At present, the mainstream synthesis route of methyl-chloride at home and abroad adopts phosphorus pentasulfide and methanol as raw materials, O-dimethyl S-hydrogen-phosphorodithioate (methyl sulfide for short, the same below) is synthesized firstly, and then the methyl-chloride is obtained by chlorination. The route can well avoid the generation of O, O, O-trimethyl thiophosphate (the compound can cause liver injury or immunosuppression of human body and is an impurity strictly controlled by food and agriculture organization of the United nations).
At present, the mainstream enterprises adopt a method of introducing excessive saturated chlorine gas in the chlorination process to completely convert sulfur into disulfide dichloride, then react the reaction liquid with an aqueous solution of sodium sulfide to reduce the disulfide dichloride into sulfur, and finally filter the reaction liquid to separate the sulfur from methyl-chloride (modern pesticides, 14(4), 2015 and 18-19).
Although the method solves the problem of disulfide dichloride, the reaction process of disulfide dichloride and sodium sulfide releases heat violently, and the temperature of the reaction system rises faster; due to the poor stability of methyl-chloride, it is susceptible to thermal decomposition above a certain temperature, leading to the risk of flushing or explosion. The by-product elastic sulfur has large viscosity, difficult filtration, large odor and large quantity, and can only be treated as waste residue. Meanwhile, a large amount of sulfur and phosphorus-containing foul smell waste water is generated after alkalization and hydrolysis, and the environmental protection pressure for treating waste water and waste residues is huge.
Disclosure of Invention
The invention aims to solve the technical problem of providing a green and environment-friendly methyl-chloride green synthesis method with mild reaction aiming at the defects of the prior art, the method not only can prepare high-purity methyl-chloride and improve the yield, but also can obtain crystal sulfur with excellent properties and can be reused; effectively avoids a large amount of salt-containing wastewater and elastic sulfur waste residues, also avoids pollution caused by waste gas, accords with the development directions of environmental protection, energy conservation and emission reduction, and has remarkable social and environmental benefits.
The invention relates to the following main reaction equation:
in order to solve the technical problems, the technical scheme provided by the invention is as follows:
a green synthesis method of methyl-chloride, comprising the following steps:
s1, in a reaction system for preparing methyl-chloride by taking methyl sulfide and chlorine as raw materials, utilizing the characteristic that disulfide dichloride can chlorinate the methyl sulfide, and continuously reacting disulfide dichloride generated in the reaction process with the methyl sulfide to convert the disulfide dichloride into the methyl-chloride and sulfur by controlling the introduction amount of the chlorine;
s2, after the reaction is finished, adding a catalyst A and a catalyst B into the reaction system to separate out sulfur in the system in loose crystals, separating to obtain sulfur and a methyl-chloride crude product, and carrying out reduced pressure rectification to obtain the high-purity methyl-chloride.
In the green synthesis method of methyl-chloride, the molar weight of the chlorine gas introduced is preferably 1.0 to 1.1 times of the molar weight of the methyl sulfide.
In the green synthesis method of methyl-chloride, preferably, in step S1, the reaction temperature is controlled at 30-50 ℃; the time of chlorination reaction is 1-5 h.
In the green synthesis method of methyl-chloride, preferably, the catalyst a is at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide; the catalyst B is at least one of an iron oxide desulfurizer and a PDS desulfurizer.
Preferably, in the step S2, after the reaction is completed, adding the catalyst a, stirring for 1-2 hours, continuing to add the catalyst B, stirring for 0.5-2 hours, performing crystallization, and after the crystallization is completed, filtering out sulfur to obtain a methyl-chloride crude product.
In the green synthesis method of methyl-chloride, preferably, the addition amount of the catalyst A is 0.5-1.5% of the mass of methyl sulfide; the catalyst A is added at the temperature of 50-60 ℃.
In the green synthesis method of methyl-chloride, preferably, the addition amount of the catalyst B is 0.5-1.5% of the mass of methyl sulfide; and adding the catalyst B at the temperature of 50-60 ℃.
