CN101870712B - Production method of dimethyl phosphite - Google Patents
Production method of dimethyl phosphite Download PDFInfo
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- CN101870712B CN101870712B CN2009100590135A CN200910059013A CN101870712B CN 101870712 B CN101870712 B CN 101870712B CN 2009100590135 A CN2009100590135 A CN 2009100590135A CN 200910059013 A CN200910059013 A CN 200910059013A CN 101870712 B CN101870712 B CN 101870712B
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Abstract
The invention relates to a production method of dimethyl phosphate, which takes phosphorus trichloride and methyl alcohol as raw materials for reaction. The method comprises the steps of: in a reaction chamber space having cross injection angle and the injection structures of the raw materials, respectively and continuously injecting and sending the phosphorus trichloride and the methyl alcohol which are based on the molar ratio of 1: (3.0-3.1) into the reaction chamber space through respective injection structures by corresponding pumping mechanisms for mixing together and reaction; then, introducing reaction material into a centrifugal cyclone separator with the pressure lower than that of the reaction chamber space along the tangential direction, and leading noncondensable gas and condensing liquid product to have centrifugal cyclone separation; and collecting the liquid dimethyl phosphate product descending along the inner wall of the centrifugal cyclone separator. The method can rapidly complete the reaction and the separation for products, effectively reduces the contact between HCl and the dimethyl phosphate, inhibits the occurrence of side reaction, improves the yield and the quality of the product, and greatly reduces the energy consumption.
Description
Technical field
What the present invention relates to is a kind of working method of improved dimethylphosphite.
Background technology
Dimethylphosphite is a staple product in the fine chemistry industry.It is a midbody of producing agricultural chemicals such as Glyphosate 62 IPA Salt, Trichlorphon, EBP, omethoate; It is again the raw material of organophosphor agent, dye additive, additives for plastics and fire retardant; Can be used for the synthetic water treatment agent, also can be used as the products such as sterilant, static inhibitor, softening agent that methylating reagent is used for synthetic quaternary ammonium salts.
Dimethylphosphite generally is to be that raw material reaction makes with phosphorus trichloride and methyl alcohol in industry:
PCl
3+3CH
3OH→(CH
3O)
2POH+2HCl↑+CH
3Cl↑
Reaction process and mechanism are:
PCl
3+CH
3OH→CH
3OPCl
2+HCl↑ (1)
CH
3OPCl
2+CH
3OH→(CH
3O)
2PCl+HCl↑ (2)
(CH
3O)
2+CH
3OH→(CH
3O)
3P+HCl↑ (3)
(CH
3O)
3P+HCl→(CH
3O)
2POH+CH
3Cl↑ (4)
Trimethyl phosphite in the reaction process in (3) formula is extremely unstable, as long as there is HCl to exist, just can react the generation dimethylphosphite.And the existence of HCl also very easily makes the product dimethylphosphite continue to take place following side reaction simultaneously:
(CH
3O)
2POH+HCl→CH
3OP(OH)
2+CH
3Cl↑
CH
3OP(OH)
2+HCl→H
3PO
3+CH
3Cl↑
Temperature in the reaction process is high more and/or the time is long more, and side reaction is many more.Because the above-mentioned reaction of phosphorus trichloride and methyl alcohol is the instantaneous reaction of strong heat release; Therefore guarantee the key that reaction is carried out and accomplished smoothly; Be the condition that two reactants are fully contacted of as far as possible creating, and shorten the reaction times, remove reaction heat effectively; And remove the HCl in the reaction product as much as possible, to suppress the generation of side reaction.
What at present the industrial production of dimethylphosphite is continued to use always is the interrupter method of single pot of reaction and single still rectifying; Its reaction mass is sent into via header tank; The measure control difficulty is big, and needs control to be reflected at the carrying out below 55 ℃, and operation is frequent; Labour intensity is big, and the production cycle is long, capacity of equipment is low.Simultaneously, in reaction process, need shift out the heat of reaction with freezing mode, and need material be heated during depickling, the capacity usage ratio in the production process is low.
Summary of the invention
To above-mentioned situation, the present invention will provide a kind of new dimethylphosphite working method, to address the above problem.
