CN110483568A - Methyl-chloride green synthesis method - Google Patents
Methyl-chloride green synthesis method Download PDFInfo
- Publication number
- CN110483568A CN110483568A CN201910730112.5A CN201910730112A CN110483568A CN 110483568 A CN110483568 A CN 110483568A CN 201910730112 A CN201910730112 A CN 201910730112A CN 110483568 A CN110483568 A CN 110483568A
- Authority
- CN
- China
- Prior art keywords
- methyl
- chloride
- catalyst
- synthesis method
- sulphur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229940050176 methyl chloride Drugs 0.000 title claims abstract description 61
- 238000001308 synthesis method Methods 0.000 title claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000005864 Sulphur Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 19
- 239000012043 crude product Substances 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 14
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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
- 238000000034 method Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000003009 desulfurizing effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000012267 brine Substances 0.000 abstract description 4
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 13
- CZGGKXNYNPJFAX-UHFFFAOYSA-N Dimethyldithiophosphate Chemical compound COP(S)(=S)OC CZGGKXNYNPJFAX-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000005924 Pirimiphos-methyl Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 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
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010563 solid-state fermentation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 1
- 239000005945 Chlorpyrifos-methyl Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 chlopyrifos Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NBAUXRCSDWYKRP-UHFFFAOYSA-N dimethyl phosphorochloridothioate Chemical compound COP(Cl)(=O)SC NBAUXRCSDWYKRP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008629 immune suppression Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
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 kind of green synthesis methods of methyl-chloride, include the following steps: S1, prepared in methyl-chloride reaction system using methyl sulfide and chlorine as raw material, it can make the characteristic of methyl sulfide chlorination using disulphur dichloride, by controlling the intake of chlorine, the disulphur dichloride continuation for generating reaction process is reacted with methyl sulfide is converted into methyl-chloride and sulphur；S2, to after the reaction was completed, catalyst A and catalyst B is added into reaction system, the sulphur in system is precipitated with loose shape crystal, isolated sulphur and methyl-chloride crude product obtain high-purity methyl-chloride through rectification under vacuum.The present invention can not only prepare high-purity methyl-chloride, improve yield, and can obtain the excellent crystal sulphur of character, can utilize again；It effectively prevents a large amount of brine wastes and elastic sulfur waste residue generates, also avoid the pollution of exhaust gas bring, environmentally protective, social benefit obvious environment benefit.
Description
Technical field
The invention belongs to the preparation technical fields of pesticide intermediate, and in particular to methyl-chloride green synthesis method.
Background technique
O, O- dimethyl thiophosphoryl chloride (abbreviation Methochloride, similarly hereinafter) are the dedicated of synthesis group thiophosphate pesticide
Intermediate.Methyl-chloride can be used for preparing nearly 20 kinds efficient, middle less toxic organophosphorus pesticides, such as pirimiphos-methyl, methyl
Chlopyrifos, fenifrothion, tolelofos-methyl etc..Wherein chlorpyrifos-methyl, chlopyrifos, pirimiphos-methyl etc. are the United Nations's grain farmer's groups
Knit the organic phosphorus species of high-efficiency low-toxicity that (FAO) is recommended to use.Methyl-chloride demand is presented year by year in pesticide market in recent years
Growing trend.
Methyl-chloride synthetic route of mainstream is to use phosphorus pentasulfide and methanol for raw material both at home and abroad at present, first
O, O- dimethyl S- hydrogen-phosphorodithioate (abbreviation methyl sulfide, similarly hereinafter) are synthesized, then obtains methyl-chloride through chlorination.
This route can avoid O well, and O, (compound can cause human body hepatic injury or immune suppression to O- trimethyl phosphorothioate
System, be the impurity of FAO's strict control) generation.
Mainstream enterprise uses the method that excessive saturation chlorine is passed through in chlorination process at present, thoroughly converts two for sulphur
Two sulphur of chlorination, then by reaction solution and akali sulphide reactant aqueous solution, disulphur dichloride is reduced to sulphur, is finally filtered, reaches sulphur
Sulphur separates (modern, 14 (4), 2015,18-19) with methyl-chloride.