In the green synthesis method of methyl-chloride, preferably, the crystallization time is 1-2 hours, and the crystallization temperature is 10-20 ℃.
In the green synthesis method of methyl-chloride, preferably, the catalyst B is added to the reaction system in an aqueous solution state, and the mass fraction of the catalyst B in the aqueous solution of the catalyst B is 1-10%.
In the green synthesis method of methyl-chloride, hydrogen chloride generated in the chlorination reaction process is preferably absorbed by water.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the problems of potential safety hazard existing in the existing methyl-chloride preparation method and the problems that the generated by-products not only waste resources, but also cause pressure to the environment and the like. The invention is researched to prepare the methyl-chloride by controlling the chlorination depth in the chlorination process of the methyl sulfide. However, the inventor finds that sulfur generated in the system can not be precipitated, the system only depends on a physical method (standing or cooling), not only needs longer time or consumes more energy, but also has less precipitated amount of sulfur, and is not suitable for industrial production.
(2) The method is developed based on a green chemical concept, no chlorine and sulfur atoms are wasted, the atom economy is basically realized, and the comprehensive cost of raw materials is far lower than that of the traditional method.
(3) In the invention, the crystallized sulfur is loose and uniform, is easy to separate and can be reused.
(4) The yield of the methyl-chloride obtained by the invention is more than 90 percent, and the product content reaches 99 percent.
(5) The method avoids the stink elastic sulfur and a large amount of salt-containing wastewater generated by alkaline hydrolysis, has little three wastes and is easy to treat.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
According to the invention, the chlorination depth is controlled, and a specific reagent is added to precipitate sulfur with excellent properties, so that the sulfur can be separated from a product, high-purity methyl-chloride can be prepared, and the yield is improved; the crystal sulfur can be reused; effectively avoids a large amount of salt-containing wastewater and elastic sulfur waste residues, accords with the development direction of environmental protection, energy conservation and emission reduction, and has remarkable social and environmental benefits.
The invention is based on the green chemical synthesis concept, controls the chlorination depth in the chlorination process of the methyl sulfide, fully utilizes the chlorination characteristics of chlorine and disulfur dichloride to synthesize the methyl chloride, promotes sulfur to be separated out in a dispersed crystal state by adding a specific reagent, and obtains the high-purity methyl chloride by rectification subsequently, thereby not generating foul-smell elastic sulfur and a large amount of salt-containing wastewater, having high atom utilization value and remarkable environmental benefit.
A green synthesis method of methyl-chloride comprises the following steps:
s1, in a reaction system for preparing methyl-chloride by taking methyl sulfide and chlorine as raw materials, utilizing the characteristic that disulfide dichloride can chlorinate the methyl sulfide, and continuously reacting disulfide dichloride generated in the reaction process with the methyl sulfide to convert the disulfide dichloride into the methyl-chloride and sulfur by controlling the introduction amount of the chlorine;
s2, after the reaction is finished, adding a catalyst A and a catalyst B into the reaction system to separate out sulfur in the system in loose crystals, separating to obtain sulfur and a methyl-chloride crude product, and carrying out reduced pressure rectification to obtain the high-purity methyl-chloride. In the technical scheme, the catalysts A and B must be added simultaneously, otherwise, the precipitation of sulfur cannot be realized difficultly or the precipitation rate is low, and the character of precipitated sulfur is poor.
Wherein the methyl sulfide is O, O-dimethyl S-hydrogen-dithiophosphate.
In the scheme, the total molar weight of chlorine gas is preferably 1.0-1.1 times of the molar weight of methyl sulfide.
The chlorination reaction temperature is controlled to be 30-50 ℃.
The chlorination reaction time is 1-5 h, preferably 1-3 h.
