CN104447855A - Rectification method of triethyl phosphate crude product - Google Patents
Rectification method of triethyl phosphate crude product Download PDFInfo
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- CN104447855A CN104447855A CN201310426587.8A CN201310426587A CN104447855A CN 104447855 A CN104447855 A CN 104447855A CN 201310426587 A CN201310426587 A CN 201310426587A CN 104447855 A CN104447855 A CN 104447855A
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- triethyl phosphate
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Abstract
The invention relates to a rectification method of a triethyl phosphate crude product. The method employs a double tower continuous negative pressure distillation process and is as below: mixing the triethyl phosphat crude product with an antioxidant, continuously pumping the mixture into a light component removal tower by a metering pump, recovering a diethyl phosphate light component at the top of the tower, recovering a triethyl phosphate semi-finished product at the bottom of the tower, then continuously pumping the semi-finished product into a product rectification tower, and continuously recovering the triethyl phosphate product at the top of the tower. The continuous distillation process adopted by the invention the can realize scale production, inhibit decomposition of by-products in the crude product under a high vacuum degree and antioxidant function, ensure the yield and quality of the product. The rectification yield is more than 95%, the product purity is more than 99.8%, and the acid value can be controlled below 0.02 mg KOH / 100g.
Description
Technical field:
The invention belongs to chemical production technical field, be specifically related to a kind of with phosphorus oxychloride and ethanol for raw material, obtain the method for the triethyl phosphate crude product rectifying of content 94 ~ 98% through esterification, dealcoholysis de-chlorine hydride technique.Background technology:
Triethyl phosphate is of many uses, in rubber and plastics, it can be used as softening agent, also can be used for catalyzer, solvent, stablizer, solidifying agent and tenderizer etc., be one of main raw material preparing agricultural chemicals, also can be used for the production of dyeing auxiliary, luminescent lamp glass paint etc. of plant-growth regulator, defoamer, acetate fiber.
At present both at home and abroad triethyl phosphate mainly adopts phosphorus oxychloride and excess ethyl alcohol to carry out esterification, then carries out dealcoholysis de-chlorine hydride, neutralization, distillation, rectifying obtains product.
Triethyl phosphate esterification equation is as follows:
POCl
3+3C
2H
5OH→(C
2H
5O)
3PO+3HC1
This reaction divides 3 steps to carry out, specific as follows:
POCl
3+C
2H
5OH→(C
2H
5O)POC1
2+HC1 (1)
(C
2H
5O)POC1
2+C
2H
5OH→(C
2H
5O)
2POC1+HCl (2)
(C
2H
5O)
2POC1+C
2H
5OH→(C
2H
5O)
3PO+HC1 (3)
1st, the 2nd step speed of response is very fast, and produce a large amount of hydrogen chloride gas, the 3rd step speed of response is slower.Byproduct phosphoric acid diethyl ester (C is also generated while above-mentioned esterification occurs
2h
5o)
2pOOH, monochloroethane C
2h
5c1, diethyl chlorophosphate (C
2h
5o)
2pOCl etc.
Within 2007, Hubei University Of Technology Shao You unit waits people to report the article of " research of triethyl phosphate new synthetic process ", phosphorus oxychloride and ethanol is adopted to be raw material, what total system produced employing is that negative pressure is produced, and technique is made up of esterification, dealcoholysis, neutralization, distillation, rectifying, absorption production line.Through improving, in and operation reduce liquid caustic soda consumption, decrease the production of water, but still in adopting and process for refining remove the by product such as diethyl phosphoric acid and diethyl chlorophosphate to ensure the quality of products.
Within 2011, Zhang Junxiao has delivered " triethyl phosphate preparation method " patent (application number 201110085702.0), mention triethyl phosphate crude product in this patent and adopt that a step negative pressure is rectified purified obtains product, but this technique rectifying adopts single tower to be separated, rectification temperature is higher, cause by-product destruction in crude product, although can obtain content comparatively high product, rectification yield is low, product acid number is high, has had a strong impact on quality product.
Summary of the invention:
The object of the present invention is to provide a kind of with phosphorus oxychloride and ethanol for raw material, obtain the method for the triethyl phosphate crude product rectifying of content 94 ~ 98% through esterification, dealcoholysis de-chlorine hydride technique.
The rectificating method of triethyl phosphate crude product of the present invention, is adopted the rectifying of double tower continuous negative pressure, and is realized by following steps:
After the triethyl phosphate crude product of content 94 ~ 98% and oxidation inhibitor mixing, squeeze into lightness-removing column preheater by volume pump and be heated to 75 ~ 80 DEG C, enter de-light rectifying tower and carry out negative pressure rectifying, control bottom temperature and reflux ratio, at overhead extraction diethyl phosphoric acid light constituent, the low continuous extraction triethyl phosphate work in-process of tower; Work in-process are squeezed into product rectifying tower continuously by volume pump again and are carried out negative pressure rectifying, control bottom temperature and reflux ratio, at tower top continuous extraction triethyl phosphate product.