Although this method solves the problems, such as disulphur dichloride, but disulphur dichloride is acutely put with vulcanized sodium reaction process
Heat, reaction system heating are very fast；Since methyl-chloride stability is poor, more than certain temperature vulnerable to thermal decomposition, cause to rush
Material or risk of explosion.The elastic sulfur of by-product, viscosity is big, and filtration difficulty, stink is big, and quantity is more, can only be used as Solid state fermentation.Simultaneously
A large amount of sulfur-bearing, phosphorus foul smell waste water are generated after alkalization hydrolysis, waste water, the environmental protection pressure of Solid state fermentation are huge.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide, one kind is environmentally protective, reaction is mild
Methyl-chloride green synthesis method, this method can not only prepare high-purity methyl-chloride, improve yield, Er Qieneng
The excellent crystal sulphur of character is obtained, can be utilized again；It effectively prevents a large amount of brine wastes and elastic sulfur waste residue generates, also keep away
Exempt from the pollution of exhaust gas bring, meets environmentally protective, energy-saving and emission-reduction developing direction, social benefit obvious environment benefit.
It is as follows that the present invention relates to key reaction equations:
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
Methyl-chloride green synthesis method, includes the following steps:
S1, it is prepared in methyl-chloride reaction system using methyl sulfide and chlorine as raw material, utilizes disulphur dichloride energy
The characteristic for making methyl sulfide chlorination, by control chlorine intake, make reaction process generate disulphur dichloride continue with
Methyl sulfide reaction is converted into methyl-chloride and sulphur；
S2, to after the reaction was completed, catalyst A and catalyst B is added into reaction system, makes the sulphur in system with loose shape crystal
It is precipitated, isolated sulphur and methyl-chloride crude product obtain high-purity methyl-chloride through rectification under vacuum.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the mole that the chlorine is passed through is methyl vulcanization
1.0~1.1 times of object mole.
Above-mentioned methyl-chloride green synthesis method, it is preferable that in step S1, reaction temperature is controlled 30~50
℃；The time of chlorination reaction is 1~5h.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the catalyst A is sodium hydroxide, hydroxide
At least one of potassium, magnesium hydroxide, calcium hydroxide；The catalyst B be ferric oxide desulfurizer, in PDS desulfurizing agent at least
It is a kind of.
Above-mentioned methyl-chloride green synthesis method, it is preferable that in the step S2, after complete reaction, be added
Catalyst A stirs 1~2h, continuously adds catalyst B, stirs 0.5~2h, carries out crystallization, after filter out sulphur after the completion of crystallization,
Obtain methyl-chloride crude product.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the additional amount of the catalyst A is methyl vulcanization
The 0.5~1.5% of amount of substance；The catalyst A is added at 50~60 DEG C of temperature.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the additional amount of the catalyst B is methyl vulcanization
The 0.5~1.5% of amount of substance；The catalyst B is added at 50~60 DEG C of temperature.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the time of the crystallization is 1~2h, the temperature of crystallization
Degree is 10~20 DEG C.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the catalyst B is added to instead with aqueous solution state
It answers in system, in the aqueous solution of catalyst B, the mass fraction of catalyst B is 1~10%.
Above-mentioned methyl-chloride green synthesis method, it is preferable that the hydrogen chloride water generated in chlorination reaction process
It absorbs.
Compared with the prior art, the advantages of the present invention are as follows:
(1) for security risk existing for existing methyl-chloride preparation method, and the not only waste of the by-product that generates
Resource, and the problems such as caused stress to environment.The present invention is through studying, by controlling chlorine in the chlorination process of methyl sulfide
Change depth, to prepare methyl-chloride.However inventors have found that the sulphur generated in the system can not be precipitated, merely by physics
Not only required time is longer or energy consumption is big, but also the amount of precipitation of sulphur is less for method (stand or cool down), is not suitable for industrial production,
The present inventor has found through numerous studies, by the group that specific compound catalyst A and catalyst B are added in system
Conjunction is handled, and by crystallizing and separating, can be made in system more than 97% sulphur to evacuate uniform crystal precipitation.