And after the chlorination reaction is completed, adding a catalyst A, stirring and reacting for 1-2 h, continuously adding a catalyst B solution, stirring for 0.5-2 h, then performing crystallization, and filtering sulfur to obtain a methyl-chloride crude product. The catalyst A is added and stirred firstly, and then the catalyst B is added and stirred, so that the crystallization effect can be improved, the character of the separated sulfur can be improved, and the obtained sulfur can be better ensured to be separated out in the form of easily separated, uniformly dispersed crystals. The crystallization is preferably: the temperature is kept after being reduced to separate out sulfur, and the sulfur separation speed is improved. Preferably, the temperature is reduced to 10-20 ℃, and the heat preservation time is 1-2 h.
Adding a catalyst A accounting for 0.5-1.5% of the mass of the methyl sulfide at 50-60 ℃, wherein the catalyst A is at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, and preferably sodium hydroxide.
Adding a catalyst B accounting for 1-5% of the mass of the methyl sulfide at 50-60 ℃, wherein the catalyst B is at least one of an iron oxide desulfurizer and a PDS desulfurizer, and the catalyst B is preferably a PDS desulfurizer.
The catalyst B is added into the reaction system in the state of aqueous solution, and the mass fraction of the catalyst B is 1-10%, and the preferred mass fraction is 1-5%.
The hydrogen chloride produced during the reaction was absorbed with water.
The materials and equipment used in the following examples are commercially available.
Example 1:
the green synthesis method of methyl-chloride of the invention comprises the following steps:
(1) 150g (98%) of methyl sulfide (O, O-dimethyl S-hydrogen-phosphorodithioate) is added into a 500ml four-mouth reaction bottle provided with a thermometer, an aeration device, an air outlet, a stirring device and a tail gas absorption device, 66g of chlorine is introduced into the reaction bottle within about 3 hours at the temperature of 30-40 ℃, the reaction tail gas (hydrogen chloride) is absorbed by water, and the chlorine introduction is finished.
(2) Heating to 50 ℃ (raising the temperature to increase the subsequent reaction speed), adding 2g of sodium hydroxide, carrying out heat preservation stirring reaction for 1h, adding 75g of PDS desulfurizer aqueous solution with the mass fraction of 4%, stirring at constant temperature for 1h, then cooling to 20 ℃ (cooling can increase the crystallization speed), carrying out heat preservation for 2h, filtering to obtain loose crystal sulfur, and separating liquid to obtain a methyl-chloride crude product. The crude product was transferred to a distillation flask and rectified under-0.099 MPa high vacuum at 60 ℃ to give 136.2g of methyl-chloride (purity 99%) with a yield of 91.2%.
Example 2:
the green synthesis method of methyl-chloride of the invention comprises the following steps:
(1) adding 300g (98%) of methyl sulfide (O, O-dimethyl S-hydrogen-phosphorodithioate) into a 500ml four-mouth reaction bottle provided with a thermometer, an aeration device, an air outlet, a stirring device and a tail gas absorption device, introducing 132g of chlorine gas within about 2 hours at the temperature of 30-40 ℃, absorbing the reaction tail gas by water, and finishing chlorine introduction.
(2) Heating to 50 ℃, adding 3g of sodium hydroxide, stirring and reacting for 1h under heat preservation, adding 200g of PDS desulfurizer aqueous solution with the mass fraction of 3%, stirring for 0.5h under constant temperature, cooling to 20 ℃, preserving heat for 1h, filtering to obtain loose crystal sulfur, and separating to obtain a methyl-chloride crude product. The crude product was transferred to a distillation flask and rectified under-0.099 MPa high vacuum at 60 ℃ to give 268.8g of methyl-chloride (purity 99%) with 90.1% yield.
Example 3:
the green synthesis method of methyl-chloride of the invention comprises the following steps:
(1) adding 500g (98%) of methyl sulfide (O, O-dimethyl S-hydrogen-phosphorodithioate) into a 1000ml four-mouth reaction bottle provided with a thermometer, an aeration device, an air outlet, a stirring device and a tail gas absorption device, introducing 220g of chlorine gas into the reaction bottle at 40-50 ℃ within about 2.5h, and absorbing the reaction tail gas by water, wherein the chlorine introduction is finished.
