CN100374450C - Triethyl phosphite producing process - Google Patents
Triethyl phosphite producing process Download PDFInfo
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- CN100374450C CN100374450C CNB2006100860554A CN200610086055A CN100374450C CN 100374450 C CN100374450 C CN 100374450C CN B2006100860554 A CNB2006100860554 A CN B2006100860554A CN 200610086055 A CN200610086055 A CN 200610086055A CN 100374450 C CN100374450 C CN 100374450C
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Abstract
The triethyl phosphite producing process with ethanol, phosphorus trichloride, o-dichloro benzene and N, N-dimethyl aniline as material includes the main steps of introducing ammonia, synthesis, water washing, layering, drying and distilling. It has sealed operation process, one distilling step, up reflux system and circular utilization of residual liquid and tail gas, and adopts enamel reactor, conic bottom water washing kettle, serially connected drying tower and other apparatus. The triethyl phosphate is used as plasticizer, stabilizer and additive in producing medicine, pesticide, plastic, dye and lubricant grease. The producing process has high yield, high product purity, no environmental pollution and low production cost.
Description
Technical field
The present invention relates to phosphorus trichloride, dehydrated alcohol is the method that main raw material prepares triethyl-phosphite.
Background technology
Triethyl-phosphite is a kind of important medicine, pesticide intermediate, also is the main raw material of producing the softening agent be used for plastics, dyestuff, lubricating grease, stablizer, whitening agent, additive, and its development prospect is wide.All adopting with phosphorus trichloride, dehydrated alcohol both at home and abroad at present is main raw material, selecting organic amine or tertiary amines mostly for use is acid binding agent synthesizing phosphorous acid triethyl, feed ammonia again and parse acid binding agent, the compound of building-up reactions obtains product after suction filtration, washing, distillation.Because suction filtration, washing are carried out under the non-tight state, have the volatilization of partial solvent and product, cause the waste of environmental pollution and raw material, and moisture content causes decomposition and reduces quality and yield in the product meeting ingress of air; Because still-process adopts thick earlier steaming, smart method of steaming, and return-flow system again to adopt backflow down, makes the product distillation time long, vacuum loss is big, increases production cost; Because the gas that vinasse and vacuum pump are extracted out does not carry out effective recycling, also pollute the environment again, reduce product yield; Especially in existing the production, the not enough standard of important technical parameter, processing condition and equipment used, reasonable inadequately directly influences the quality and the yield of product, also is awkward, and is difficult to guarantee the stable of quality product.The triethyl-phosphite purity of existing explained hereafter is 98%～99.5%, and yield is 92%～98%.
Summary of the invention
The technical problem to be solved in the present invention is the weak point that overcomes existing production technique, and a kind of working specification is provided, and production cost is low, does not pollute the environment, and can improve the triethyl phosphite producing process of product quality and yield.
Technical scheme of the present invention is: with dehydrated alcohol, phosphorus trichloride is a main raw material, through synthetic reaction, washing, layering, dry, the distillation key step makes desired product, feed ammonia in the building-up reactions, improvements are to also have orthodichlorobenzene in raw materials used, N, accelerine, the weight percent that above-mentioned various raw material accounts for all raw material total amounts is: dehydrated alcohol 9.50%～10.30%, phosphorus trichloride 9.39%～10.26%, orthodichlorobenzene 58.37%～68.53%, N, accelerine 12.32%～21.41%, concrete operation method is as follows:
Building-up reactions: earlier will be by orthodichlorobenzene and N, the ethanol of mixed solvent that accelerine prepares and content 〉=99.00% adds synthesis reactor, and stir, simultaneously chilled brine is fed synthesis reactor chuck and still inner coil pipe, when temperature in the kettle is lower than 10 ℃, beginning drips the phosphorus trichloride of content 〉=98.50% that measures in still, simultaneously ammonia is fed Polycondensation Reactor and Esterification Reactor, control pH value is 6～7 in the reaction, control reaction temperature is 20 ℃～30 ℃, phosphorus trichloride drips off in 2h～5h, when temperature drift, to reduce phosphorus trichloride rate of addition and ammonia flow simultaneously, after phosphorus trichloride drips and finishes, continue to feed chilled brine, be lower than 10 ℃ until temperature in the kettle;
Washing, layering, drying: implantation concentration is 1.0%～1.3% buck in the washing still, chilled brine is fed the still inner coil pipe, and stir, when buck temperature in the still is reduced to below 10 ℃, synthetic material after the building-up reactions is put into the washing still to be washed, washing time 10～12m i n, then will wash sedimentation 0.8～1.5h in the good material suction layering still, again the upper strata mixture suction after the layering is filled up in the drying tower of crude salt and dehydrate, obtain the thick ester of triethyl-phosphite, it is standby that this thick ester enters thick ester storage tank;
Distillation: in thick ester suction still kettle, adjusting the interior vapor pressure of control still is 0.04～0.045MP a, and open cold condenser water pump is regulated the vacuum micrometering valve, and keeping the distillation tower roof pressure is by force 7.325 * 10
3Pa to 9.325 * 10
3Pa, make material in system, be in the total reflux state, after tower top temperature t reaches 62 ℃～64 ℃ and backflow balance, begin front-end volatiles, when reaching 72 ℃～74 ℃ and sampling analysis triethyl-phosphite content 〉=99.2%, opens t finished product rewinding valve, collect finished product, when t reaches 82 ℃～84 ℃, and sampling content≤99.2% o'clock, change the receipts after cut, when t reached 108 ℃ and sampling analysis triethyl-phosphite content≤6%, the blowdown system vacuum was closed down steam and water pump, raffinate in the still is put into fluid infusion groove cooling back recycle, every batch of front-end volatiles, after cut drops into next still and distills with thick ester, is used further to building-up reactions, the end product metering packing after the gas of extracting out in the still is reclaimed with orthodichlorobenzene; More than operation is all carried out under sealed state.
Further scheme is: use enamel still in the building-up reactions, mixing speed is 250～280r/min in the still, to reduce the generation of the dregs of fat such as iron trichloride, be easy to layering when making the washing layering, and create ethanol and the condition that phosphorus trichloride fully contacts, and shorten the reaction times, suppress side reaction and produce.In the building-up reactions, every interval 5～10min surveys a pH value, and when pH＜6, reduce phosphorus trichloride and drip flow, the increase ammonia flow is then opposite when pH＞7.Used ammonia is to be transformed after the heating of distillation waste heat by liquid ammonia, with save energy, reduces cost.Use the bottom to become cone shape washing still in the water washing process, the abundant transfer that helps washing material is reduced the loss.Use three placed in-line drying towers in the drying process, make the moisture complete drying in the thick ester, reduce the decomposition of triethyl-phosphite, improve yield.In the still-process, the reflux in tower system uses to go up and refluxes, and improves separating effect, shortens distillation time, reduces product loss.The vacuum pump exhaust ports of still kettle adapted is equipped with device for absorbing tail gas, in adorn the orthodichlorobenzene of 2/3rds volumes, and with the spiral coil cooling tube in the chilled brine access equipment, when the triethyl-phosphite mass percentage content reaches 8%～10% in collecting liquid, to collect liquid emits and is used for building-up reactions, reduce environmental pollution, improve product yield.Thick ester storage tank is lowered the temperature, keep thick ester temperature≤20 ℃, avoid the high temperature loss.The fluid infusion groove is lowered the temperature, vinasse is cooled to≤10 ℃ standby, be beneficial to cycling and reutilization, improve yield, reduce cost.
Above technical scheme, processing parameter, clear complete, the normative and reasonable of processing condition are convenient to operation, are fit to suitability for industrialized production, can guarantee constant product quality.In the production, the reaction of material, transfer, purification are all carried out under sealed state, solvent recuperation is utilized, do not pollute the environment, reduce production costs, effectively improve the quality and the yield of product, product purity reaches 99.2%～99.9%, yield reaches 117.5%～119.0% in phosphorus trichloride, and its structural formula is:
Embodiment
The invention will be further described below by embodiment.
With measure by orthodichlorobenzene and N, accelerine drops in the 3000L enamel synthesis reactor successively by weight the mixed solvent 1700L of 2.5: 1 ratio preparation and the dehydrated alcohol 253kg of content 99.0%, and stir, rotating speed is 270r/min, simultaneously chilled brine is fed synthesis reactor chuck and still inner coil pipe, in the time of 8 ℃, begin to drip the phosphorus trichloride 252kg of the content 98.6% that measures, and at the bottom of will feeding still by the ammonia of liquid ammonia through changing into after the heating of distillation waste heat, reaction times 2h30min, control pH value is 6～7, temperature of reaction is 24 ℃～28 ℃. when temperature drift, reduce phosphorus trichloride rate of addition and ammonia flow simultaneously, when pH＜6, reduce phosphorus trichloride and drip flow, increase ammonia flow, then opposite when pH＞7.Reaction finishes back cooling 20min, makes material reduce to 8 ℃.
