CN1962064A - Method for processing waste catalyst in production of pentafluoro ethane - Google Patents

Method for processing waste catalyst in production of pentafluoro ethane Download PDF

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Publication number
CN1962064A
CN1962064A CNA2006100703801A CN200610070380A CN1962064A CN 1962064 A CN1962064 A CN 1962064A CN A2006100703801 A CNA2006100703801 A CN A2006100703801A CN 200610070380 A CN200610070380 A CN 200610070380A CN 1962064 A CN1962064 A CN 1962064A
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CN
China
Prior art keywords
dead catalyst
pentafluoroethane
processing method
produced
cat head
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Pending
Application number
CNA2006100703801A
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Chinese (zh)
Inventor
宋学章
孙百开
赵永晓
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Shandong Dongyue Polymer Material Co Ltd
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Shandong Dongyue Polymer Material Co Ltd
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Priority to CNA2006100703801A priority Critical patent/CN1962064A/en
Publication of CN1962064A publication Critical patent/CN1962064A/en
Pending legal-status Critical Current

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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 relates to a method for treating the waste catalyst in hydrofluoeic ether production, wherein it comprises: mixing catalyst, reacting with alkali, and distilling in distilling tower. The invention has low energy consumption and high quality, with low cost.

Description

The processing method of dead catalyst during a kind of pentafluoroethane is produced
Technical field
The present invention relates to the processing method of dead catalyst in a kind of pentafluoroethane production, belong to the chemical industry technical field of three-waste treatment.
Background technology
Prepare in pentafluoroethane (HFC-125) production process with tetrafluoroethene and anhydrous hydrogen fluoride, need carry out catalytic reaction with catalyst, CN200410035429.0 discloses and has a kind ofly prepared the method for pentafluoroethane with tetrafluoroethene and anhydrous hydrogen fluoride, and to be binary system be made up of tertiary amine compounds and the compound that contains carbonyl its used catalyst.Tertiary amine compounds can be a kind of, also can be some kinds mixture.As: triethylamine, Tri-n-Propylamine, NN-dimethylaniline, tri-n-butylamine, isopropyl diethylamine, tripropyl amine (TPA), triphenylamine etc.The compound that contains carbonyl can be a kind of carbonyls, also can be the mixture of some kinds of carbonyls.As: phosphorous acid diethyl fat, cyclohexanone, 3-phenylacrolein, acetone, butanone, acetophenone, ketenes, propiophenone etc.Above-mentioned catalyst can lose efficacy in the process of using gradually, loses the catalyst of catalytic action, must often change, and it is a difficult problem that the dead catalyst that changes is handled.Dead catalyst main component tertiary amine compounds generates HNFR after fluoridizing 3With another kind of stable material etc., belong to hazardous chemical.Press the regulation of " the hazardous chemical management rules " of China, can not at will dispose or abandon.Processing method generally is to burn in incinerator now, and this method environmental pollution and three wastes treating capacity are big, and power consumption is high.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of processing method of dead catalyst of from pentafluoroethane (HFC-125) production process, being replaced, can reduce environmental pollution, reduce cost recovery, purposes such as the quality of raising product and the rate of recovery.
The processing method of dead catalyst was that tertiary amine compounds generates HNFR after fluoridizing to the dead catalyst composition mainly during pentafluoroethane of the present invention was produced 3Processing, the recovery of dead catalyst, hereinafter to be referred as dead catalyst.
The processing method of dead catalyst during pentafluoroethane of the present invention is produced is characterized in that the main component tertiary amine compounds of dead catalyst is recycled with the compound that contains carbonyl.
The processing method of dead catalyst during pentafluoroethane of the present invention is produced, step is as follows:
(1) dead catalyst is inserted in the reactor, add certain pure water dilution, stir, the equivalent proportion according to chemical reaction adds liquid base then, and normal temperature is fully reaction down.
(2) material in the reactor inserted after vacuum filtration carry out rectifying in the rectifying column, control the temperature of tower still well, utilize the boiling point difference of each material and water to separate:
When tower top temperature was 30～100 ℃, the cat head separate fraction was a kind of tertiary amine compounds;
When tower top temperature was 20～120 ℃, the cat head separate fraction was moisture foam-like material;
When tower top temperature was 50～180 ℃, the cat head separate fraction was a kind of compound that contains carbonyl.
Preferably, the reaction time of above-mentioned steps (1) is 1～2 hour.
Preferably, the liquid caustic soda of above-mentioned steps (1) is NaOH, KOH, NH 3H 2O or Na 2CO 3The aqueous solution.Concentration 20～50%wt is advisable.
Preferably, the dead catalyst mixing time of above-mentioned steps (1) is 5～20min.
Major technique characteristics of the inventive method are that the main component tertiary amine compounds of dead catalyst and the compound that contains carbonyl are recycled, and have opened up a kind of processing method of brand-new dead catalyst.
Method of the present invention at first uses a kind of liquid caustic soda and the dead catalyst that is changed from pentafluoroethane (HFC-125) is produced fully to react, with HNFR 3Reduce, dispose unnecessary fluorine ion simultaneously, carry out distillation operation then, thereby obtain the catalyst prod of purity height, Functionality, quality and appealing design.
The preferred alkali NaOH of the present invention, KOH, NH 3H 2O or Na 2CO 3Have sufficient reacting, can well reclaim the effect of catalyst for dead catalyst, product recovery rate and purity height like this, Functionality, quality and appealing design, the catalyst that reclaims can be used for pentafluoroethane (HFC-125) and produces normal, and can effectively reduce cost recovery, reduce characteristics such as environmental pollution, use the inventive method from economically or all have crucial meaning in the environmental protection.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:
