CN101486731B - Production method of O, O-dimethyl thiophosphoryl chloride - Google Patents
Production method of O, O-dimethyl thiophosphoryl chloride Download PDFInfo
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- CN101486731B CN101486731B CN200810236831A CN200810236831A CN101486731B CN 101486731 B CN101486731 B CN 101486731B CN 200810236831 A CN200810236831 A CN 200810236831A CN 200810236831 A CN200810236831 A CN 200810236831A CN 101486731 B CN101486731 B CN 101486731B
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- dimethyl
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- phosphorus trichloride
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- phosphorus
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- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- NBAUXRCSDWYKRP-UHFFFAOYSA-N dimethyl phosphorochloridothioate Chemical compound COP(Cl)(=O)SC NBAUXRCSDWYKRP-UHFFFAOYSA-N 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 62
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- -1 thiophosphoryl amide Chemical class 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 abstract 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 abstract 1
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 14
- 125000003963 dichloro group Chemical group Cl* 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 229940063675 spermine Drugs 0.000 description 7
- 238000011084 recovery Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 1
- KVILUFYYUJUTDJ-UHFFFAOYSA-N benzene;n,n-diethylethanamine Chemical compound C1=CC=CC=C1.CCN(CC)CC KVILUFYYUJUTDJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 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
- 239000012467 final product Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a production method of O, O-dimethyl phosphoramide thioate, which takes phosphorus trichloride, absolute methanol, sulphur and ammonia as raw materials and is characterized in that: the phosphorus trichloride reacts with the absolute methanol to generate trimethyl phosphate which reacts with the phosphorus trichloride at the temperature of 20 DEG C to 100 DEG C to generate O, O-dimethyl phosphorus monochloride and sulphur is added to generate O, O-dimethyle thiophosphoryl chloride which is separated then; and ammonia is added to the separated O, O-dimethyle thiophosphoryl chloride to generate rough O, O-dimethyle thiophosphoryl amide and refined O, O-dimethyle thiophosphoryl amide is obtained through dehydration. The overall yield of the method can be more than 94 percent and the content of obtained O, O- dimethyle thiophosphoryl can reach 99 percent. The production method is characterized by no sewage discharge and no environmental pollution.
Description
Technical field
The present invention relates to make O the O-dimethyl thiophosphoryl amide with chemical process.
Background technology
O, the O-dimethyl thiophosphoryl amide abbreviates spermine as.The production of present domestic spermine is to adopt the phosphorus thiochloride method to produce spermine, and main raw material has phosphorus trichloride, sulphur, methyl alcohol, ammoniacal liquor and sodium hydroxide.Its working method is: generate phosphorus thiochloride with phosphorus trichloride and reaction of Salmon-Saxl earlier, phosphorus thiochloride and excessive methanol reaction generate the O-methyl thio-phosphoryl dichloride, are called for short dichloro; Dichloro generates O with the excessive methanol reaction again in the presence of alkali, O-dimethyl-thiophosphoryl one chlorine is called for short a chlorine; One chlorine promptly generates O with ammonia react again, and O-dimethyl thiophosphoryl amide bullion promptly gets elaboration through aftertreatment.
During production, the reaction of sulphur and phosphorus trichloride, its yield and content all can reach 97%, and this is due to the multiple isomer of or sulphur on the low side owing to phosphorus trichloride content.
Phosphorus thiochloride and methyl alcohol reaction, when generating dichloro, methyl alcohol must be excessive in a large number, and its mol ratio is 1:5.Temperature of reaction must maintain about 0 ℃, and exothermic heat of reaction is big, and cold consumption is big.Dichloro is 95% to the yield of phosphorus thiochloride.
When dichloro generates a chlorine, do not have alkali in the presence of, dichloro and methyl alcohol are difficult to reaction, therefore the generation of a chlorine must be under alkali and excessive methyl alcohol react and just can obtain.Because the existence of alkali is arranged, two chlorine atoms in the dichloro are replaced by methoxyl group easily, thereby generate useless O, O, and the O-trimethyl phosphorothioate is called for short trimethyl.Temperature of reaction must maintain one 3～0 ℃.Temperature is high more, and trimethyl generates many more.The exothermic heat of reaction amount is big, consumes cold highly especially, otherwise that useless trimethyl generates is many.The content of monochloride also only has 90-93%, and trimethyl content is up to 6%, and its yield to dichloro also only has 88-90%.
One chlorine and content are the ammoniacal liquor reaction of 17-18%, generate O, and the O-dimethyl thiophosphoryl amide is through taking off the spermine that trimethyl promptly generates 92-94%, yield 98%.
The main reaction formula in above-mentioned each step is:
④
Side reaction:
③
When dichloro is made a chlorine, the content of alkali, the temperature that adds the amount of alkali and add alkali is extremely relevant to the growing amount of harmful useless trimethyl, and the major impurity of a chlorine is the thiophosphoric acid trimethyl, is called for short trimethyl.The total recovery of its four-step reaction has only 79-83%.
Besides because dichloro and a chlorine production all will be controlled at operation lesser temps under, therefore, for 20000 tons of spermine institute chilling requirements of annual output 1,000 ten thousand kilocalories/hour more than.
In addition, when dichloro and a chlorine were produced, methyl alcohol all was excessive, if methyl alcohol does not reclaim, causes first environment is polluted greatly, second causes great loss economically.So this technology must have powerful methanol recovery system, spermine per ton will consume steam 7-9 ton.
Aspect environmental improvement, because yield is low, pollutent generates many, and a large amount of organophosphorus materials will be through biochemical treatment, and this has brought a lot of difficulties to waste water control, consume substantial contribution and administer the three wastes.
Fig. 1 is seen in its technical process: the phosphorus thiochloride method is produced the spermine technological process block-diagram
Summary of the invention:
The objective of the invention is O, the working method of O-dimethyl thiophosphoryl amide is improved, and to improve O, the O-dimethyl thiophosphoryl amide reduces and pollutes the yield and the product gas purity of phosphorus trichloride.
The technical scheme that realizes above-mentioned purpose is:
The present invention adopts trimethyl phosphite to produce O; The working method of O-dimethyl thiophosphoryl amide; Its raw material is phosphorus trichloride, anhydrous methanol, sulphur, ammoniacal liquor, and its working method is: in the presence of solvent benzol and acid binding agent triethylamine, react the generation trimethyl phosphite with phosphorus trichloride and anhydrous methanol; This step reaction, trimethyl phosphite can reach more than 98% the total recovery of phosphorus trichloride.Trimethyl phosphite reacts with phosphorus trichloride again, generates O, O-dimethyl-monochlor(in)ate phosphorus; Add sulphur again and can generate O, the O-dimethyl thiophosphoryl chloride promptly adds ammoniacal liquor and just generates O after separating, and O-dimethyl thiophosphoryl amide bullion just obtains O, O-dimethyl thiophosphoryl amide elaboration through dehydration; Its temperature of reaction is all at 20 ℃, and cold consumption is low, its O, and the O-dimethyl thiophosphoryl amide can reach more than 96% to the yield of trimethyl phosphite; Its O, the O-dimethyl thiophosphoryl amide can reach more than 94% the total recovery of phosphorus trichloride.
The main reaction formula in above-mentioned each step is:
①
②(C
2H
5)
3N·HCl+NaOH→(C
2H
5)
3N+NaCl+H
2O
③2(CH
3O)
3P+PCl
3→3ClP(CH
3O)
2
④
⑤
The main side reaction in above-mentioned each step does
①2(CH
3O)
3P+4PCl
36CH
3OPCl
2
②
③
Side reaction mainly is to have generated the methoxyl group phosphorus dichloride, just generates dichloro after this product sulfuration, and dichloro just generates the methyl thio-phosphoryl diamines through amination.This product is very easily water-soluble, thereby gets in the sewage and can not get in the product.Can find out that from above-mentioned reaction reaction does not have the thiophosphoric acid trimethyl to generate from start to finish, therefore, the monochloride of producing with this operational path does not contain any thiophosphoric acid trimethyl, and the content of monochloride can reach more than 97%.Thereby, making O, the content of O-dimethyl thiophosphoryl amide just reaches 99%.
Fig. 2 is a Production Flow Chart skeleton diagram of the present invention.
Advantage of the present invention is following:
1, good product quality of the present invention: the O of former phosphorus thiochloride explained hereafter, the content of O-dimethyl thiophosphoryl amide can only reach 90-93%; And the O of trimethyl phosphite explained hereafter of the present invention, the content of O-dimethyl thiophosphoryl amide reaches 99%.
2, energy consumption of the present invention is low: former phosphorus thiochloride technology will reclaim a large amount of methyl alcohol; And trimethyl phosphite technology of the present invention is to separate with triethylamine benzene with trimethyl phosphite; The isolating amount of two technologies institute is similar; But the vaporization heat of benzene, triethylamine is much little more than the vaporization heat of methyl alcohol, so the amount of phosphorus thiochloride technology consumption steam is more much bigger than the amount of the present invention trimethyl phosphite consumption steam.
Secondly, the dichloro in the former phosphorus thiochloride production technique and the temperature of reaction of a chlorine must have powerful freezing supportingly all about 0 ℃ in its production equipment, and its cold consumption is very high, and the temperature of the present invention's reaction has only recirculated water to get final product generally about 70 ℃.
3, environmental pollution:
Because the yield of former phosphorus thiochloride technology is more much lower than the yield of trimethyl phosphite technology of the present invention; So the former by product is just many, its sewage has one foul smell, and the difficulty of its processing is very big; Consume a large amount of funds and handle the three wastes; And the present invention has basically no pollution, and is therefore, free from environmental pollution.
Compare with former phosphorus thiochloride technology, the present invention has obtained to improve the unusual effect of yield and product purity.With the O that the present invention produces, the O-dimethyl thiophosphoryl amide can obviously improve the quality of derived product, reduces the consumption of derived product.
Description of drawings
Fig. 1 produces O, O-dimethyl thiophosphoryl amide technological process of production skeleton diagram for the phosphorus thiochloride method before improving;
Fig. 2 is a Production Flow Chart skeleton diagram of the present invention.
Embodiment
Embodiments of the invention are:
The synthetic used raw material of this product is phosphorus trichloride, anhydrous methanol, sulphur and ammoniacal liquor; In the presence of solvent benzol and acid binding agent triethylamine, generate trimethyl phosphite with phosphorus trichloride and anhydrous methanol earlier in the trimethyl reaction kettle for reaction; Trimethyl phosphite again with phosphorus trichloride reacted O in chlorinator, O-dimethyl-monochlor(in)ate phosphorus; In vulcanizing apparatus, add sulphur again and can generate O, the O-dimethyl thiophosphoryl chloride promptly adds ammoniacal liquor and just can generate O in ammoniator after separating, the O-dimethyl thiophosphoryl amide, and its temperature of reaction is 20 ℃.
The input amount of the phosphorus trichloride in the present embodiment is 1037kg, and the input amount of anhydrous methanol is 483kg, and the input amount of sulphur is 242kg, and the input amount of ammoniacal liquor is 256kg, product volume 1000kg, total recovery 94%, product content 99%.
Claims (1)
1. O, the working method of O-dimethyl thiophosphoryl amide, its raw material is phosphorus trichloride, anhydrous methanol, sulphur and ammoniacal liquor; It is characterized in that: phosphorus trichloride and anhydrous methanol react in the presence of solvent benzol and acid binding agent triethylamine and generate trimethyl phosphite, and reaction generates O, O-dimethyl-monochlor(in)ate phosphorus to trimethyl phosphite with phosphorus trichloride again; Add sulphur again and promptly generate O, the O-dimethyl thiophosphoryl chloride adds ammoniacal liquor and generates O after separating; O-dimethyl thiophosphoryl amide bullion, its temperature of reaction are 20 ℃, after dehydration, are O; O-dimethyl thiophosphoryl amide elaboration
Its reaction formula is:
①
②(C
2H
5)
3N·HCl+NaOH→(C
2H
5)
3N+NaCl+H
2O
③2(CH
3O)
3P+PCl
3→3ClP(CH
3O)
2
④
⑤
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810236831A CN101486731B (en) | 2008-12-12 | 2008-12-12 | Production method of O, O-dimethyl thiophosphoryl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810236831A CN101486731B (en) | 2008-12-12 | 2008-12-12 | Production method of O, O-dimethyl thiophosphoryl chloride |
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| Publication Number | Publication Date |
|---|---|
| CN101486731A CN101486731A (en) | 2009-07-22 |
| CN101486731B true CN101486731B (en) | 2012-08-29 |
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|---|---|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724371A (en) * | 2013-12-18 | 2014-04-16 | 沙隆达集团公司 | Production method of high-content and low-trimethyl ester spermine |
| CN107417720B (en) * | 2017-08-23 | 2019-07-02 | 湖北三才堂化工科技有限公司 | A kind of ammonia amination legal system takes O, the production technology of O- dimethyl thiophosphoryl amide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127566A (en) * | 1998-09-16 | 2000-10-03 | Bayer Corporation | Process for the synthesis of O,O-dimethyl phosphoroamidothioate |
-
2008
- 2008-12-12 CN CN200810236831A patent/CN101486731B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6127566A (en) * | 1998-09-16 | 2000-10-03 | Bayer Corporation | Process for the synthesis of O,O-dimethyl phosphoroamidothioate |
Non-Patent Citations (2)
| Title |
|---|
| 董勇章.三乙胺法亚磷酸三甲酯连续合成新工艺小试总结.《安徽化工》.1984,(第3期),第2页. * |
| 龙洁等.O,O-二甲基硫代磷酰氯的合成进展.《精细与专用化学品》.2004,第12卷(第7期),第10页. * |
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