CN109928993A - A kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual - Google Patents
A kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual Download PDFInfo
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- CN109928993A CN109928993A CN201910308867.6A CN201910308867A CN109928993A CN 109928993 A CN109928993 A CN 109928993A CN 201910308867 A CN201910308867 A CN 201910308867A CN 109928993 A CN109928993 A CN 109928993A
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Abstract
The invention discloses the commercial recovery methods that a kind of fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual, use the kettle of phosphorous diethyl phthalate and sodium methoxide residual for raw material, under without acidulated condition, directly depressurize high temperature disproportionated reaction, triethyl phosphate and disodium hydrogen phosphate are generated, then disodium hydrogen phosphate is reacted through high temperature polymerization generates sodium pyrophosphate.Compared with prior art, commercial recovery method of the invention has reaction condition neutrality, without considering that the selection of high-temperature reaction equipment material under acid condition, lectotype selection are easy；All reactions can be completed in a reactor, and operating process is few, be easy to factory's realization；It is not acidified the salt of generation, avoids the generation of the three wastes；Reaction yield is high, is not lost substantially；Kettle is residual to be completely converted into product, without waste, the good advantage of environment protecting.
Description
Technical field
The present invention relates to the commercial recovery methods that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual, specifically with phosphoric acid diethyl
The residual fluorescent whitening agent kettle of ester is raw material, prepares ethyl phosphate with high purity and sodium pyrophosphate by depressurizing high temperature disproportionated reaction
Friendly process.
Background technique
Triethyl phosphate and sodium pyrophosphate it is widely used.Triethyl phosphate can be used as high boiling solvent, rubber and modeling
The plasticizer of material, catalysts produce the raw material of agricultural chemical insecticide, and are used as ethylating agent, produce for ketenes
Deng.Sodium pyrophosphate is used as stripping agent and Blankit for preparing electroplate liquid, woolen industry in electroplating industry, and paper industry is used
In the bleaching of paper and plant fiber, printing and dyeing industry is used as auxiliary agent when printing and dyeing, essence drift, is used as water softener in water process, mechanical
It is used as rust remover in processing, is used as dispersing agent and emulsifier in Chemical Manufacture, it may also be used for the side such as water treatment agent, oil drilling
Face.
With the extensive use of distyrene type fluorescent whitening agent, the kettle for generating phosphorous diethyl phthalate is residual more and more, should
Kettle remains in pollution environment, is difficult to the problems such as handling.
CN101891761B patent discloses a kind of method of catalytically synthesizing triethyl phosphate by phase transfer, this method reaction knot
Repeatedly, treatment process generates a large amount of useless for Shu Houyong saturated sodium bicarbonate aqueous solution, water and saturated sodium-chloride water solution washing
Water needs to handle.
CN101941988B discloses that a kind of acidification of diethyl phosphate sodium neutralizes, Pintsch process and rectification under vacuum obtain phosphoric acid
The technique of triethyl, Pintsch process, production equipment acid-resistant and anti-high-temperature have higher requirement to the technique in acid condition；The technique
Reaction process step is more, and production operation is not easy, while the salt removed after its acidification is solid residue, needs subsequent processing；Cracking
The liquid waste liquid generated after distillation also needs to handle.
Prepare that triethyl phosphate technological reaction process steps are more, industrial operation is not easy, is acidified item to solve diethyl phosphate
The problem of lectotype selection is difficult under part, waste liquid nocuousness need to post-process after solid residue and cracking distillation after acidification, the present invention proposes
A kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual, with the fluorescent whitening agent kettle of phosphorous diethyl phthalate
Residual is raw material, prepares ethyl phosphate with high purity and sodium pyrophosphate by depressurizing high temperature disproportionated reaction.
Summary of the invention
In view of the above-mentioned drawbacks of the prior art, being former the invention proposes a kind of kettle by phosphorous diethyl phthalate is residual
Material, not acidified direct high temperature disproportionated reaction generate triethyl phosphate, while the method for the residual synthesis sodium pyrophosphate of kettle.
Technical scheme is as follows:
A kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual, which is characterized in that use phosphoric acid diethyl
The kettle of ester and sodium methoxide it is residual be raw material, under without acidulated condition, directly decompression high temperature disproportionated reaction, generate triethyl phosphate with
Disodium hydrogen phosphate, then disodium hydrogen phosphate is reacted through high temperature polymerization generates sodium pyrophosphate.
It is as follows to react specific equation:
A kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual, which comprises the following steps:
(1) will in the residual investment reactor of kettle, depressurize slowly heating, be distilled to recover kettle it is residual in moisture content.
(2) after moisture content is collected, decompression continues slowly heating, and disproportionated reaction occurs and generates triethyl phosphate；Collect life
At triethyl phosphate fraction, carry out rectifying, the triethyl phosphate finished product of 99.5% or more content can be obtained.
(3) continue after disproportionated reaction heating to bottoms carry out polymerization reaction, end of reaction can obtain content 95.0% with
On sodium pyrophosphate.
In a kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual of the present invention, the not production of waste
Raw, raw material is totally converted as product.
The residual commercial recovery method of the fluorescent whitening agent kettle of the phosphorous diethyl phthalate, which is characterized in that the kettle is residual to be
The kettle of phosphorous diethyl phthalate and sodium methoxide that fluorescent whitening agent production process generates is residual, pH value 6.0-7.0, essentially neutral item
Part, production are easily achieved；The residual main component of kettle are as follows: the sodium methoxide of 70% or so diethyl phosphate, 17% or so, 10% or so
Water and a little organic impurities.
The residual commercial recovery method of the fluorescent whitening agent kettle of the phosphorous diethyl phthalate, which is characterized in that the di(2-ethylhexyl)phosphate
Ethyl ester is the byproduct that fluorescent whitening agent condensation reaction generates, and the sodium methoxide is that fluorescent whitening agent condensation reaction is added
Catalyst.
The residual commercial recovery method of the fluorescent whitening agent kettle of the phosphorous diethyl phthalate, which is characterized in that the moisture warp
The process for refining that fluorescent whitening agent is returned after collection is recycled, and does not generate pollution and waste.
The residual commercial recovery method of the fluorescent whitening agent kettle of the phosphorous diethyl phthalate, which is characterized in that the step (2)
Disproportionated reaction process conditions are as follows: vacuum degree 0.085-0.098MPa, preferably 0.092-0.098MPa, reaction temperature 160-300
DEG C, it preferably 200-240 DEG C, reacts within this temperature range, reaction speed is moderate, easily controllable reaction process.Temperature is lower than 200
DEG C, reaction speed is excessively slow, and simultaneous reactions yield is low.Temperature is higher than 240 DEG C will not too big raising to product purity and yield,
But because temperature is high, reaction speed is fast, and the triethyl phosphate excessive velocities of generation acquire a certain degree of difficulty to reaction controlling.When reaction
Between 1-5h, preferably 2-3h.
The residual commercial recovery method of the fluorescent whitening agent kettle of the phosphorous diethyl phthalate, which is characterized in that the step (2)
Middle rectification process condition are as follows: vacuum degree 0.085-0.098MPa, preferably 0.092-0.098MPa.Collect fraction temperature 102-110
DEG C, preferably 102-105 DEG C.
The residual commercial recovery method of the fluorescent whitening agent kettle of the phosphorous diethyl phthalate, which is characterized in that the step (3)
The process conditions of polymerization reaction are as follows: reaction temperature is 300-600 DEG C, preferably 350-400 DEG C, is reacted within this temperature range, instead
Answer speed moderate, easily controllable reaction process, product purity can achieve requirement.Temperature is lower than 350 DEG C, and reaction speed is excessively slow,
Simultaneous reactions yield is low, and product purity is not high.Temperature is higher than 400 DEG C will not too big raising to product purity and yield, but
It will cause the waste of the energy since temperature raises.Reaction time 1-12h, preferably 3-4h.
The beneficial effects of the present invention are:
(1) compared with prior art, the present invention reaction condition is neutral, without acidification, simplify operation, factory is easily achieved；No
It is acidified the salt generated, avoids the generation of the three wastes；Without considering the selection of high-temperature reaction equipment material under acid condition, lectotype selection
It is easy.
(2) all reactions of the present invention can be completed in a reactor, and operating process is few, be easy to factory's realization.
(3) reaction yield is high, is not lost substantially；Kettle is residual to be completely converted into product, and without waste, environment protecting is good.
Specific embodiment
Analysis instrument and equipment used in embodiment: gas chromatography mass spectrometry (MS-GC), (U.S.'s Agilent is public by 7890B-5977
Department)；Nuclear magnetic resonance, Bruker company, AVANCE III HD(Germany)；Gas chromatograph GC-2014C(Japan, Shimadzu Corporation),
Moisture determination instrument KF-1(Town in Shanghai pavilion instrument).
Embodiment 1.
Weigh the residual 600g(p diethylaminobenzoic acid containing 2.72mol of fluorescent whitening agent kettle of phosphorous diethyl phthalate 70% and sodium methoxide 17%
Ester and 1.89mol sodium methoxide), it puts into 1000ml four-hole bottle, under the conditions of vacuum degree 0.098MPa, is warming up to 50 DEG C, collects water
Fraction 67.01g.220-240 DEG C is then raised temperature to, 3 hours disproportionated reactions are kept the temperature.Collection fraction is triethyl phosphate crude product
397.14g, gas spectrum are detected as 15.2% methanol and the triethyl phosphate of 83.1% content.
Triethyl phosphate fraction rectification process, vacuum degree 0.098MPa collect 102-103 DEG C of fraction, can obtain tricresyl phosphate second
Ester 332.74g, G/C content: 99.68%, acid value: 0.033mgKOH/g moisture content: 0.10%.Product structure confirmation:
GC-MS (m/e): 182,167,155,139,127,109,99,81,65,45,29,15
1HNMR(300MHz, CDCl3) δ ppm:1.308-1.390(t, J=7.1Hz, 9H, CH3), 4.087-4.159(m, 6H,
CH2)
13CNMR(25.16MHz, CDCl3) δ ppm:16.04,16.31,63.61,63.84
Bottoms is continuously heating to 350-370 DEG C, polymerization reaction 4 hours, obtains sodium pyrophosphate 122.81g, content 97.01%.
Embodiment 2.
The disproportionated reaction time is 5 hours, remaining condition is the same as embodiment 1.The methanol and 84.0% that content is 14.9% is obtained to contain
The triethyl phosphate crude product 398.62g of amount.Rectifying can obtain triethyl phosphate 332.74g, G/C content: 99.70%, acid value:
0.035mgKOH/g moisture content: 0.11%.Sodium pyrophosphate 122.23g, content 97.25% are obtained after bottoms polymerization
Embodiment 3.
Disproportionated reaction temperature is changed to 160-180 DEG C, remaining condition is the same as embodiment 1.Obtain content be 23.9% methanol and
The triethyl phosphate crude product 375.23g of 75.2% content.Rectifying can obtain triethyl phosphate 282.83g, G/C content: 99.55%, acid
Value: 0.058mgKOH/g moisture content: 0.19%.Sodium pyrophosphate 125.85g, content 95.31% are obtained after bottoms polymerization.
Embodiment 4.
Disproportionated reaction vacuum degree is 0.085MPa, remaining condition is the same as embodiment 1.Obtain content be 27.15% methanol and
The triethyl phosphate crude product 382.45g of 70.75% content.Rectifying can obtain triethyl phosphate 270.58g, G/C content: 99.60%, acid
Value: 0.031mgKOH/g moisture content: 0.17%.Sodium pyrophosphate 123.12g, content 96.12% are obtained after bottoms polymerization.
Embodiment 5.
Triethyl phosphate crude product rectifying vacuum degree is 0.085MPa, collects 108-110 DEG C of fraction temperature, remaining condition is the same as real
Apply example 1.Obtain the triethyl phosphate crude product 397.86g of the content methanol for being 15.1% and 82.9% content.Rectifying obtains tricresyl phosphate second
Ester 331.14g, G/C content: 99.51%, acid value: 0.042mgKOH/g moisture content: 0.18%.Sodium pyrophosphate is obtained after bottoms polymerization
123.49g content 96.89%.
Embodiment 6.
Bottoms polymerization temperature is 300 DEG C, remaining condition is the same as embodiment 1.Obtain the methanol and 83.5% that content is 15.3%
The triethyl phosphate crude product 395.75g of content.Rectifying obtains triethyl phosphate 331.05g, G/C content: 99.68%, acid value:
0.030mgKOH/g moisture content: 0.13%.Sodium pyrophosphate 119.72g, content 95.20% are obtained after bottoms polymerization.
Embodiment 7.
Bottoms polymerization time is 12 hours, remaining condition is the same as embodiment 1.Obtain the methanol and 83.6% that content is 15.2%
The triethyl phosphate crude product 395.01g of content.Rectifying obtains triethyl phosphate 330.99g, G/C content: 99.70%, acid value:
0.032mgKOH/g moisture content: 0.12%.Sodium pyrophosphate 122.23g, content 99.01% are obtained after bottoms polymerization.
Embodiment 8.
Bottoms polymerization time is 1 hour, remaining condition is the same as embodiment 1.Obtain the methanol and 83.7% that content is 14.9%
The triethyl phosphate crude product 394.97g of content.Rectifying obtains triethyl phosphate 331.09g, G/C content: 99.67%, acid value:
0.037mgKOH/g moisture content: 0.14%.Sodium pyrophosphate 120.42g, content 95.34% are obtained after bottoms polymerization.
Claims (10)
1. a kind of commercial recovery method that the fluorescent whitening agent kettle of phosphorous diethyl phthalate is residual, which is characterized in that use phosphoric acid two
The residual kettle of ethyl ester and sodium methoxide is raw material, under without acidulated condition, directly depressurizes high temperature disproportionated reaction, generates triethyl phosphate
And disodium hydrogen phosphate, then disodium hydrogen phosphate is reacted through high temperature polymerization generates sodium pyrophosphate.
2. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 1, feature exist
In, comprising the following steps:
(1) will in the residual investment reactor of kettle, depressurize slowly heating, be distilled to recover kettle it is residual in moisture content；
(2) after moisture content is collected, decompression continues slowly heating, and disproportionated reaction occurs and generates triethyl phosphate；Collect generation
Triethyl phosphate fraction carries out rectifying, can obtain the triethyl phosphate finished product of 99.5% or more content；
(3) continue heating after disproportionated reaction and polymerization reaction is carried out to bottoms, end of reaction can obtain 95.0% or more content
Sodium pyrophosphate.
3. the commercial recovery method residual with the fluorescent whitening agent kettle of 2 any phosphorous diethyl phthalates according to claim 1,
It is characterized in that, the kettle of the residual phosphorous diethyl phthalate generated for fluorescent whitening agent production process of the kettle and sodium methoxide is residual, and pH value is
6.0-7.0, essentially neutrallty condition, production are easily achieved；The residual main component of kettle are as follows: 70% or so diethyl phosphate, 17% left side
Right sodium methoxide, 10% or so water and a little organic impurities.
4. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 3, feature exist
In the diethyl phosphate is the byproduct that fluorescent whitening agent condensation reaction generates, and the sodium methoxide is fluorescent whitening agent
The catalyst that condensation reaction is added.
5. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 2, which is characterized in that
The process for refining that the moisture returns to fluorescent whitening agent after collecting is recycled, and does not generate pollution and waste.
6. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 2, which is characterized in that
The disproportionated reaction process conditions of the step (2) are as follows: vacuum degree 0.085-0.098MPa, preferably 0.092-0.098MPa, reaction
160-300 DEG C of temperature, preferably 200-240 DEG C, reaction time 1-5h, preferably 2-3h.
7. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 2, which is characterized in that
The disproportionated reaction process conditions of the step (2) are as follows: vacuum degree 0.092-0.098MPa, 200-240 DEG C of reaction temperature, when reaction
Between 2-3h.
8. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 2, which is characterized in that
Rectification process condition in the step (2) are as follows: vacuum degree 0.085-0.098MPa, preferably 0.092-0.098MPa；Collect fraction
102-110 DEG C of temperature, preferably 102-105 DEG C.
9. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate according to claim 2, which is characterized in that
The process conditions of step (3) polymerization reaction are as follows: reaction temperature be 300-600 DEG C, preferably 350-400 DEG C, reaction time 1-
12h, preferably 3-4h.
10. the residual commercial recovery method of the fluorescent whitening agent kettle of phosphorous diethyl phthalate, feature exist according to claim 2
In the process conditions of step (3) polymerization reaction are as follows: reaction temperature is 350-400 DEG C, reaction time 3-4h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606295A (en) * | 2019-10-22 | 2019-12-24 | 郭小龙 | Full-crushing dustbin |
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|---|---|---|---|---|
| CN101891761A (en) * | 2010-07-19 | 2010-11-24 | 吉林大学 | Method for catalytically synthesizing triethyl phosphate by phase transfer |
| CN101941988A (en) * | 2010-03-04 | 2011-01-12 | 浙江医药股份有限公司维生素厂 | Process for preparing triethyl phosphate by utilizing sodium diethyl phosphate |
| CN102206230A (en) * | 2011-04-02 | 2011-10-05 | 吉林市永林化工有限公司 | Method for preparing triethyl phosphate |
| CN103435222A (en) * | 2013-08-21 | 2013-12-11 | 山西青山化工有限公司 | Method for treating flourescent brightener wastewater with phosphorus |
-
2019
- 2019-04-17 CN CN201910308867.6A patent/CN109928993A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941988A (en) * | 2010-03-04 | 2011-01-12 | 浙江医药股份有限公司维生素厂 | Process for preparing triethyl phosphate by utilizing sodium diethyl phosphate |
| CN101891761A (en) * | 2010-07-19 | 2010-11-24 | 吉林大学 | Method for catalytically synthesizing triethyl phosphate by phase transfer |
| CN102206230A (en) * | 2011-04-02 | 2011-10-05 | 吉林市永林化工有限公司 | Method for preparing triethyl phosphate |
| CN103435222A (en) * | 2013-08-21 | 2013-12-11 | 山西青山化工有限公司 | Method for treating flourescent brightener wastewater with phosphorus |
Non-Patent Citations (2)
| Title |
|---|
| 林茵，李想主编: "《无机化学词典》", 31 December 2006 * |
| 马世昌等: "《化学物质词典》", 31 December 1999 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606295A (en) * | 2019-10-22 | 2019-12-24 | 郭小龙 | Full-crushing dustbin |
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