CN103880786B - A kind of method reclaiming useful component in careless ammonium phosphine production process mixing solvent slop - Google Patents
A kind of method reclaiming useful component in careless ammonium phosphine production process mixing solvent slop Download PDFInfo
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- CN103880786B CN103880786B CN201410098473.XA CN201410098473A CN103880786B CN 103880786 B CN103880786 B CN 103880786B CN 201410098473 A CN201410098473 A CN 201410098473A CN 103880786 B CN103880786 B CN 103880786B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/48—Phosphonous acids R—P(OH)2; Thiophosphonous acids including RHP(=O)(OH); Derivatives thereof
Abstract
The invention discloses a kind of adopt integrated rectification process reclaim careless ammonium phosphine production process produce mixing solvent slop in tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, the method of the useful components such as trimethylbenzene, the integrated rectification process of single tower distillation is connect after adopting the rectifying of single tower lateral line discharging, from the direct extraction tetrahydrofuran (THF) of side line rectifying tower tower top, tower reactor obtains trimethylbenzene, simultaneously from the mixed solution of side take-off methylisothiouronium methylphosphite diethyl ester and triethyl-phosphite, send into rectifying tower and carry out single tower separation, tower top obtains methylisothiouronium methylphosphite diethyl ester, tower reactor obtains triethyl-phosphite.The inventive method adopts integrated rectification process to reclaim useful component in careless ammonium phosphine production process mixing solvent slop, and the overall rate of recovery of mixed solvent is more than 98%, and quality all reaches the standard of reusing.The present invention is compared with three conventional tower conventional distillation methods, and equipment cost and energy consumption all obviously reduce.
Description
Technical field
The present invention relates to a kind of separation method of chemical industry, particularly relate to the method for the useful component such as tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene in a kind of adopt integrated rectification process to reclaim mixing solvent slop that careless ammonium phosphine production process produces.
Background technology
The new herbicides that Cao Anlinshi Hirst company (be the Beyer Co., Ltd subordinate enterprise at present) 1980s develops, except having weeding activity, also has bactericidal and insecticidal activity, can with agrochemical mixture, reach the effect of simultaneously preventing and treating.The features such as this weedicide has efficiently, low toxicity, environmental friendliness, easily degraded.
The common technology flow process of current production grass ammonium phosphine is: take tetrahydrofuran (THF) as solvent, first with phosphorus trichloride cheap and easy to get and triethyl-phosphite for diethyl chlorophosphite prepared by raw material, obtain diethyl methyl-phosphonite through grignard reaction; Then diethyl methyl-phosphonite and ethylene dibromide are obtained by reacting methyl (2-bromotrifluoromethane) phosphinic acid ethyl ester under catalyst; Last and acetamino diethyl malonate negative ion reacts in trimethylbenzene, and through hcl acidifying, ammoniacal liquor ammonium obtains careless ammonium phosphine ammonium salt.Inevitably produce the mixing solvent slop comprising useful component in a large number in the production process of grass ammonium phosphine, its main component is: tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene.Based on the requirement of environmental protection and production cost, for this part solvent slop, must pursue the proper method recycling.
At present, for the mixing solvent slop produced in careless ammonium phosphine production process, through collecting, after preliminary treatment, the conventional separation methods adopted uses with three atmospheric distillation tower series connection, for mixed solution (tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene) according to the height rectifying separation successively of component boiling point, concrete steps are: First rectifying tower tower top obtains light constituent tetrahydrofuran (THF), heavy constituent at the bottom of tower is sent to second tower and continues rectifying, trimethylbenzene is obtained at the bottom of second tower tower, tower top obtains light constituent methylisothiouronium methylphosphite diethyl ester, the mixed solution of triethyl-phosphite, send into the 3rd rectifying tower again and continue rectifying, 3rd rectifying tower tower top obtains methylisothiouronium methylphosphite diethyl ester, tower reactor obtains triethyl-phosphite.
The shortcoming of three tower cascade connected atmospheric distillation is mainly in two: one is have employed three-column process flow, equipment manufacturing cost and process cost higher; Two is that sepn process is evaporated through three times, and energy consumption is bigger than normal.This also directly has influence on careless ammonium phosphine production cost.
