CN101934239A - Method for treating waste liquor containing catalyst in pentafluoroethane prodcution - Google Patents
Method for treating waste liquor containing catalyst in pentafluoroethane prodcution Download PDFInfo
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- CN101934239A CN101934239A CN2010102302826A CN201010230282A CN101934239A CN 101934239 A CN101934239 A CN 101934239A CN 2010102302826 A CN2010102302826 A CN 2010102302826A CN 201010230282 A CN201010230282 A CN 201010230282A CN 101934239 A CN101934239 A CN 101934239A
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- catalyst
- waste liquid
- pentafluoroethane
- contain
- processing method
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for treating waste liquor containing catalyst in pentafluoroethane production, including the following steps: 1) waste liquor containing catalyst is placed into a storage tank to be subject to standing for 22-26 hours, thus obtaining the waste liquor subject to standing; 2) 50% volume ratio of waste liquor subject to standing at the upper part is taken as waste liquor to be treated; the waste liquor to be treated is transferred into a kettle, and the waste liquor is set to be all composed of (n-C4H9)3N.2. 6HF; then equivalent alkali liquor is added, and stirring reaction is carried out at room temperature; 3) material after reaction which is obtained by the step 2) is filtered and is sent to a distillation device to be distilled, and fraction at 150-220 DEG C is collected. The method is environmentally friendly when being used for collecting butyl amine.
Description
Technical field
The present invention relates to contain in a kind of pentafluoroethane production the processing method of catalyst waste solution, particularly the recycling of catalyst tri-n-butylamine belongs to technical field of three-waste treatment.
Background technology
It is catalyst with the organic amine that U.S. Pat 5912392, US5969199 and U6118033 disclose a kind of, is the synthetic method of the pentafluoroethane (F125) of raw material with tetrafluoroethene and hydrogen fluoride.Amines catalyst can be triethylamine, tri-n-butylamine, tripropyl amine (TPA), N, accelerine and diisopropylethylamine etc.Above-mentioned catalyst is in recycling process, and along with cycle-index increases, impurity increase such as polymer causes the reaction system viscosity to increase in the reaction system, and catalyst activity reduces, and often needs more catalyst changeout.Contain in the waste liquid of catalyst, mainly contain and have plenty of catalyst, catalyst and hydrogen fluoride complex (shown in S-1, B is an amines catalyst) and the stable macromolecule polyalcohol of a class, these waste liquids can not directly abandon or at will dispose, unfriendly to environment like this, and can cause production cost to improve.Now main processing method is directly to deliver in the incinerator and burn containing catalyst waste solution, this method pollute big and three wastes treating capacity big.
B·nHF
S-1
In addition, it is raw material with tetrafluoroethene and hydrogen fluoride that patent CN1962064 discloses a kind of, is the processing method of waste liquid of the production pentafluoroethane of catalyst with organic amine and carbonyls.This method is diluted by water, and alkali lye neutralization and three steps of rectifying are reclaimed catalyst.The required amount of disposing waste liquid of this method is bigger, and energy consumption is higher, does not take into full account the initial gross separation of waste liquid material, and catalyst is the binary system that contains organic amine and carbonyls.
Summary of the invention
The technical problem to be solved in the present invention provides the processing method that contains catalyst waste solution in a kind of pentafluoroethane production, and this method is simple to operate, technology is succinct, the waste liquid amount of required processing is little, has reduced to a certain extent to produce and has polluted, and has reduced production cost.
In order to solve the problems of the technologies described above, the invention provides the processing method that contains catalyst waste solution in a kind of pentafluoroethane production, may further comprise the steps:
1), the waste liquid that will contain catalyst places storage tank to leave standstill 22～26 hours, must leave standstill the back waste liquid;
2), fetch bit is left standstill the back waste liquid as pending waste liquid in 50% volume ratio of the first half; Above-mentioned pending waste liquid is moved in the reactor, pending waste liquid is set at all by (n-C
4H
9)
3N2.6HF forms; The alkali lye that adds equivalent then, stirring reaction under the room temperature;
3), with step 2) reacting rear material of gained after filtering, deliver to distilling apparatus and distill, collect 150-220 ℃ cut.