Present embodiment prepares the method for pentafluoroethane so that CN200410035429.0 is disclosed with tetrafluoroethene and anhydrous hydrogen fluoride, and the 2kg dead catalyst that is changed from pentafluoroethane (HFC-125) is produced is treated to example, and its processing method is:
48%NaOH is stand-by for A, selection liquid caustic soda;
B, stirring: add dead catalyst 2kg in 3 liters of reactors, the back adds pure water 1000～2000ml dilution, opens and stirs, and stirs evenly 6 minutes;
C, reaction: the equivalent proportion according to chemical reaction adds the liquid caustic soda 48%NaOH that is prepared in reactor, and it was fully reacted 1～2 hour, and reaction equation is as follows:
HNFR 3+NaOH＝NR 3+NaF+H 2O
D, fractionation purify: the material in the reactor is inserted carry out fractionation in the fractionating column, control the temperature of tower still well, utilize the boiling point difference of each material and water to separate.When tower top temperature was 20～120 ℃, the cat head separate fraction was a kind of tertiary amine compounds, and quality is 604g; When tower top temperature was 80～100 ℃, the cat head separate fraction was moisture foam-like material, and quality is 506g; When tower top temperature was 50～180 ℃, the cat head separate fraction was a kind of compound that contains carbonyl, and the quality that obtains is 297g.
Embodiment 2:
Present embodiment discloses with CN200410035429.0 and has a kind ofly prepared the method for pentafluoroethane with tetrafluoroethene and anhydrous hydrogen fluoride, and the 1kg dead catalyst that is changed from pentafluoroethane (HFC-125) is produced is treated to example, and its processing method is:
32%KOH is stand-by for A, selection liquid caustic soda;
B, stirring: add a certain amount of dead catalyst 2kg in 3 liters of reactors, the back adds pure water 400～500ml dilution, opens and stirs, and stirs evenly 8 minutes;
C, reaction: the equivalent according to chemical reaction adds the liquid caustic soda KOH that is prepared in reactor, and it was fully reacted 1.5 hours, and reaction equation is as follows:
HNFR 3+KOH＝NR 3+KF+H 2O
D, fractionation purify: the material in the reactor is put into fractionating column carry out fractionation, control the temperature of tower still well, utilize the boiling point difference of each material and water to separate.When 20～120 ℃ of tower top temperatures, the cat head separate fraction is a kind of tertiary amine compounds, and quality is 435g; When tower top temperature was 80～100 ℃, the cat head separate fraction was moisture foam-like material, and quality is 180g; When tower top temperature was 50～180 ℃, the cat head separate fraction was a kind of compound that contains carbonyl, and the quality that obtains is 65g.
Embodiment 3:
Present embodiment discloses with CN200410035429.0 and has a kind ofly prepared the method for pentafluoroethane with tetrafluoroethene and anhydrous hydrogen fluoride, and the dead catalyst of the 1.5kg that changes is treated to example from pentafluoroethane (HFC-125) is produced, and its processing method is:
A, selection liquid caustic soda 28%NH 3H 2O is stand-by;
B, stirring: add a certain amount of dead catalyst 2kg in 3 liters of reactors, the back adds pure water 800～1000ml dilution, opens and stirs, and stirs evenly about 5 minutes;
C, reaction: the equivalent according to chemical reaction adds the liquid caustic soda of being prepared in reactor, and it was fully reacted 2 hours, and reaction equation is as follows:
HNFR 3+NH 3·H 2O＝NR 3+NH 4F+H 2O
D, fractionation purify: the material in the reactor is put into rectifying column carry out fractionation, control the temperature of tower still well, utilize the boiling point difference of each material and water to separate.When tower top temperature was 20～120 ℃, the cat head separate fraction was a kind of tertiary amine compounds, and quality is 501g; When tower top temperature was 80～100 ℃, the cat head separate fraction was moisture foam-like material, and quality is 400g; When tower top temperature was 50～180 ℃, the cat head separate fraction was a kind of compound that contains carbonyl, and the quality that obtains is 300g.
Embodiment 4:
Present embodiment discloses with CN200410035429.0 and has a kind ofly prepared the method for pentafluoroethane with tetrafluoroethene and anhydrous hydrogen fluoride, and the dead catalyst of the 2kg that changes is treated to example from pentafluoroethane (HFC-125) is produced, and its processing method is:
A, selection liquid caustic soda 32%Na 2CO 3Stand-by;
B, stirring: add a certain amount of dead catalyst 2kg in 3 liters of reactors, the back adds pure water 1000～2000ml dilution, opens and stirs, and stirs evenly about 5 minutes;
C, reaction: the equivalent according to chemical reaction adds the liquid caustic soda of being prepared in reactor, and it was fully reacted 2 hours, and reaction equation is as follows:
2HNFR 3+Na 2CO 3＝2NR 3+2NaF+H 2O+CO 2
D, fractionation purify: the material in the reactor is put into rectifying column carry out fractionation, control the temperature of tower still well, utilize the boiling point difference of each material and water to separate.When tower top temperature was 20～120 ℃, the cat head separate fraction was a kind of tertiary amine compounds, and quality is 415g; When tower top temperature was 80～100 ℃, the cat head separate fraction was moisture foam-like material, and quality is 302g; When tower top temperature was 50～180 ℃, the cat head separate fraction was a kind of compound that contains carbonyl, and the quality that obtains is 218g.
The recovery product result of the foregoing description is compiled in the following table:
Embodiment The amount of tertiary amine compounds (g) Moisture foam quality (g) The amount (g) that contains the compound of carbonyl
1 604 506 297
2 435 180 65
3 501 400 300
4 415 302 218
Handle necessarily having raffinate and residue later, at will do not abandon, concentrate post processing.Concrete method is to add calcium compound, after the reaction, obtains the calcirm-fluoride precipitation, makes content of fluoride ion in the water after the processing reach the permission discharge standard of country.

Claims (6)

1. the processing method of dead catalyst during a pentafluoroethane is produced is characterized in that the main component tertiary amine compounds of dead catalyst is recycled with the compound that contains carbonyl.
2. the processing method of dead catalyst during a pentafluoroethane is produced, step is as follows:
(1) dead catalyst is inserted in the reactor, stir, the equivalent proportion according to chemical reaction adds liquid base then, and normal temperature is fully reaction down;
(2) material in the reactor inserted after vacuum filtration carry out rectifying in the rectifying column, control the temperature of tower still well, utilize the boiling point difference of each material and water to separate:
When tower top temperature was 20～120 ℃, the cat head separate fraction was a kind of tertiary amine compounds;
When tower top temperature was 80～100 ℃, the cat head separate fraction was moisture foam-like material;
When tower top temperature was 50～180 ℃, the cat head separate fraction was a kind of compound that contains carbonyl.
3. the processing method of dead catalyst during pentafluoroethane as claimed in claim 2 is produced, the reaction time that it is characterized in that described step (1) is 1～2 hour.
4. the processing method of dead catalyst during pentafluoroethane as claimed in claim 2 is produced, the liquid caustic soda that it is characterized in that described step (1) is NaOH, KOH, NH 3H 2O or Na 2CO 3The aqueous solution.
5. the processing method of dead catalyst is characterized in that described NaOH, KOH, NH during pentafluoroethane as claimed in claim 4 was produced 3H 2O or Na 2CO 3Concentration of aqueous solution 20～50%wt.
6. the processing method of dead catalyst during pentafluoroethane as claimed in claim 2 is produced, the dead catalyst mixing time that it is characterized in that described step (1) is 5～20min.
CNA2006100703801A 2006-11-29 2006-11-29 Method for processing waste catalyst in production of pentafluoro ethane Pending CN1962064A (en)

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Application Number Priority Date Filing Date Title
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101934239A (en) * 2010-07-19 2011-01-05 浙江大学 Method for treating waste liquor containing catalyst in pentafluoroethane prodcution
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
CN110902655A (en) * 2018-09-18 2020-03-24 中昊晨光化工研究院有限公司 Method and device for treating waste catalyst in difluoroethane production

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101934239A (en) * 2010-07-19 2011-01-05 浙江大学 Method for treating waste liquor containing catalyst in pentafluoroethane prodcution
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
CN110902655A (en) * 2018-09-18 2020-03-24 中昊晨光化工研究院有限公司 Method and device for treating waste catalyst in difluoroethane production
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

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