(2) the present invention is based on green chemical concept exploitation, no chlorine is wasted without sulphur atom, realizes atom economy substantially,
Raw material overall cost is far below conventional method.
(3) in the present invention, crystallization sulphur is in loose uniform shape, be can be easily separated, and can utilize again.
(4) the obtained methyl-chloride yield of the present invention is greater than 90%, and product content is up to 99%.
(5) present method avoids stench elastic sulfur and a large amount of brine wastes that alkaline hydrolysis generates, quantity of three wastes is few, and easily
In processing.
Specific embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection scope.
The sulphur that merit is precipitated in specific reagent is added by control depth of chlorination in the present invention, can separate with product,
High-purity methyl-chloride can be prepared, yield is improved；Crystal sulphur can utilize again；Effectively prevent a large amount of brine wastes and
Elastic sulfur waste residue generates, and meets environmentally protective, energy-saving and emission-reduction developing direction, social benefit obvious environment benefit.
The present invention is to be controlled depth of chlorination based on green chemical synthesis theory in the chlorination process of methyl sulfide, filled
Divide the chlorination characteristic synthesizing methyl chloride using chlorine and disulphur dichloride, promotes sulphur by the way that specific reagent is added to dredge
It dissipates crystal state to be precipitated, obtains high-purity methyl chloride subsequently through rectifying, do not generate stench elasticity sulphur and a large amount of saliferous
Waste water, atom utility value is high, obvious environment benefit.
A kind of green synthesis method of methyl-chloride, includes the following steps:
S1, it is prepared in methyl-chloride reaction system using methyl sulfide and chlorine as raw material, utilizes disulphur dichloride energy
The characteristic for making methyl sulfide chlorination, by control chlorine intake, make reaction process generate disulphur dichloride continue with
Methyl sulfide reaction is converted into methyl-chloride and sulphur；
S2, to after the reaction was completed, catalyst A and catalyst B is added into reaction system, makes the sulphur in system with loose shape crystal
It is precipitated, isolated sulphur and methyl-chloride crude product obtain high-purity methyl-chloride through rectification under vacuum.The technical program
In, it is necessary to while catalyst A and B is added, precipitation or the precipitation ratio that otherwise can not be difficult to realize sulphur are low, and the property of sulphur is precipitated
Shape is poor.
Wherein, methyl sulfide O, O- dimethyl S- hydrogen-phosphorodithioate.
In above scheme, the integral molar quantity that chlorine is passed through is preferably 1.0~1.1 times of methyl sulfide mole.
Chlorination reaction temperature is controlled at 30~50 DEG C.
The chlorination reaction time is 1~5h, preferably 1~3h.
After chlorination reaction is complete, catalyst A is added and is stirred to react 1~2h, continuously adds Catalyst B solution and is stirred
0.5~2h, then crystallization is carried out, sulphur is filtered out, methyl-chloride crude product is obtained.By first adding catalyst A stirring, rear plus catalysis
Agent B stirring can improve crystallization effect simultaneously and improve the character of sulphur be precipitated, the sulphur of acquisition can be better ensured that with easy
Isolated evacuation uniform crystal is precipitated.Crystallization is preferred are as follows: is kept the temperature after being cooled down to analyse sulphur, improves analysis sulphur speed.It is preferred that dropping
For temperature to 10~20 DEG C, the time of heat preservation is 1~2h.
0.5~1.5% catalyst A, the catalyst A of addition methyl sulfide quality is at 50~60 DEG C of temperature
At least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, preferably sodium hydroxide.
The catalyst B, the catalyst B that the 1~5% of methyl sulfide quality is added at 50~60 DEG C of temperature are oxidation
At least one of iron desulfurizing agent, PDS desulfurizing agent, preferably PDS desulfurizing agent.