The working method of dimethylphosphite of the present invention is that raw material reacts with phosphorus trichloride and methyl alcohol still.Its detailed process; Be in the reaction chamber space that is provided with each the raw material injection structure with staggered form spray angle, in molar ratio 1: the phosphorus trichloride of (3.0～3.1) metering and methyl alcohol warp injection structure are separately respectively sent into the mutual hybrid reaction in reaction chamber space by each corresponding pumping mechanism continuous injection.Because reaction raw materials is through spraying; Particularly the atomizing after high-velocity jet can make it be separated into tiny droplet; Helping stock yard realizes rapidly, fully and uniformly mixes; And be in contact with one another, collide with bigger contact area, thereby make reaction can be in the several seconds (for example 3～5 seconds) rapidly, carry out fully and accomplish.Then reaction mass is tangentially introduced pressure and be lower than the centrifugal cyclone separation device of reaction chamber spatial.Because this reaction is a strong exothermal reaction; Therefore the reaction mass after hybrid reaction is accomplished; When being introduced into centrifugal cyclone separation device in the rapid expansible process of volume; Can make full use of reaction heat and accomplish vaporization,, between the interface of material, accomplish thermal exchange along doing in the cyclone separation device in the circumferential motion.Non coagulating gases such as HCl wherein and methyl chloride utilize the reaction heat dimethylphosphite product of back with the liquefaction that is condensed that heated up to be separated, and the upstream that forms the internal screw shape is discharged by the top and sent to down the step processing; By the dimethylphosphite of cooling condensation liquefaction, descending and form descending liquid film and be collected at the inner-wall surface of device along spiral way.Thereby realized making gaseous state compositions such as HCl to separate quickly and removed, effectively suppressed the generation of side reaction with the dimethylphosphite of condensation liquefaction.
Through test; In above-mentioned method; Collide the phosphorus trichloride and methyl alcohol two reaction raw materials of hybrid reaction in the said reaction chamber space with the cross jet mode each other, make the effect of its mutual hybrid reaction of injection stream that becomes 40～120 ° of angle modes more preferred with employing.
As above-mentioned; Remove the duration of contact that as far as possible shortens reaction raw materials; It can be mixed rapidly accomplish outside the reaction, temperature of reaction also is the influence factor that should note, by present mode; Temperature of reaction is controlled to be no more than under 55 ℃ of conditions all allows, the hybrid reaction temperature that is more preferably phosphorus trichloride and methyl alcohol in above-mentioned reaction chamber space is controlled to be under the condition that is not higher than 45 ℃.
Because two reaction raw materials are to be admitted to the spray regime with fair speed to carry out hybrid reaction in the reaction chamber space, so the travelling speed of material is corresponding also comparatively rapid.For helping guaranteeing that two raw materials can have the time of thorough mixing reaction; Can be according to actual needs; Make the reaction mass in the said reaction chamber space be introduced into centrifugal cyclone separation device, in the operational process of this centrifugal cyclone separation device, continuing fully to accomplish reaction in order to material through the duct type reaction extended structure of suitable length.
When adopting centrifugal cyclone separation device to carry out the mixture separation, generally all should have lower pressure in the rotational flow separation chamber of this cyclone separation device.For further improving separating effect to reaction mass; Through test; In above-mentioned method; The pressure that makes said centrifugal cyclone separation device with employing to be being higher than gauge pressure-0.075MPa, and/or makes said reaction mass more preferred with the mode that the speed of 5～10m/s tangentially is introduced into centrifugal cyclone separation device.
In sepn process, under as yet by complete isolating HCl influence, do not carry out disadvantageous side reaction for reduce reaction mass as far as possible, said reaction mass carries out the isolating temperature of centrifugal cyclone to be controlled at 60 ℃～80 ℃ for well.
For helping controlling and regulating the temperature of hybrid reaction and/or centrifugal cyclone sepn process, what above-mentioned said hybrid reaction and/or centrifugal cyclone separation were best is to adopt as the reaction chamber space and/or the centrifugal cyclone separation device that have jacketed type thermal insulation layer equitemperature control/adjustment structure commonly used.For example, for the above-mentioned strong exothermal reaction of the present invention, can be temperature required accordingly through in chuck, feeding the medium control/adjusting that cools such as icy salt solution.
According to the different production scale, the above-mentioned working method of the present invention can have different concrete operations modes.For example, can said raw material phosphorus trichloride and methyl alcohol be accomplished reaction by said molar ratio disposable feeding intake in same said reaction chamber space.
The above-mentioned working method of the present invention can also adopt the mode of two-stage reaction, makes said phosphorus trichloride and methyl alcohol accomplish reaction through the said reaction chamber of the two-stage space that is provided with continuously respectively by said molar ratio.When adopting the two-stage reaction mode; In first step reaction chamber space; By the methyl alcohol of the phosphorus trichloride of whole amounts and 1/2～3/4 amount with the mutual hybrid reaction of said spray regime; After said centrifugal cyclone separates, the methyl alcohol of separated product of collecting and residual content sent in the said reaction chamber space, the second stage with same spray regime again carry out hybrid reaction, and carry out follow-up centrifugal cyclone separation.According to aforesaid reaction process and mechanism, particularly when big, adopt the mode of this two-stage reaction can obtain even more ideal effect for industrial scale.