Above-mentioned method, the one in single Tert. Butyl Hydroquinone or di-tert-butyl hydroquinone or 2,4 dimethyl 6 tert butyl phenol selected by the oxidation inhibitor described in it, and add-on is triethyl phosphate crude product 200 ~ 400mg/Kg.
Above-mentioned method, the lightness-removing column described in it is 28 ~ 32 pieces of theoretical stages; Product rectifying tower is 32 ~ 36 pieces of theoretical stages; All adopt Stainless Steel Wire corrugated wire gauze packing.
Above-mentioned method, the de-light rectifying tower described in it and product rectifying tower vacuum degree are 6 ~ 10mmHg.
Above-mentioned method, the de-light rectifying tower reboiler temperature described in it controls at 102 ~ 112 DEG C, and control of reflux ratio is at 12 ~ 18:1, and overhead extraction temperature controls at 52 ~ 60 DEG C.
Above-mentioned method, the product rectifying tower reboiler temperature described in it controls at 118 ~ 130 DEG C, and control of reflux ratio is at 3 ~ 5:1, and overhead extraction temperature controls at 64 ~ 72 DEG C.
Document and patent report triethyl phosphate crude product is refining before, one method adopts neutralization, rectifying two step operation, by in and operation first remove the impurity such as diethyl phosphoric acid and diethyl chlorophosphate, to ensure the acid number index of product after rectifying, these technique three wastes are larger, phosphatizing difficulty simultaneously after neutralization is very big, adds labour intensity.And earlier patents " triethyl phosphate preparation method " describes triethyl phosphate crude product rectification process, but it is lower to there is distillation system negative pressure in this technique, rectification temperature is high, product is long at dwell time in the tower, causes the decomposition of triethyl phosphate product and the by product such as diethyl phosphoric acid, diethyl chlorophosphate.Triethyl phosphate, along with the increase of temperature and the growth in the system residence time, can decompose gradually, make product yield low, and the decomposition of by product has a strong impact on again the acid number index of product, adopts a step rectification process product acid number to be generally not less than 0.05mgKOH/100g.
The present invention compared with prior art comparatively, has following significant effect:
(1) the present invention adopts double tower continuous negative pressure rectification process, shortens material in the intrasystem residence time, improves the vacuum tightness of system simultaneously, reduce rectification temperature, avoid the decomposition of triethyl phosphate and by product in crude product.
Find by studying active higher diethyl chlorophosphate by product, diethyl chlorophosphate boiling point 98 DEG C (10mmHg), boiling point 80 DEG C (6mmHg), boiling point 61 DEG C (2mmHg), namely vacuum tightness improves 4mmHg, boiling point lowering 20 DEG C, so gas clean-up, ensure product tower bottom of rectifying tower temperature less than 140 DEG C operations (150 DEG C of diethyl chlorophosphate can decompose, and triethyl phosphate easily can decompose gradually), avoid it to decompose, ensure product acid number index.
(2) the present invention is by adding oxidation inhibitor, avoids the generation that byproduct phosphoric acid diethyl ester is oxidized, is polymerized in lightness-removing column, can successfully be separated diethyl ester by product in lightness-removing column.
(3) the present invention adopts double tower continuous negative pressure rectification process, by adding of lightness-removing column oxidation inhibitor, reduce rectification temperature and the material residence time at rectification system, rectification yield can be made to be greater than 95%, product purity is greater than 99.8%, acid number can be controlled in below 0.02mgKOH/100g, can meet large-scale continuous need of production simultaneously.
Embodiment:
Now by embodiment, the present invention is described in detail as follows:
Embodiment 1
Will with phosphorus oxychloride and ethanol for raw material, obtain the triethyl phosphate crude product of content 94.6% through esterification, dealcoholysis de-chlorine hydride technique and oxidation inhibitor list Tert. Butyl Hydroquinone mixes in storage tank, added quantity of antioxidant is triethyl phosphate crude product 200mg/Kg.Squeeze into lightness-removing column preheater by volume pump after mixing and be heated to 75 ~ 80 DEG C, be fed to de-light rectifying tower in tower and carry out negative pressure rectifying.De-light rectifying tower theoretical stage 28 ~ 32 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 6 ~ 8mmHg, control tower reactor reboiler temperature 102 ~ 108 DEG C, reflux ratio is 16 ~ 18:1, overhead extraction temperature 52 ~ 55 DEG C, continuous extraction diethyl phosphoric acid byproduct, tower reactor extraction triethyl phosphate work in-process, squeeze into product rectifying tower continuously with volume pump and carry out negative pressure rectifying.