Catalyst B is added in reaction system with aqueous solution state, and mass fraction is 1~10%, and preferred mass score is 1
~5%.
The hydrogen chloride generated in reaction process is absorbed with water.
Material employed in following embodiment and instrument are commercially available.
Embodiment 1:
A kind of methyl-chloride green synthesis method of the invention, includes the following steps:
(1) it will be equipped in tetra- mouthfuls of reaction flasks of 500ml of thermometer, air-breather, gas outlet, agitating device, device for absorbing tail gas
150g(98% is added) methyl sulfide (O, O- dimethyl S- hydrogen-phosphorodithioate), chlorine is passed through in about 3h at 30~40 DEG C
Gas 66g, reaction end gas (hydrogen chloride) are absorbed with water, and logical chlorine finishes.
(2) it is warming up under 50 DEG C (improving temperature to improve subsequent reaction speed) and sodium hydroxide 2g, insulated and stirred is added
1h is reacted, 4% mass fraction PDS desulfurization agent aqueous solution 75g is added, being cooled to 20 DEG C after constant temperature stirring 1h, (analysis can be improved in cooling
Brilliant speed), loose shape crystal sulphur is obtained by filtration after keeping the temperature 2h, liquid separation obtains methyl-chloride crude product.Crude product is gone into distillation
In bottle, rectifying obtains 136.2g methyl-chloride (purity 99%), yield 91.2% at -0.099 MPa high vacuum, 60 DEG C.
Embodiment 2:
A kind of methyl-chloride green synthesis method of the invention, includes the following steps:
(1) it will be equipped in tetra- mouthfuls of reaction flasks of 500ml of thermometer, air-breather, gas outlet, agitating device, device for absorbing tail gas
300g(98% is added) methyl sulfide (O, O- dimethyl S- hydrogen-phosphorodithioate), chlorine is passed through in about 2h at 30~40 DEG C
Gas 132g, reaction end gas are absorbed with water, and logical chlorine finishes.
(2) it is warming up to addition sodium hydroxide 3g at 50 DEG C, insulated and stirred reacts 1h, and 3% mass fraction PDS desulfurizing agent is added
20 DEG C are cooled to after aqueous solution 200g, constant temperature stirring 0.5h, loose shape crystal sulphur is obtained by filtration after keeping the temperature 1h, liquid separation obtains first
Base-chloride crude product.Crude product is gone in cucurbit, rectifying obtains 268.8g methyl-at -0.099 MPa high vacuum, 60 DEG C
Chloride (purity 99%), yield 90.1%.
Embodiment 3:
A kind of methyl-chloride green synthesis method of the invention, includes the following steps:
(1) it will be equipped in tetra- mouthfuls of reaction flasks of 1000ml of thermometer, air-breather, gas outlet, agitating device, device for absorbing tail gas
500g(98% is added) methyl sulfide (O, O- dimethyl S- hydrogen-phosphorodithioate), it is passed through in about 2.5h at 40~50 DEG C
Chlorine 220g reaction end gas is absorbed with water, and logical chlorine finishes.
(2) it is warming up to addition sodium hydroxide 7.0g at 60 DEG C, insulated and stirred reacts 1h, and 2% mass fraction PDS desulfurization is added
20 DEG C are cooled to after agent aqueous solution 350g, constant temperature stirring 1h, loose shape crystal sulphur is obtained by filtration after keeping the temperature 1h, liquid separation obtains first
Base-chloride crude product.Crude product is gone in cucurbit, rectifying obtains 454.2g methyl-at -0.099 MPa high vacuum, 60 DEG C
Chloride (purity 99%), yield 91.3%.