Test shows that aforementioned production method of the present invention can shorten the reaction times greatly; Avoid the acidolysis side reaction of dimethylphosphite effectively; Improved effective transformation efficiency of raw material, the yield of dimethylphosphite can reach more than 90%, and the hydrogenchloride decreasing ratio in the thick ester product can reach 98%.And the employing produced in conventional processes; The yield of dimethylphosphite is generally 80～88%, and the decreasing ratio of HCl is about 90%, and owing to mainly be in the depickling device, to accomplish to removing of HCl; Therefore the load of depickling device is big, and HCl remove the untimely many problems of side reaction of also having brought.In addition, aforesaid method of the present invention can make dimethylphosphite realize the production of serialization, for the lifting of production capacity with further reduce running cost significantly great development space is provided.
Below in conjunction with the embodiment of accompanying drawing illustrated embodiment, foregoing of the present invention is remake further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following instance.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Description of drawings
Fig. 1 is a kind of reaction/separation schematic representation of apparatus applicable to working method of the present invention.
Embodiment
In device shown in Figure 1; Respectively with the mode of methyl alcohol 810kg/h and phosphorus trichloride 1160kg/h, through its volume pump 1 metering separately after send into the reaction chamber space 3 that has reaction extension tube and cooling jacket structure with high pressure spray nozzle 2 continuous injections that become 70 ° of angles.Under the jetting action of high pressure spray nozzle 2; The pressure-controlling that raw material gets into conversion zone cavity space 3 be gauge pressure-0.085～-0.090MPa; Under the cooling jacket control that feeds icy salt solution; Make raw material under 40～45 ℃ of temperature, collide hybrid reaction each other with spray regime; And make reaction mass tangentially get into centrifugal eddy flow (wind) separator 4 of pressure for-0.090～0.092 (gauge pressure) along reacting the speed of extension tube with 8.5m/s, under～70 ℃ of conditions, separate thick product of liquid product dimethylphosphite and noncondensable gases such as HCl, methyl chloride.In the thick product of dimethylphosphite that obtains after centrifugal cyclone separator 4 separation, the removing hydrogen chloride rate reaches 95%, and the yield of thick product dimethylphosphite after rectification process is 89.1%.
Form the second order reaction flow process by the same apparatus of two structures as shown in Figure 1.Raw material is respectively with methyl alcohol 890kg/h, the mode of phosphorus trichloride 1257kg/h, and through after volume pump 1 metering separately the methyl alcohol injection of the phosphorus trichloride of full dose and 594kg being sent into the reaction chamber space 3 of first step device, its injection stream angle is 120 °.First order reaction device pressure-controlling gauge pressure-0.075～-0.080MPa, 48～50 ℃ of control reaction temperature, the speed that gets into eddy flow (wind) separator is 5.5m/s, temperature control is 75 ± 1 ℃ in the cyclonic separator.Second stage reaction unit gauge pressure-0.085～-0.090MPa, the injection stream angle is 90 °, 50～53 ℃ of temperature of reaction, the speed that gets into eddy flow (wind) separator is 7.5m/s, temperature control is 65 ± 1 ℃ in the cyclonic separator.Parting liquid by the collection of second stage reaction unit.Through detecting, the decreasing ratio of its HCl reaches 98%, and the yield of bullion after rectification and purification is 91.5%.
Claims (8)
1. the working method of dimethylphosphite; With phosphorus trichloride and methyl alcohol is that raw material reacts; It is characterized in that in the reaction chamber space that is provided with each raw material injection structure with staggered form spray angle; In molar ratio 1: the phosphorus trichloride of (3.0～3.1) metering and methyl alcohol warp injection structure are separately respectively sent into the mutual hybrid reaction in reaction chamber space by each corresponding pumping mechanism continuous injection; Then reaction mass is tangentially introduced pressure and be lower than the centrifugal cyclone separation device of reaction chamber spatial; Under 60 ℃～80 ℃, make non-condensable gas attitude composition and liquid condensed product carry out centrifugal cyclone and separate, collect along the descending liquid dimethylphosphite product of centrifugal cyclone separation device inwall.
2. the working method of dimethylphosphite as claimed in claim 1 is characterized in that in said reaction chamber space, and phosphorus trichloride collides hybrid reaction with methyl alcohol with the injection stream that becomes 40～120 ° of angles each other.
3. the working method of dimethylphosphite as claimed in claim 1 is characterized in that the hybrid reaction temperature of phosphorus trichloride and methyl alcohol is not higher than 45 ℃ in said reaction chamber space.