Summary of the invention
The object of this invention is to provide a kind of adopt integrated rectification process reclaim careless ammonium phosphine production process produce mixing solvent slop in tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, the method of the useful components such as trimethylbenzene, the integrated rectification process of single tower distillation is connect after adopting the rectifying of single tower lateral line discharging, from the direct extraction tetrahydrofuran (THF) of side line rectifying tower tower top, tower reactor obtains trimethylbenzene, simultaneously from the mixed solution of side take-off methylisothiouronium methylphosphite diethyl ester and triethyl-phosphite, send into common rectifying tower to be separated, tower top obtains methylisothiouronium methylphosphite diethyl ester, tower reactor obtains triethyl-phosphite.The present invention can reduce rectifying tower in removal process and evaporative process, and while ensure that useful component reclaims quality and yield, equipment manufacturing cost, energy consumption obviously reduce.
The technical scheme completing foregoing invention task is: a kind of method adopting integrated rectification process to reclaim tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene in careless ammonium phosphine production process mixing solvent slop, and step is as follows:
(1) careless ammonium phosphine production process mixing solvent slop obtains the mixture of tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene after pretreatment, with described mixture for raw material, sends into side line rectifying tower rectifying separation continuously.
(2) side line rectifying tower tower top cuts the cut of 65 ~ 66 DEG C, controls reflux ratio, the tetrahydrofuran (THF) of overhead extraction mass percent >=99.5%; Trim the top of column is than being 2:1 ~ 6:1, and optimum reflux ratio is: 4:1.
(3) the middle part side line of side line rectifying tower cuts the cut of 120 ~ 158 DEG C, and control reflux ratio, the methylisothiouronium methylphosphite diethyl ester of extraction and the mixed solution of triethyl-phosphite enter the rectifying tower of connecting with side line rectifying tower; Side reflux is than being 3:1 ~ 4:1, and optimum reflux ratio is: 3.5:1.
(4) side line rectifying kettle material is heated by reboiler, control temperature 170 ~ 185 DEG C, the trimethylbenzene of extraction mass percent >=98% after partial material cooling.
(5) methylisothiouronium methylphosphite diethyl ester is separated in rectifying tower continuous rectification with the mixed solution of triethyl-phosphite, and rectifying tower tower top cuts the cut of 124 ~ 126 DEG C, controls reflux ratio, the methylisothiouronium methylphosphite diethyl ester of overhead extraction mass percent >=98.5%; Trim the top of column is than being 2:1 ~ 4:1, and optimum reflux ratio is: 3:1.
(6) tower bottom of rectifying tower material is heated by reboiler, control temperature 155 ~ 160 DEG C, the triethyl-phosphite of extraction mass percent >=95% after partial material cooling.
Grass ammonium phosphine production process mixing solvent slop carries out preliminary treatment by method of the prior art, obtains the mixture of useful component tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene composition.Based on careless ammonium phosphine synthesis technique, in the mixture of described tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene, usual each constituent mass percentage ratio is: tetrahydrofuran (THF) 34-36%, methylisothiouronium methylphosphite diethyl ester 13-17%, triethyl-phosphite 1-3%, trimethylbenzene 46-50%.
In the inventive method mixing solvent slop, the technical process of sepn process as shown in Figure 1, adopts the processing condition of optimization, can obtain highly purified tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite and trimethylbenzene after separation simultaneously in sepn process.
Preferably, described side line theoretical number of plates of rectifying tower is 40 ~ 60,18th ~ 22 pieces, feedstock position column plate (from lower to upper), 25th ~ 27 pieces, lateral line discharging position column plate (from lower to upper).
Preferably, described theoretical number of plates of rectifying tower is 13 ~ 18,7th ~ 9 pieces, feedstock position column plate (from lower to upper).
Advantage of the present invention: integrated rectification process of the present invention, adopt the processing parameter of technical process and optimization shown in Fig. 1, the rectifying tower that side line rectifying tower overhead extraction mass percent is the tetrahydrofuran (THF) of 99.9%, the mixed solution of side take-off methylisothiouronium methylphosphite diethyl ester and triethyl-phosphite is transported to series connection continues process, tower reactor obtains the trimethylbenzene of mass percent more than 98%, rectifying tower tower top obtains the methylisothiouronium methylphosphite diethyl ester of mass percent more than 98.5%, and tower reactor obtains the triethyl-phosphite of mass percent more than 95%.The integrated rectification process of employing of the present invention reclaims the method for useful component in careless ammonium phosphine production process mixing solvent slop, and the overall rate of recovery of mixed solvent is more than 98%, and quality all reaches the standard of reusing.Compared with the three tower conventional distillation methods that the present invention and routine use, save a rectifying tower, decrease single vaporization process, equipment cost and energy consumption all obviously reduce.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that integrated rectification process of the present invention reclaims the useful component such as tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene in the mixing solvent slop that careless ammonium phosphine production process produces.In figure: 1 is side line rectifying tower T-1 overhead condenser, 2 is tetrahydrofuran (THF) receiving tank, and 3 is side line condenser, and 4 is the receiving tank of methylisothiouronium methylphosphite diethyl ester and triethyl-phosphite mixed solution, 5 is side line rectifying tower T-1 reboiler, 6 is side line rectifying tower T-1 tower reactor water cooler, and 7 is trimethylbenzene receiving tank, and 8 is rectifying tower T-2 overhead condenser, 9 is methylisothiouronium methylphosphite diethyl ester receiving tank, 10 is rectifying tower T-2 reboiler, and 11 is rectifying tower T-2 tower reactor water cooler, and 12 is triethyl-phosphite receiving tank.
Embodiment
Embodiment 1
The method of the useful component such as tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene in the mixing solvent slop that careless ammonium phosphine production process produces is reclaimed in a kind of integrated rectifying, technical process as shown in Figure 1, with reference to the processing parameter shown in table 1, step is as follows:
(1) mixing solvent slop is produced for raw material, with being pumped into side line rectifying tower with the careless ammonium phosphine after factory's preliminary treatment;
(2) side line rectifying tower tower top cuts the cut of 65 ~ 66 DEG C, and control reflux ratio, overhead extraction is as the product introduction tetrahydrofuran (THF) storage tank of tetrahydrofuran (THF);
(3) the middle part side line of side line rectifying tower cuts the cut of 120 ~ 158 DEG C, and after interchanger heat exchange, control reflux ratio, the mixed solution of extraction methylisothiouronium methylphosphite diethyl ester and triethyl-phosphite enters the rectifying tower of series connection;
(4) side line rectifying tower reactor is heated by reboiler, control temperature 170 ~ 185 DEG C, as trimethylbenzene product introduction trimethylbenzene finished product storage tank after partial material extraction cooling;
(5) the rectifying tower tower top connect after cuts the cut of 124 ~ 126 DEG C, and control reflux ratio, overhead extraction is as the product introduction methylisothiouronium methylphosphite diethyl ester storage tank of methylisothiouronium methylphosphite diethyl ester;
(6) tower bottom of rectifying tower material is heated by reboiler, control temperature 155 ~ 160 DEG C, as triethyl-phosphite product introduction triethyl-phosphite finished product storage tank after partial material extraction cooling.
See table 2, each material stream is described in detail as follows.1. raw material mixes solvent slop for after factory's preliminary treatment, and wherein the mass percentage of tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene is respectively 35%, 15%, 2%, 48%, and flow is 80Kg/h.The absolute pressure of top of the tower of side line rectifying tower T-1 is 1atm, and temperature is 65 ~ 66 DEG C, and control of reflux ratio is about 4, and overhead extraction thing 2. flow is 27.9Kg/h, and composition (massfraction) is X
tetrahydrofuran (THF)=0.9990, X
methylisothiouronium methylphosphite diethyl ester+triethyl-phosphite=0.0008, X
trimethylbenzene=0.0002,3., temperature is 120 ~ 158 DEG C to lateral line discharging, and flow is 13.3Kg/h, consists of X
tetrahydrofuran (THF)=0.0090, X
methylisothiouronium methylphosphite diethyl ester+triethyl-phosphite=0.9760, X
trimethylbenzene=0.0150, tower reactor discharging 4. flow is 38.8Kg/h, consists of X
tetrahydrofuran (THF)=0.0001, X
methylisothiouronium methylphosphite diethyl ester+triethyl-phosphite=0.0189, X
trimethylbenzene=0.9810; The absolute pressure of top of the tower of rectifying tower T-2 is 1atm, and temperature is 124 ~ 126 DEG C, and control of reflux ratio is about 3, and overhead extraction thing 5. flow is 11.2Kg/h, consists of X
tetrahydrofuran (THF)=0.0030, X
methylisothiouronium methylphosphite diethyl ester=0.9860, X
triethyl-phosphite=0.0100, X
trimethylbenzene=0.0010, tower reactor discharging 6. flow is 2.1Kg/h, consists of X
tetrahydrofuran (THF)=0.0001, X
methylisothiouronium methylphosphite diethyl ester=0.0080, X
triethyl-phosphite=0.9509, X
trimethylbenzene=0.0410.
Table 1 rectifying tower processing condition
Table 2 flows stock explanation
Embodiment 2
Substantially the same manner as Example 1, but wherein side line rectifying tower T-1 trim the top of column is 2:1 than controlling to be the control of 3:1, rectifying tower T-2 trim the top of column ratio.
Embodiment 3
Substantially the same manner as Example 1, but wherein side line rectifying tower T-1 trim the top of column is 4:1 than controlling to be the control of 5:1, rectifying tower T-2 trim the top of column ratio.
Embodiment 4
Substantially the same manner as Example 1, but the proportion of composing of its Raw is: tetrahydrofuran (THF) 34%, methylisothiouronium methylphosphite diethyl ester 16%, triethyl-phosphite 3%, trimethylbenzene 47%.Reclaim its mass percentage of each useful component obtained originally identical with embodiment 1 phase.
Claims (6)
1. adopt integrated rectification process to reclaim a method for tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene in careless ammonium phosphine production process mixing solvent slop, it is characterized in that, described method comprises the steps:
(1) careless ammonium phosphine production process mixing solvent slop obtains the mixture of tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene after pretreatment, in the mixture of described tetrahydrofuran (THF), methylisothiouronium methylphosphite diethyl ester, triethyl-phosphite, trimethylbenzene, each constituent mass percentage ratio is: tetrahydrofuran (THF) 34-36%, methylisothiouronium methylphosphite diethyl ester 13-17%, triethyl-phosphite 1-3%, trimethylbenzene 46-50%; With described mixture for raw material, send into side line rectifying tower rectifying separation continuously;
(2) side line rectifying tower tower top cuts the cut of 65 ~ 66 DEG C, and trim the top of column is than being 2:1 ~ 6:1, the tetrahydrofuran (THF) of overhead extraction mass percent >=99.5%;
(3) the middle part side line of side line rectifying tower cuts the cut of 120 ~ 158 DEG C, and control side reflux than being 3:1 ~ 4:1, the methylisothiouronium methylphosphite diethyl ester of extraction and the mixed solution of triethyl-phosphite enter the rectifying tower of connecting with side line rectifying tower;
(4) side line rectifying kettle material is heated by reboiler, control temperature 170 ~ 185 DEG C, the trimethylbenzene of extraction mass percent >=98% after partial material cooling;
(5) methylisothiouronium methylphosphite diethyl ester is separated in rectifying tower continuous rectification with the mixed solution of triethyl-phosphite, rectifying tower tower top cuts the cut of 124 ~ 126 DEG C, controlling tower top reflux ratio is 2:1 ~ 4:1, the methylisothiouronium methylphosphite diethyl ester of overhead extraction mass percent >=98.5%;
(6) tower bottom of rectifying tower material is heated by reboiler, control temperature 155 ~ 160 DEG C, the triethyl-phosphite of extraction mass percent >=95% after partial material cooling.
2. method according to claim 1, is characterized in that, in step (2), described reflux ratio is: 4:1.
3. method according to claim 1, is characterized in that, in step (3), described reflux ratio is: 3.5:1.
4. method according to claim 1, is characterized in that, in step (5), described reflux ratio is: 3:1.
5. method according to claim 1, is characterized in that, described side line theoretical number of plates of rectifying tower is 40 ~ 60, and feedstock position is 18th ~ 22 blocks of column plates from lower to upper, and lateral line discharging position is 25th ~ 27 blocks of column plates from lower to upper.
6. method according to claim 1, is characterized in that, described theoretical number of plates of rectifying tower is 13 ~ 18, and feedstock position is 7th ~ 9 blocks of column plates from lower to upper.
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| CN106630357B (en) * | 2015-03-16 | 2020-02-21 | 浙江新安化工集团股份有限公司 | Treatment method and treatment system for glufosinate-ammonium magnesium-containing wastewater |
| CN104725416B (en) * | 2015-03-25 | 2017-09-15 | 江苏皇马农化有限公司 | Glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester continuous separation method and device |
| CN104874196B (en) * | 2015-03-26 | 2016-09-14 | 南京师范大学 | A kind of method processing sodium and ammonium acetate salt-diazonium Organic substance-methanol-water mixed solution |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151118 Termination date: 20190318 |