Embodiment 4:
A kind of methyl-chloride green synthesis method of the invention, includes the following steps:
(1) it will be equipped in tetra- mouthfuls of reaction flasks of 1000ml of thermometer, air-breather, gas outlet, agitating device, device for absorbing tail gas
500g(98% is added) methyl sulfide (O, O- dimethyl S- hydrogen-phosphorodithioate), chlorine is passed through in about 3h at 30~40 DEG C
Gas 225g, reaction end gas are absorbed with water, and logical chlorine finishes.
(2) it is warming up to addition sodium hydroxide 7.5g at 60 DEG C, insulated and stirred reacts 1h, and 4% mass fraction PDS desulfurization is added
20 DEG C are cooled to after agent aqueous solution 175g, constant temperature stirring 1h, loose shape crystal sulphur is obtained by filtration after keeping the temperature 2h, liquid separation obtains first
Base-chloride crude product.Crude product is gone in cucurbit, rectifying obtains 457.9g methyl-at -0.099 MPa high vacuum, 60 DEG C
Chloride (purity 99%), yield 92.1%.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form.Though
So the present invention is disclosed as above with preferred embodiment, and however, it is not intended to limit the invention.It is any to be familiar with those skilled in the art
Member, in the case where not departing from Spirit Essence of the invention and technical solution, all using in the methods and techniques of the disclosure above
Appearance makes many possible changes and modifications or equivalent example modified to equivalent change to technical solution of the present invention.Therefore,
Anything that does not depart from the technical scheme of the invention are made to the above embodiment any simple according to the technical essence of the invention
Modification, equivalent replacement, equivalence changes and modification, all of which are still within the scope of protection of the technical scheme of the invention.
Claims (10)
1. methyl-chloride green synthesis method, which comprises the steps of:
S1, it is prepared in methyl-chloride reaction system using methyl sulfide and chlorine as raw material, utilizes disulphur dichloride energy
The characteristic for making methyl sulfide chlorination, by control chlorine intake, make reaction process generate disulphur dichloride continue with
Methyl sulfide reaction is converted into methyl-chloride and sulphur；
S2, to after the reaction was completed, catalyst A and catalyst B is added into reaction system, makes the sulphur in system with loose shape crystal
It is precipitated, isolated sulphur and methyl-chloride crude product obtain high-purity methyl-chloride through rectification under vacuum.
2. the green synthesis method of methyl-chloride as described in claim 1, which is characterized in that the chlorine was passed through rubs
Your amount is 1.0~1.1 times of methyl sulfide mole.
3. the green synthesis method of methyl-chloride according to claim 1, which is characterized in that in step S1, reaction temperature
Degree control is at 30~50 DEG C；The time of chlorination reaction is 1~5h.
4. the green synthesis method of methyl-chloride as claimed in any one of claims 1 to 3, which is characterized in that the catalysis
Agent A is at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide；The catalyst B is iron oxide desulfurization
At least one of agent, PDS desulfurizing agent.
5. the green synthesis method of methyl-chloride according to claim 4, which is characterized in that in the step S2, to
After fully reacting, catalyst A is added, stirs 1~2h, continuously adds catalyst B, stirs 0.5~2h, crystallization is carried out, to crystallization
Sulphur is filtered out after the completion, obtains methyl-chloride crude product.
6. the green synthesis method of methyl-chloride as claimed in claim 4, which is characterized in that the addition of the catalyst A
Amount is the 0.5~1.5% of methyl sulfide quality；The catalyst A is added at 50~60 DEG C of temperature.
7. the green synthesis method of methyl-chloride as claimed in claim 4, which is characterized in that the addition of the catalyst B
Amount is the 0.5~1.5% of methyl sulfide quality；The catalyst B is added at 50~60 DEG C of temperature.
8. the green synthesis method of methyl-chloride as claimed in claim 5, which is characterized in that the time of the crystallization is 1
~2h, the temperature of crystallization are 10~20 DEG C.
9. the green synthesis method of methyl-chloride as claimed in claim 5, which is characterized in that the catalyst B is with water-soluble
Liquid status adds in reaction system, and in the aqueous solution of catalyst B, the mass fraction of catalyst B is 1~10%.