(2) Heating to 60 ℃, adding 7.0g of sodium hydroxide, keeping the temperature, stirring and reacting for 1h, adding 350g of PDS desulfurizer aqueous solution with the mass fraction of 2%, stirring for 1h at the constant temperature, cooling to 20 ℃, keeping the temperature for 1h, filtering to obtain loose crystal sulfur, and separating to obtain a methyl-chloride crude product. The crude product was transferred to a distillation flask and rectified under-0.099 MPa high vacuum at 60 ℃ to give 454.2g of methyl-chloride (purity 99%) with a yield of 91.3%.
Example 4:
the green synthesis method of methyl-chloride of the invention comprises the following steps:
(1) adding 500g (98%) of methyl sulfide (O, O-dimethyl S-hydrogen-phosphorodithioate) into a 1000ml four-mouth reaction bottle provided with a thermometer, an aeration device, an air outlet, a stirring device and a tail gas absorption device, introducing 225g of chlorine gas within about 3 hours at the temperature of 30-40 ℃, absorbing the reaction tail gas by water, and finishing chlorine introduction.
(2) Heating to 60 ℃, adding 7.5g of sodium hydroxide, keeping the temperature, stirring and reacting for 1h, adding 175g of PDS desulfurizer aqueous solution with the mass fraction of 4%, stirring for 1h at the constant temperature, cooling to 20 ℃, keeping the temperature for 2h, filtering to obtain loose crystal sulfur, and separating to obtain a methyl-chloride crude product. The crude product was transferred to a distillation flask and rectified under-0.099 MPa high vacuum at 60 ℃ to give 457.9g of methyl-chloride (purity 99%) in 92.1% yield.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (4)
1. The green synthesis method of methyl-chloride is characterized by comprising the following steps:
s1, in a reaction system for preparing methyl-chloride by taking methyl sulfide and chlorine as raw materials, utilizing the characteristic that disulfide dichloride can chlorinate the methyl sulfide, and continuously reacting disulfide dichloride generated in the reaction process with the methyl sulfide to convert the disulfide dichloride into the methyl-chloride and sulfur by controlling the introduction amount of the chlorine;
s2, after the reaction is finished, adding a catalyst A and a catalyst B into the reaction system to separate out sulfur in the system in a loose product, separating to obtain sulfur and a methyl-chloride crude product, and carrying out reduced pressure rectification to obtain high-purity methyl-chloride;
in the step S1, the reaction temperature is controlled to be 30-50 ℃, and the chlorination reaction time is 1-5 h;
in the step S2, after the reaction is completed, adding a catalyst A at the temperature of 50-60 ℃, stirring for 1-2 h while maintaining the temperature, continuing adding a catalyst B, stirring for 0.5-2 h while maintaining the temperature, crystallizing for 1-2 h at the crystallization temperature of 10-20 ℃, filtering sulfur after the crystallization is completed to obtain a methyl-chloride crude product, wherein the catalyst A is sodium hydroxide, and the catalyst B is a PDS desulfurizer.
2. The green synthesis method of methyl-chloride as claimed in claim 1, characterized in that the molar quantity of chlorine fed in step Sl is 1.0-1.1 times the molar quantity of methyl sulfide.
3. The green synthesis method of methyl-chloride as claimed in claim 1, wherein the chlorination time in step S1 is preferably 1-3 h.
4. The green synthesis method of methyl-chloride as claimed in claim 1, characterized in that the addition amount of the catalyst A is 0.5-1.5% of the mass of the methyl sulfide; the addition amount of the catalyst B is 0.5-1.5% of the mass of the methyl sulfide, the catalyst B is added into a reaction system in an aqueous solution state, and the mass fraction of the aqueous solution of the catalyst B is 1-10%.
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