The NaOH alkali lye 1400L of implantation concentration 1.2% in the bottom becomes cone shape washing still feeds still inner coil pipe and stirring with chilled brine, when the buck temperature is reduced to 5 ℃, puts into reacted synthetic material and washes time 10min; The material suction layering still sedimentation 1h that washing is good, isolate and recycle after lower layer of water enters water-and-oil separator, with the speed of 800L/h the upper materials suction is filled up three series connection drying tower inner drying dehydrations of crude salt again, it is standby that the thick ester of the triethyl-phosphite that obtains enters thick ester storage tank, storage tank has heat sink, keeps 5 ℃～15 ℃ of temperature.
Extract the thick ester of 4200L out with vacuum pump from thick ester storage tank and enter the 5000L still kettle, adjust the Distallation systm valve, vapor pressure is 0.045MPa in the control still, and open cold condenser water pump is regulated the vacuum micrometering valve, and keeping cat head pressure is 7.325 * 10
3Pa-9.325 * 10
3Pa, make material in system, be in reflux state, reach 64 ℃ and reflux when steady as tower top temperature t behind the backflow 1h30min, open the under meter valve, control reflux ratio 120L/h goes out front-end volatiles, sampling analysis triethyl-phosphite content is 99.2% o'clock behind the 30min, the accent reflux ratio is 160L/h, change the harvest product, sampling analysis content is 99.8% behind the harvest product 30min, transferring reflux ratio is that 180L/h continues the harvest product, sampling analysis content is 99.6% behind the 2h50min, transfer reflux ratio 160L/h harvest product again, t sharply rises behind the 20min, sampling analysis content is 99.24%, transferring reflux ratio is that 80L/h changes the receipts after cut, t reaches 118 ℃ behind the 3h20min, during sampling analysis content 5.8%, the row's of closing Distallation systm vacuum, close down steam, water pump, raffinate is put into the fluid infusion groove of heat sink and is kept temperature to utilize for 5 ℃～8 ℃ again in the still, front-end volatiles, after cut drops into next still and distills with thick ester, still kettle adapted vacuum pump exhaust ports has device for absorbing tail gas, in adorn the orthodichlorobenzene of 2/3rds volumes, and with chilled brine access equipment internal cooling coil pipe, when triethyl-phosphite content reaches 8%～10% in collecting liquid, to collect liquid and emit and be used for building-up reactions, carry out the finished product metering packing at last.More than operation is all carried out under sealed state.
In the present embodiment, obtain product 626kg, purity reaches 99.72%, and yield counts 118.4% with phosphorus trichloride.
Claims (10)
1. triethyl phosphite producing process, with dehydrated alcohol, phosphorus trichloride is a main raw material, through synthetic reaction, washing, layering, dry, the distillation key step makes desired product, feed ammonia in the building-up reactions, it is characterized in that also having orthodichlorobenzene in raw materials used, N, accelerine, the weight percent that above-mentioned various raw material accounts for all raw material total amounts is: dehydrated alcohol 9.50%～10.30%, phosphorus trichloride 9.39%～10.26%, orthodichlorobenzene 58.37%～68.53%, N, accelerine 12.32%～21.41%, concrete operation method is as follows:
Building-up reactions: earlier will be by orthodichlorobenzene and N, the ethanol of mixed solvent that accelerine prepares and content 〉=99.00% adds synthesis reactor, and stir, simultaneously chilled brine is fed synthesis reactor chuck and still inner coil pipe, when temperature in the kettle is lower than 10 ℃, beginning drips the phosphorus trichloride of content 〉=98.50% that measures in still, simultaneously ammonia is fed Polycondensation Reactor and Esterification Reactor, control pH value is 6～7 in the reaction, control reaction temperature is 20 ℃～30 ℃, phosphorus trichloride drips off in 2h～5h, when temperature drift, to reduce phosphorus trichloride rate of addition and ammonia flow simultaneously, after phosphorus trichloride drips and finishes, continue to feed chilled brine, be lower than 10 ℃ until temperature in the kettle;
Washing, layering, drying: implantation concentration is 1.0%～1.3% buck in the washing still, chilled brine is fed the still inner coil pipe, and stir, when buck temperature in the still is reduced to below 10 ℃, synthetic material after the building-up reactions is put into the washing still to be washed, washing time 10～12min, then will wash sedimentation 0.8～1.5h in the good material suction layering still, again the upper strata mixture suction after the layering is filled up in the drying tower of crude salt and dehydrate, obtain the thick ester of triethyl-phosphite, it is standby that this thick ester enters thick ester storage tank;
Distillation: in thick ester suction still kettle, adjusting the interior vapor pressure of control still is 0.04～0.045MPa, and open cold condenser water pump is regulated the vacuum micrometering valve, and keeping the distillation tower roof pressure is by force 7.325 * 10
3Pa to 9.325 * 10
3Pa, make material in system, be in the total reflux state, after tower top temperature t reaches 62 ℃～64 ℃ and backflow balance, begin front-end volatiles, when reaching 72 ℃～74 ℃ and sampling analysis triethyl-phosphite content 〉=99.2%, opens t finished product rewinding valve, collect finished product, when t reaches 82 ℃～84 ℃, and sampling content≤99.2% o'clock, change the receipts after cut, when t reached 108 ℃ and sampling analysis triethyl-phosphite content≤6%, the blowdown system vacuum was closed down steam and water pump, raffinate in the still is put into fluid infusion groove cooling back recycle, every batch of front-end volatiles, after cut drops into next still and distills with thick ester, is used further to building-up reactions, the end product metering packing after the gas of extracting out in the still is reclaimed with orthodichlorobenzene; More than operation is all carried out under sealed state.