As the improvement that contains the processing method of catalyst waste solution in the pentafluoroethane production of the present invention: the alkali lye step 2) is that mass content is 20～40% the NaOH aqueous solution, NaOH and (n-C
4H
9)
3The mol ratio of N2.6HF is 2.6: 1.
Another kind as the processing method that contains catalyst waste solution in the pentafluoroethane production of the present invention improves: the alkali lye step 2) is that mass content is 20～40% the KOH aqueous solution, KOH and (n-C
4H
9)
3The mol ratio of N2.6HF is 2.6: 1.
Another kind as the processing method that contains catalyst waste solution in the pentafluoroethane production of the present invention improves: the alkali lye step 2) is that mass content is 20～40% Na
2CO
3The aqueous solution, Na
2CO
3With (n-C
4H
9)
3The mol ratio of N2.6HF is 1.3: 1.
Advance～go on foot improvement as the processing method that contains catalyst waste solution in the pentafluoroethane production of the present invention: the reaction time is 0.5～2 hour step 2).
Among the present invention handled waste liquid be in the pentafluoroethane production process, catalyst through repeatedly recycle the back, by the still liquid that stays behind the rectifying products of separated.Mainly contain the catalyst tri-n-butylamine in the still liquid, and tri-n-butylamine and hydrofluoric complex compound, and some macromolecule polyalcohol accessory substances of reaction generation, hereinafter to be referred as containing catalyst waste solution.Contain the processing method of catalyst waste solution in the pentafluoroethane production of the present invention, its purpose is the recycling to the catalyst tri-n-butylamine.
Among the present invention, to contain catalyst waste solution through leaving standstill processing, get the 50% waste liquid (volume ratio on upper strata then, down together) as pending waste liquid, add equivalent alkali lye (be about to the compound 1 of quality such as pending waste liquid is designated as, the chemical reaction equivalent according to following reaction equation adds alkali lye then) again and after reaction a period of time, deliver to the distilling apparatus distillation again, collect 150-220 ℃ of cut, reclaim and obtain tri-n-butylamine.
(n-C
4H
9)
3N·2.6HF+2.6OH
-——→(n-C
4H
9)
3N+2.6F
-+2.6H
2O
Compound 1
It is that a kind of brand-new dead catalyst is handled means for the tri-n-butylamine recycling that contains catalyst waste solution that produces in the pentafluoroethane production that technical characterstic of the present invention is.By the catalyst activity function admirable that recovery obtains, can proceed to produce and utilize.
The inventor fully takes into account following content in the invention process: mainly comprise following material owing to contain the waste liquid of catalyst: some macromolecule polyalcohol accessory substances that catalyst tri-n-butylamine, tri-n-butylamine and hydrofluoric complex compound and reaction generate; Catalyst is different with macromolecule polyalcohol density, can be after the less catalyst of density leaves standstill in the upper strata enrichment, and macromolecule polyalcohol is then in lower floor's enrichment.The inventor found through experiments, and will contain catalyst waste solution and leave standstill processing, gets upper strata 50% (volume ratio, down with) and contains catalyst waste solution and carry out catalyst recovery and handle, and recovering effect is good; Lower floor then can't reclaim and obtain catalyst.So only need the upper strata waste liquid of catalyst enrichment is recycled, required processing like this to contain the catalyst waste solution amount few, alkali charge reduces, energy consumption is low.So the present invention is to contain the raw material of catalyst waste solution as catalyst recovery through the upper strata 50% of leaving standstill processing.
Contain in the pentafluoroethane production of the present invention catalyst waste solution processing method have a following advantage:
(1) the present invention adopts and to leave standstill treating method, by the simple separation technology, heavy ends impurity etc. is at first separated with hydrogen fluoride complex with catalyst tri-n-butylamine and tri-n-butylamine, reduces the treating capacity of subsequent step, reduces cost recovery.