Product rectifying tower theoretical stage 32 ~ 36 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 6 ~ 8mmHg, control tower reactor reboiler temperature 118 ~ 124 DEG C, reflux ratio is 3 ~ 4:1, and overhead extraction temperature controls at 64 ~ 68 DEG C, continuous extraction triethyl phosphate product.After steady running, rectification yield is 95.8%, triethyl phosphate product purity 99.93%, acid number 0.018mgKOH/100g.
Embodiment 2
Will with phosphorus oxychloride and ethanol for raw material, obtain the triethyl phosphate crude product of content 97.3% through esterification, dealcoholysis de-chlorine hydride technique and oxidation inhibitor di-tert-butyl hydroquinone mixes in storage tank, added quantity of antioxidant is triethyl phosphate crude product 300mg/Kg.Squeeze into lightness-removing column preheater by volume pump after mixing and be heated to 75 ~ 80 DEG C, be fed to de-light rectifying tower in tower and carry out negative pressure rectifying.De-light rectifying tower theoretical stage 28 ~ 32 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 6 ~ 8mmHg, control tower reactor reboiler temperature 102 ~ 108 DEG C, reflux ratio is 16 ~ 18:1, overhead extraction temperature 52 ~ 55 DEG C, continuous extraction diethyl phosphoric acid byproduct, tower reactor extraction triethyl phosphate work in-process, squeeze into product rectifying tower continuously with volume pump and carry out negative pressure rectifying.
Product rectifying tower theoretical stage 32 ~ 36 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 6 ~ 8mmHg, control tower reactor reboiler temperature 118 ~ 124 DEG C, reflux ratio is 3 ~ 4:1, and overhead extraction temperature controls at 64 ~ 68 DEG C, continuous extraction triethyl phosphate product.After steady running, rectification yield is 96.1%, triethyl phosphate product purity 99.87%, acid number 0.015mgKOH/100g.
Embodiment 3
Will with phosphorus oxychloride and ethanol for raw material, triethyl phosphate crude product and the oxidation inhibitor 2 of content 97.3% is obtained through esterification, dealcoholysis de-chlorine hydride technique, 4-dimethyl-6-tert.-butyl phenol mixes in storage tank, and added quantity of antioxidant is triethyl phosphate crude product 400mg/Kg.Squeeze into lightness-removing column preheater by volume pump after mixing and be heated to 75 ~ 80 DEG C, be fed to de-light rectifying tower in tower and carry out negative pressure rectifying.De-light rectifying tower theoretical stage 28 ~ 32 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 6 ~ 8mmHg, control tower reactor reboiler temperature 102 ~ 108 DEG C, reflux ratio is 16 ~ 18:1, overhead extraction temperature 52 ~ 55 DEG C, continuous extraction diethyl phosphoric acid byproduct, tower reactor extraction triethyl phosphate work in-process, squeeze into product rectifying tower continuously with volume pump and carry out negative pressure rectifying.
Product rectifying tower theoretical stage 32 ~ 36 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 6 ~ 8mmHg, control tower reactor reboiler temperature 118 ~ 124 DEG C, reflux ratio is 3 ~ 4:1, and overhead extraction temperature controls at 64 ~ 68 DEG C, continuous extraction triethyl phosphate product.After steady running, rectification yield is 97.3%, triethyl phosphate product purity 99.90%, acid number 0.012mgKOH/100g.
Embodiment 4
Will with phosphorus oxychloride and ethanol for raw material, triethyl phosphate crude product and the oxidation inhibitor 2 of content 94.6% is obtained through esterification, dealcoholysis de-chlorine hydride technique, 4-dimethyl-6-tert.-butyl phenol mixes in storage tank, and added quantity of antioxidant is triethyl phosphate crude product 200mg/Kg.Squeeze into lightness-removing column preheater by volume pump after mixing and be heated to 75 ~ 80 DEG C, be fed to de-light rectifying tower in tower and carry out negative pressure rectifying.De-light rectifying tower theoretical stage 28 ~ 32 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 8 ~ 10mmHg, control tower reactor reboiler temperature 106 ~ 112 DEG C, reflux ratio is 16 ~ 18:1, overhead extraction temperature 55 ~ 60 DEG C, continuous extraction diethyl phosphoric acid byproduct, tower reactor extraction triethyl phosphate work in-process, squeeze into product rectifying tower continuously with volume pump and carry out negative pressure rectifying.
Product rectifying tower theoretical stage 32 ~ 36 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 8 ~ 10mmHg, control tower reactor reboiler temperature 124 ~ 130 DEG C, reflux ratio is 3 ~ 4:1, and overhead extraction temperature controls at 69 ~ 72 DEG C, continuous extraction triethyl phosphate product.After steady running, rectification yield is 96.6%, triethyl phosphate product purity 99.97%, acid number 0.018mgKOH/100g.
Embodiment 5
Will with phosphorus oxychloride and ethanol for raw material, obtain the triethyl phosphate crude product of content 94.6% through esterification, dealcoholysis de-chlorine hydride technique and oxidation inhibitor di-tert-butyl hydroquinone mixes in storage tank, added quantity of antioxidant is triethyl phosphate crude product 200mg/Kg.Squeeze into lightness-removing column preheater by volume pump after mixing and be heated to 75 ~ 80 DEG C, be fed to de-light rectifying tower in tower and carry out negative pressure rectifying.De-light rectifying tower theoretical stage 28 ~ 32 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 8 ~ 10mmHg, control tower reactor reboiler temperature 106 ~ 112 DEG C, reflux ratio is 16 ~ 18:1, overhead extraction temperature 55 ~ 60 DEG C, continuous extraction diethyl phosphoric acid byproduct, tower reactor extraction triethyl phosphate work in-process, squeeze into product rectifying tower continuously with volume pump and carry out negative pressure rectifying.
Product rectifying tower theoretical stage 32 ~ 36 pieces, adopt JW-700 Stainless Steel Wire corrugated wire gauze packing, system vacuum is 8 ~ 10mmHg, control tower reactor reboiler temperature 124 ~ 130 DEG C, reflux ratio is 3 ~ 4:1, and overhead extraction temperature controls at 69 ~ 72 DEG C, continuous extraction triethyl phosphate product.After steady running, rectification yield is 97.5%, triethyl phosphate product purity 99.90%, acid number 0.020mgKOH/100g.
Claims (6)
1. the rectificating method of a triethyl phosphate crude product, it is characterized in that: will with phosphorus oxychloride and ethanol for raw material, after the triethyl phosphate crude product obtaining content 94 ~ 98% through esterification, dealcoholysis de-chlorine hydride technique and oxidation inhibitor mixing, squeeze into lightness-removing column preheater by volume pump and be heated to 75 ~ 80 DEG C, enter de-light rectifying tower and carry out negative pressure rectifying, control bottom temperature and reflux ratio, at tower top continuous extraction diethyl phosphoric acid light constituent, the low continuous extraction triethyl phosphate work in-process of tower; Work in-process are squeezed into product rectifying tower continuously by volume pump and are carried out negative pressure rectifying, control bottom temperature and reflux ratio, at tower top continuous extraction triethyl phosphate product.
2. method according to claim 1, is characterized in that: the one in single Tert. Butyl Hydroquinone or di-tert-butyl hydroquinone or 2,4 dimethyl 6 tert butyl phenol selected by oxidation inhibitor, and add-on is triethyl phosphate crude product 200 ~ 400mg/Kg.
3. method according to claim 1, is characterized in that: described lightness-removing column adopts Stainless Steel Wire corrugated wire gauze packing, 28 ~ 32 pieces of theoretical stages; Product rectifying tower adopts Stainless Steel Wire corrugated wire gauze packing, 32 ~ 36 pieces of theoretical stages.
4. method according to claim 1, is characterized in that: de-light rectifying tower and product rectifying tower vacuum degree are 6 ~ 10mmHg.
5. method according to claim 1, is characterized in that: de-light rectifying tower reboiler temperature controls at 102 ~ 112 DEG C, and control of reflux ratio is at 12 ~ 18:1, and overhead extraction temperature controls at 52 ~ 60 DEG C.
6. method according to claim 1, is characterized in that: product rectifying tower reboiler temperature controls at 118 ~ 130 DEG C, and control of reflux ratio is at 3 ~ 5:1, and overhead extraction temperature controls at 64 ~ 72 DEG C.
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| CN201310426587.8A CN104447855B (en) | 2013-09-18 | 2013-09-18 | A kind of rectificating method of triethyl phosphate crude product |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3801683A (en) * | 1970-10-20 | 1974-04-02 | Toyama Chemical Co Ltd | Process for preparing trialkyophosphate |
| CN1421448A (en) * | 2001-11-27 | 2003-06-04 | 拜尔公司 | Preparation of diethyl phosphoric acid |
| CN102206230A (en) * | 2011-04-02 | 2011-10-05 | 吉林市永林化工有限公司 | Method for preparing triethyl phosphate |
-
2013
- 2013-09-18 CN CN201310426587.8A patent/CN104447855B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3801683A (en) * | 1970-10-20 | 1974-04-02 | Toyama Chemical Co Ltd | Process for preparing trialkyophosphate |
| CN1421448A (en) * | 2001-11-27 | 2003-06-04 | 拜尔公司 | Preparation of diethyl phosphoric acid |
| CN102206230A (en) * | 2011-04-02 | 2011-10-05 | 吉林市永林化工有限公司 | Method for preparing triethyl phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 杜翠红 等: ""磷酸三酯合成工艺的改进"", 《太原理工大学学报》 * |
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