4. the working method of dimethylphosphite as claimed in claim 1 is characterized in that the reaction mass in the said reaction chamber space is introduced into centrifugal cyclone separation device through duct type reaction extended structure.
5. the working method of dimethylphosphite as claimed in claim 1 is characterized in that the pressure of said centrifugal cyclone separation device is not higher than gauge pressure-0.075MPa.
6. the working method of dimethylphosphite as claimed in claim 1 is characterized in that said reaction mass tangentially is introduced into centrifugal cyclone separation device with the speed of 5～10m/s.
7. like the working method of the described dimethylphosphite of one of claim 1 to 6, it is characterized in that said phosphorus trichloride and methyl alcohol are by the disposable completion reaction that feeds intake in same said reaction chamber space of said molar ratio.
8. like the working method of the described dimethylphosphite of one of claim 1 to 6; It is characterized in that said phosphorus trichloride and methyl alcohol are by the said reaction chamber of the two-stage space completion reaction through being provided with continuously respectively of said molar ratio; In first step reaction chamber space; By the methyl alcohol of the phosphorus trichloride of whole amounts and 1/2～3/4 amount with the mutual hybrid reaction of said spray regime; After said centrifugal cyclone separates, the methyl alcohol of separated product of collecting and residual content sent in the said reaction chamber space, the second stage with same spray regime again carry out hybrid reaction, and carry out follow-up centrifugal cyclone separation.
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|---|---|---|---|
| CN2009100590135A CN101870712B (en) | 2009-04-21 | 2009-04-21 | Production method of dimethyl phosphite |
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|---|---|---|---|
| CN2009100590135A CN101870712B (en) | 2009-04-21 | 2009-04-21 | Production method of dimethyl phosphite |
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|---|---|
| CN101870712A CN101870712A (en) | 2010-10-27 |
| CN101870712B true CN101870712B (en) | 2012-07-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2581378A1 (en) | 2011-10-13 | 2013-04-17 | Straitmark Holding AG | Method for the esterification of P-O components |
| CN107501318A (en) * | 2017-07-13 | 2017-12-22 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate intermediate dimethylphosphite |
| TWI648217B (en) | 2017-08-25 | 2019-01-21 | 國立清華大學 | Halogen-doped phosphonium particle and method of producing the same |
| CN111675638B (en) * | 2020-05-04 | 2021-12-31 | 曲靖师范学院 | Method for synthesizing organic sulfone molecule by novel sulfone methylation reagent |
| CN112110837B (en) * | 2020-08-19 | 2022-04-22 | 曲靖师范学院 | Method for synthesizing organic sulfone molecule by using novel sulfone benzylation reagent |
| CN115282873B (en) * | 2022-07-25 | 2023-07-28 | 湖北泰盛化工有限公司 | Dimethyl phosphite synthesis device and process |
| CN116178317A (en) * | 2023-03-14 | 2023-05-30 | 台山市新宁制药有限公司 | Furosemide production process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373845A (en) * | 1999-09-08 | 2002-10-09 | 格拉默器材有限公司 | Refrigerator with cyclone liquid gas separator |
| US7108838B2 (en) * | 2003-10-30 | 2006-09-19 | Conocophillips Company | Feed mixer for a partial oxidation reactor |
-
2009
- 2009-04-21 CN CN2009100590135A patent/CN101870712B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373845A (en) * | 1999-09-08 | 2002-10-09 | 格拉默器材有限公司 | Refrigerator with cyclone liquid gas separator |
| US7108838B2 (en) * | 2003-10-30 | 2006-09-19 | Conocophillips Company | Feed mixer for a partial oxidation reactor |
Non-Patent Citations (2)
| Title |
|---|
| 季诚建.亚磷酸二甲酯反应动力学及合成工艺研究.《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑 B016-18》.2005,(第6期),23-24. * |
| 陈晓祥等.亚磷酸二甲酯的绿色生产工艺.《化学世界》.2000,(第12期),638-640,631. * |
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Correction item: Patentee Correct: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. False: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. Number: 27 Volume: 28 |
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Correction item: Patentee Correct: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. False: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. Number: 27 Page: The title page Volume: 28 |
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Address after: 614803 Jinsu Town, Wutongqiao District, Leshan City, Sichuan Province Patentee after: Fuhua Tongda Chemical Co.,Ltd. Patentee after: SICHUAN University Address before: 614800 Sichuan city of Leshan province Wutongqiao District Bridge Town Fuhua agricultural investment group Patentee before: Sichuan Leshan Fuhua Tongda Pesticide Technology Co.,Ltd. Patentee before: SICHUAN University |
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