2. by the described triethyl phosphite producing process of claim 1, it is characterized in that using in the building-up reactions enamel still, mixing speed is 250～280r/min in the still.
3. by the described triethyl phosphite producing process of claim 1, it is characterized in that in the building-up reactions that every interval 5～10min surveys a pH value, when pH＜6, reduce phosphorus trichloride and drip flow, the increase ammonia flow is then opposite when pH＞7.
4. by the described triethyl phosphite producing process of claim 1, it is characterized in that used ammonia is to be transformed after the heating of distillation waste heat by liquid ammonia.
5. by the described triethyl phosphite producing process of claim 1, it is characterized in that using in the water washing process bottom to become cone shape washing still.
6. by the described triethyl phosphite producing process of claim 1, it is characterized in that using in the drying process three placed in-line drying towers.
7. by the described triethyl phosphite producing process of claim 1, it is characterized in that in the still-process that the reflux in tower system uses to go up and refluxes.
8. by the described triethyl phosphite producing process of claim 1, the vacuum pump exhaust ports that it is characterized in that the still kettle adapted is equipped with device for absorbing tail gas, in adorn the orthodichlorobenzene of 2/3rds volumes, and with the spiral coil cooling tube in the chilled brine access equipment, when triethyl-phosphite content reaches 8%～10% in collecting liquid, will collect liquid and emit and be used for building-up reactions.
9. by the described triethyl phosphite producing process of claim 1, it is characterized in that thick ester storage tank is lowered the temperature, keep thick ester temperature≤20 ℃.
10. by the described triethyl phosphite producing process of claim 1, it is characterized in that the fluid infusion groove is lowered the temperature, vinasse is cooled to≤10 ℃ standby.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100860554A CN100374450C (en) | 2006-07-21 | 2006-07-21 | Triethyl phosphite producing process |
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| CNB2006100860554A CN100374450C (en) | 2006-07-21 | 2006-07-21 | Triethyl phosphite producing process |
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| CN100374450C true CN100374450C (en) | 2008-03-12 |
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| CN105413402A (en) * | 2015-11-20 | 2016-03-23 | 宁国久天化工有限公司 | Phosphorus trichloride tail gas treatment process |
| CN105503942A (en) * | 2016-01-12 | 2016-04-20 | 江苏苏源辉普化工有限公司 | Continuous production method for triethyl phosphite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN1724546A (en) * | 2005-06-27 | 2006-01-25 | 罗方明 | Production method of triethyl phosphite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493575A (en) * | 2002-10-28 | 2004-05-05 | 刘德亮 | Method of preparing phosphite ester |
| CN1724546A (en) * | 2005-06-27 | 2006-01-25 | 罗方明 | Production method of triethyl phosphite |
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| 亚磷酸三乙酯合成工艺研究. 姚建文.烟台大学学报（自然科学与工程版），第16卷第4期. 2003 * |
| 亚磷酸三乙酯的制备工艺新研究. 张荣成.连云港职业技术学院学报，第14卷第1期. 2001 * |
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Owner name: TAIZHOU TIANCHENG CHEMICAL INDUSTRY CO., LTD. Free format text: FORMER OWNER: SHEN HOUBAO Effective date: 20090522 |
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Effective date of registration: 20090522 Address after: No. 2, Wenhua Road, Jiangyan, Jiangsu Patentee after: Taizhou Tiancheng Chemical Co., Ltd. Address before: No. 2, Wenhua Road, Jiangyan, Jiangsu Patentee before: Shen Houbao |
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