10. the green synthesis method of methyl-chloride as claimed in any one of claims 1 to 3, which is characterized in that chlorination is anti-
The hydrogen chloride that should be generated in the process is absorbed with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910730112.5A CN110483568B (en) | 2019-08-08 | 2019-08-08 | Green synthesis method of methyl-chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910730112.5A CN110483568B (en) | 2019-08-08 | 2019-08-08 | Green synthesis method of methyl-chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110483568A true CN110483568A (en) | 2019-11-22 |
| CN110483568B CN110483568B (en) | 2022-03-08 |
Family
ID=68549991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910730112.5A Active CN110483568B (en) | 2019-08-08 | 2019-08-08 | Green synthesis method of methyl-chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483568B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4075292A (en) * | 1976-06-01 | 1978-02-21 | Bayer Aktiengesellschaft | Production of O,O-dialkyl-phosphorochloridothionates |
| US4078023A (en) * | 1975-08-28 | 1978-03-07 | Hoechst Aktiengesellschaft | Production of O,O-dialkylthionophosphoric acid chlorides |
| US20020017053A1 (en) * | 2000-07-04 | 2002-02-14 | Muneyoshi Yamada | Hydrogenation of carbon monoxide using sulfide catalysts |
| CN101293897A (en) * | 2008-06-06 | 2008-10-29 | 武汉工程大学 | Method for preparing O,O-ethyl thioether substituted phosphorus oxychloride |
| CN101830925A (en) * | 2010-05-14 | 2010-09-15 | 荆州市沙市东方有机化工研究所 | Production process of O, O-dialkyl thiophosphoryl chloride |
| CN104072536A (en) * | 2014-07-11 | 2014-10-01 | 武汉理工大学 | Method for desulfurizing in ethyl chloride production |
| CN108329346A (en) * | 2018-03-21 | 2018-07-27 | 湖南化工研究院有限公司 | A kind of synthetic method of O, O- dialkyl sulfide substituted phosphorus oxychloride |
| CN109369708A (en) * | 2018-12-11 | 2019-02-22 | 重庆华歌生物化学有限公司 | A kind of green synthesis process of O, O- diethyl sulfo-phosphoryl chloride |
-
2019
- 2019-08-08 CN CN201910730112.5A patent/CN110483568B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4078023A (en) * | 1975-08-28 | 1978-03-07 | Hoechst Aktiengesellschaft | Production of O,O-dialkylthionophosphoric acid chlorides |
| US4075292A (en) * | 1976-06-01 | 1978-02-21 | Bayer Aktiengesellschaft | Production of O,O-dialkyl-phosphorochloridothionates |
| US20020017053A1 (en) * | 2000-07-04 | 2002-02-14 | Muneyoshi Yamada | Hydrogenation of carbon monoxide using sulfide catalysts |
| CN101293897A (en) * | 2008-06-06 | 2008-10-29 | 武汉工程大学 | Method for preparing O,O-ethyl thioether substituted phosphorus oxychloride |
| CN101830925A (en) * | 2010-05-14 | 2010-09-15 | 荆州市沙市东方有机化工研究所 | Production process of O, O-dialkyl thiophosphoryl chloride |
| CN104072536A (en) * | 2014-07-11 | 2014-10-01 | 武汉理工大学 | Method for desulfurizing in ethyl chloride production |
| CN108329346A (en) * | 2018-03-21 | 2018-07-27 | 湖南化工研究院有限公司 | A kind of synthetic method of O, O- dialkyl sulfide substituted phosphorus oxychloride |
| CN109369708A (en) * | 2018-12-11 | 2019-02-22 | 重庆华歌生物化学有限公司 | A kind of green synthesis process of O, O- diethyl sulfo-phosphoryl chloride |
Non-Patent Citations (4)
| Title |
|---|
| 卢源禧等: ""O,O-二烷基硫代磷酰氯的制备-五硫化二磷法新工艺"", 《农药》 * |
| 李铁等: ""O,O-二乙基硫代磷酰氯精制工艺的改进"", 《现代农药》 * |
| 杨树卿等: ""PDS-脱硫催化剂的研究与应用"", 《石油化工》 * |
| 韩义民: ""O,O-二烷基硫代磷酰氯的提纯"", 《安徽化工》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110483568B (en) | 2022-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110040748A (en) | Utilize the method for incineration of refuse flyash production sylvite and sodium salt | |