(2) alkali lye selected for use of the present invention is NaOH, KOH and Na
2CO
3The aqueous solution, thorough for tri-n-butylamine and hydrogen fluoride complex reaction, tri-n-butylamine is discharged again, by simple distillation, tri-n-butylamine rate of recovery height, Functionality, quality and appealing design.The catalyst tri-n-butylamine that recovery obtains can be used for the ordinary production of pentafluoroethane.
The specific embodiment
The used waste liquid that contains catalyst is in following examples: make catalyst with tri-n-butylamine, tetrafluoroethene and hydrogen fluoride are the catalyst waste solution that contains that obtains in the production process of feedstock production pentafluoroethane.Aforementioned production method has in detail in patent US5969199 embodiment 1 informs.
Contain the processing method of catalyst waste solution in embodiment 1, a kind of pentafluoroethane production, carry out following steps successively:
1), get 500g and contain catalyst waste solution and in storage tank, leave standstill 24h, get upper strata 50% (volume ratio) waste liquid as pending waste liquid, quality is 190g.
2), the pending waste liquid of step 1) gained is added in the 500ml there-necked flask,, stir room temperature (10～30 ℃) reaction 1h down by reaction equivalent the add 20% NaOH aqueous solution 421g of (mass content, down with).
(n-C
4H
9)
3N·2.6HF+2.6NaOH——→(n-C
4H
9)
3N+2.6NaF+2.6H
2O
3), with step 2) after the reaction of gained waste liquid after filtration, filtrate is delivered to rectifier unit, collect 150-220 ℃ by distillation between cut, obtain liquid 167g, detecting the tri-n-butylamine mass fraction through chromatogram is 89.0%.Empirical tests, it can be directly used in pentafluoroethane production.
Contain the processing method of catalyst waste solution in embodiment 2, a kind of pentafluoroethane production, carry out following steps successively:
1), get 500g and contain catalyst waste solution and in storage tank, leave standstill 22h, get upper strata 50% (volume ratio) waste liquid as pending waste liquid, quality is 190g.
2), the pending waste liquid of step 1) gained is added in the 500ml there-necked flask, add the Na of 28% (mass content) by the reaction equivalent
2CO
3Aqueous solution 399g stirs normal-temperature reaction 2h down.
(n-C
4H
9)
3N·2.6HF+1.3Na
2CO
3——→(n-C
4H
9)
3N+2.6NaF+2.6H
2O+CO
2
3), with step 2) after the reaction of gained waste liquid after filtration, filtrate is delivered to rectifier unit, collect 150-220 ℃ by distillation between cut, obtain liquid 156g, detecting the tri-n-butylamine mass fraction through chromatogram is 87.1%.Empirical tests, it can be directly used in pentafluoroethane production.
Contain the processing method of catalyst waste solution in embodiment 3, a kind of pentafluoroethane production, carry out following steps successively:
1), get 500g and contain catalyst waste solution and in storage tank, leave standstill 24h, get upper strata 50% (volume ratio) waste liquid as pending waste liquid, quality is 190g.
2), the pending waste liquid of step 1) gained is added in the 500ml there-necked flask, add 30% KOH aqueous solution 393g, stir normal-temperature reaction 0.5h down by the reaction equivalent.
(n-C
4H
9)
3N·2.6HF+2.6KOH——→(n-C
4H
9)
3N+2.6KF+2.6H
2O
3), with step 2) after the reaction of gained waste liquid after filtration, filtrate is delivered to rectifier unit, collect 150-220 ℃ by distillation between cut, obtain liquid 154g, detecting the tri-n-butylamine mass fraction through chromatogram is 88.1%.Empirical tests, it can be directly used in pentafluoroethane production.
Contain the processing method of catalyst waste solution in embodiment 4, a kind of pentafluoroethane production, carry out following steps successively:
1), get 500g and contain catalyst waste solution and in storage tank, leave standstill 24h, get upper strata 50% (volume ratio) waste liquid as pending waste liquid, quality is 190g.
2), the pending waste liquid of step 1) gained is added in the 500ml there-necked flask, add 40% NaOH aqueous solution 210g, stir normal-temperature reaction 0.5h down by the reaction equivalent.
(n-C
4H
9)
3N·2.6HF+2.6NaOH——→(n-C
4H
9)
3N+2.6NaF+2.6H
2O
3), with step 2) after the reaction of gained waste liquid after filtration, filtrate is delivered to rectifier unit, collect 150-220 ℃ by distillation between cut, obtain liquid 149g, detecting the tri-n-butylamine mass fraction through chromatogram is 89.2%.Empirical tests, it can be directly used in pentafluoroethane production.
Contain the processing method of catalyst waste solution in embodiment 5, a kind of pentafluoroethane production, carry out following steps successively:
1), get 500g and contain catalyst waste solution and in storage tank, leave standstill 26h, get upper strata 50% (volume ratio) waste liquid as pending waste liquid, quality is 190g.
2), the pending waste liquid of step 1) gained is added in the 500ml there-necked flask, add 40% NaOH aqueous solution 210g, stir normal-temperature reaction 2h down by the reaction equivalent.
(n-C
4H
9)
3N·2.6HF+2.6NaOH——→(n-C
4H
9)
3N+2.6NaF+2.6H
2O
3), with step 2) after the reaction of gained waste liquid after filtration, filtrate is delivered to rectifier unit, collect 150-220 ℃ by distillation between cut, obtain liquid 166g, detecting the tri-n-butylamine mass fraction through chromatogram is 88.2%.Empirical tests, it can be directly used in pentafluoroethane production.
The comparative example, handle 500g according to the method for patent CN1962064 and contain catalyst waste solution, the content and the weight of required aqueous slkali are described in table 1 below respectively, and the weight and the mass fraction of the tri-n-butylamine of final gained are also as shown in table 1.
Table 1
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (5)
1. contain the processing method of catalyst waste solution in the pentafluoroethane production, it is characterized in that may further comprise the steps:
1), the waste liquid that will contain catalyst places storage tank to leave standstill 22～26 hours, must leave standstill the back waste liquid;
2), fetch bit is left standstill the back waste liquid as pending waste liquid in 50% volume ratio of the first half; Above-mentioned pending waste liquid is moved in the reactor, pending waste liquid is set at all by (n-C
4H
9)
3N2.6HF forms; The alkali lye that adds equivalent then, stirring reaction under the room temperature;
3), with step 2) reacting rear material of gained after filtering, deliver to distilling apparatus and distill, collect 150-220 ℃ cut.
2. contain the processing method of catalyst waste solution in the pentafluoroethane production according to claim 1, it is characterized in that: the alkali lye described step 2) is that mass content is 20～40% the NaOH aqueous solution, NaOH and (n-C
4H
9)
3The mol ratio of N2.6HF is 2.6: 1.
3. contain the processing method of catalyst waste solution in the pentafluoroethane production according to claim 1, it is characterized in that: the alkali lye described step 2) is that mass content is 20～40% the KOH aqueous solution, KOH and (n-C
4H
9)
3The mol ratio of N2.6HF is 2.6: 1.
4. contain the processing method of catalyst waste solution in the pentafluoroethane production according to claim 1, it is characterized in that: the alkali lye described step 2) is that mass content is 20～40% Na
2CO
3The aqueous solution, Na
2CO
3With (n-C
4H
9)
3The mol ratio of N2.6HF is 1.3: 1.
5. according to the processing method that contains catalyst waste solution in claim 2, the 3 or 4 described pentafluoroethane productions, it is characterized in that: the reaction time is 0.5～2 hour described step 2).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102302826A CN101934239B (en) | 2010-07-19 | 2010-07-19 | Method for treating waste liquor containing catalyst in pentafluoroethane prodcution |
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|---|---|---|---|
| CN2010102302826A CN101934239B (en) | 2010-07-19 | 2010-07-19 | Method for treating waste liquor containing catalyst in pentafluoroethane prodcution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997078A (en) * | 2018-07-27 | 2018-12-14 | 浙江巨圣氟化学有限公司 | The treating method of pentafluoroethane production process upper layer decaying catalyst |
| CN109704973A (en) * | 2019-01-15 | 2019-05-03 | 浙江巨化技术中心有限公司 | The processing method of dead catalyst in a kind of production of pentafluoroethane |
| CN110128275A (en) * | 2019-04-19 | 2019-08-16 | 浙江巨化技术中心有限公司 | A kind of processing method of waste liquor containing catalyst in pentafluoroethane prodcution |
| CN111732514A (en) * | 2020-06-16 | 2020-10-02 | 浙江大学 | Method for recovering tri-n-butylamine in byproduct-high-boiling-point substance hydrolysis wastewater in dichlorodimethylsilane monomer production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6723874B1 (en) * | 1998-11-30 | 2004-04-20 | Solvay Fluor Und Derivate Gmbh | Method of producing acid fluorides from acid chlorides |
| CN1962064A (en) * | 2006-11-29 | 2007-05-16 | 山东东岳高分子材料有限公司 | Method for processing waste catalyst in production of pentafluoro ethane |
| CN101759571A (en) * | 2010-01-28 | 2010-06-30 | 浙江大学 | Preparation method of N,N-diisopropylethylamine |
-
2010
- 2010-07-19 CN CN2010102302826A patent/CN101934239B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6723874B1 (en) * | 1998-11-30 | 2004-04-20 | Solvay Fluor Und Derivate Gmbh | Method of producing acid fluorides from acid chlorides |
| CN1962064A (en) * | 2006-11-29 | 2007-05-16 | 山东东岳高分子材料有限公司 | Method for processing waste catalyst in production of pentafluoro ethane |
| CN101759571A (en) * | 2010-01-28 | 2010-06-30 | 浙江大学 | Preparation method of N,N-diisopropylethylamine |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997078A (en) * | 2018-07-27 | 2018-12-14 | 浙江巨圣氟化学有限公司 | The treating method of pentafluoroethane production process upper layer decaying catalyst |
| CN108997078B (en) * | 2018-07-27 | 2021-04-27 | 浙江巨圣氟化学有限公司 | Method for treating upper deactivated catalyst in pentafluoroethane production process |
| CN109704973A (en) * | 2019-01-15 | 2019-05-03 | 浙江巨化技术中心有限公司 | The processing method of dead catalyst in a kind of production of pentafluoroethane |
| CN110128275A (en) * | 2019-04-19 | 2019-08-16 | 浙江巨化技术中心有限公司 | A kind of processing method of waste liquor containing catalyst in pentafluoroethane prodcution |
| CN110128275B (en) * | 2019-04-19 | 2022-06-17 | 浙江巨化技术中心有限公司 | Treatment method of catalyst-containing waste liquid in pentafluoroethane production |
| CN111732514A (en) * | 2020-06-16 | 2020-10-02 | 浙江大学 | Method for recovering tri-n-butylamine in byproduct-high-boiling-point substance hydrolysis wastewater in dichlorodimethylsilane monomer production |
| CN111732514B (en) * | 2020-06-16 | 2021-05-25 | 浙江大学 | Method for recovering tri-n-butylamine in byproduct-high-boiling-point substance hydrolysis wastewater in dichlorodimethylsilane monomer production |
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| Publication number | Publication date |
|---|---|
| CN101934239B (en) | 2012-07-25 |
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Effective date of registration: 20120525 Address after: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Applicant after: Zhejiang University Co-applicant after: Jinhua Yonghe Fluorochemical Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Applicant before: Zhejiang University |
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