| CN101760641B (en) | Technology for recovering magnesium from magnesium sulfate solution | |
| CN104672206B (en) | A kind of preparation technology of thiirane | |
| CN105732986B (en) | A kind of technique preparing Methyl Hydrogen Polysiloxane Fluid | |
| CN101318668A (en) | Method for preparing agricultural ammonium sulphate and calcined soda for industry with salt cake ammonia soda process | |
| CN105384669A (en) | Preparation method of xanthate | |
| CN104817588A (en) | Preparation method of ethyl chloride | |
| US20050220698A1 (en) | Process for recovery of sulphate of potash | |
| CN110483568A (en) | Methyl-chloride green synthesis method | |
| CN107954455A (en) | A kind of method for preparing battery-level lithium carbonate using waste liquid containing lithium | |
| CN104072536B (en) | The method of diethylaluminum monochloride production desulfurization | |
| CN110342486A (en) | A kind of preparation method of difluorophosphate | |
| JP4516023B2 (en) | How to recover potassium sulfate | |
| CN104151351B (en) | The method that diethylaluminum monochloride goes to hydrolyze chlorination production | |
| CN108329346B (en) | A kind of synthetic method of O, O- dialkyl sulfide substituted phosphorus oxychloride | |
| CN102838514B (en) | Synthetic method of hexamethylene flusulfamide | |
| CN109369708A (en) | A kind of green synthesis process of O, O- diethyl sulfo-phosphoryl chloride | |
| CN116425122A (en) | High-purity sodium hydrosulfide and synthesis method thereof | |
| CN107312032B (en) | O, O- diethyl sulfo-phosphoryl chloride and preparation method thereof | |
| TW201925096A (en) | Solidifying and manufacturing method of ferric trichloride hexahydrate and its solidifying and manufacturing system capable of satisfying the environmental protection requirements and improving the product quality | |
| CN101760643B (en) | Improved method for recovering magnesium from magnesium sulfate solution | |
| CN85107743B (en) | Hydrochloric acid recycle process for manufacturing barium sulphate and magnesium at the same time | |
| CN106946752A (en) | A kind of synthetic method of diphenyl sulfide | |
| CN110283107A (en) | A kind of inexpensive green production process of novel 3- sulfydryl propionitrile coproduction thiodipropionetrile | |
| CN105936629B (en) | The synthetic method of body of Pramipexole dihydrochloride intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xu Xianjin Inventor after: Li Min Inventor after: Chen Ming Inventor after: Du Duan Inventor after: Chen Gang Inventor after: Zhu Laifa Inventor after: Wang Shengde Inventor after: Zeng Jing Inventor after: Liu Wei Inventor after: Wu Man Inventor after: Zeng Xueyun Inventor before: Zhu Laifa Inventor before: Wang Shengde Inventor before: Zeng Jing Inventor before: Liu Wei Inventor before: Wu Man Inventor before: Zeng Xueyun Inventor before: Li Min Inventor before: Chen Ming |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211111 Address after: 435200 Mu Gang Zhen Ao tou Cun, Yangxin County, Huangshi City, Hubei Province Applicant after: Hubei chishun Chemical Co., Ltd Applicant after: Wuhan kaimeikeda Biotechnology Co., Ltd Address before: 415001 No. 2, sujiadu street, sujiadu neighborhood committee, Deshan sub district office, Changde economic and Technological Development Zone, Hunan Province Applicant before: Hunan Haili Changde Pesticide Chemical Co., Ltd |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |