CN1651144A - Regeneration method of fluorine catalyst with chromium base - Google Patents
Regeneration method of fluorine catalyst with chromium base Download PDFInfo
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- CN1651144A CN1651144A CNA2004101015528A CN200410101552A CN1651144A CN 1651144 A CN1651144 A CN 1651144A CN A2004101015528 A CNA2004101015528 A CN A2004101015528A CN 200410101552 A CN200410101552 A CN 200410101552A CN 1651144 A CN1651144 A CN 1651144A
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
A process for regenerating the fluorizing Cr-base catalyst includes such steps as treating in the mixture of air and N2 at 300-500 deg.C, treating in the mixture of H2 and HF gas at 250-350 dg.C, and fluorizing it by HF gas.
Description
Technical field
The present invention relates to a kind of regeneration treating method of catalyst, relate in particular to be used for the regeneration treating method of the chromium-based fluorination catalyst of gas phase fluorination halohydrocarbons reaction.
Background technology
Under hot conditions, carry out in the gas-phase reaction with the hydrogen fluoride fluorination of halogenated hydrocarbon, use chromium-based fluorination catalyst to be widely adopted, be well-known in the art.
The ubiquitous problem of this class catalyst is, the organic cracking or oligomeric carbonaceous residue that forms and/or the organic pollution that when between its operating period, react owing to participation, surface deposition and the duct of having stopped up catalyst at catalyst, along with the passing activity of such catalysts of time of reaction reduces gradually, so that catalyst loses activity.
In order to recover the catalytic activity of catalyst, the general method that adopts in this area is the oxidizing gases such as mist of catalyst with air or oxygen and inert gas, under 300～500 ℃ of hot conditions, handle, make the carbonaceous residue and/or the organic pollution burning of deposition, activity of such catalysts is recovered in the surface of clean catalysis agent and duct.
Yet, above-mentionedly handle deactivated catalyst with oxidizing gas and can cause Cr (III) part to be oxidized to Cr (VI), cause the loss of catalyst main component crome metal, so loss activity of such catalysts metal, make activity of such catalysts reduce the lost of life.
In addition, the Cr of generation (VI) compound is poisonous volatile materials, is very harsh to its discharge standard, and for example the Cr in waste water (VI) concentration does not allow to be higher than 1ppm, otherwise can cause the serious environmental pollution problems.And carrying out in the fluorination reaction with hydrogen fluoride, using the situation of the catalyst of said method regeneration,, generating toxic oxygen fluoride, polluted product and contaminated environment because of Cr (VI) reacts with hydrogen fluoride.
Chinese patent 97111149.9 discloses a kind of at 350～400 ℃, handles useless catalyst with air or with oxygen and noble gas mixtures, disappears until organic pollution; At 300～380 ℃, use the method for the inert gas of the hydrogen that contains the 1%-10% volume then to the further regenerated catalyst of handling of this catalyst.Can solve effectively that Cr (III) part is oxidized to Cr (VI) in the deactivated catalyst process of regeneration, cause the losing issue of catalyst main component crome metal.This catalyst recovery process does not carry out fluorination treatment to catalyst, can cause shorten the service life of regenerated catalyst.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of the chromium-based fluorination catalyst of regenerating, and overcomes disadvantages of background technology, improves the service life of regenerated catalyst.
Design of the present invention is at first to adopt in the art usual way that catalyst is carried out the air oxidation burning to remove carbonaceous residue, and then handle catalyst with the mist of hydrogen fluoride and hydrogen, make catalyst reduction, fluoridize simultaneously and carry out, reach and do not produce Cr (VI), the leakage that does not have the main component reactive metal chromium of catalyst, use the hydrogen fluoride trealment catalyst at last, regenerated catalyst is existed to fluoridize state.Avoid regenerated catalyst without the hydrogen fluoride activation processing, when gas phase fluorination, easily generate water, make catalysqt deactivation and shorten its service life.The chromium base fluorine catalyst of regeneration recovers original catalytic activity, and has original catalyst suitable service life.
Method of the present invention comprises:
(1), deactivated chromium-based fluorination catalyst is handled, disappear until organic pollution at 300 ℃～500 ℃ mists with air and nitrogen;
(2), at 250 ℃～350 ℃ mists with the hydrogen of hydrogen fluoride and 1～10% percent by volume, handle the catalyst of handling through step (1), absorption tail gas, detection is less than Cr (VI) compound;
(3), at 300 ℃～350 ℃ catalyst of handling by step (2) with hydrogen fluoride trealment.
Air in step (1) and nitrogen ratios are 1: 1～6, and preferred proportion is 1: 2.
Treatment temperature in step (2) is preferably 300 °.
The scope of the amounts of hydrogen in the hydrogen fluoride gas mixture in step (2) is preferably 5%～10% volume.
In the methods of the invention, involved pressure is generally normal pressure.
The inventive method is applicable to and is stated from AlF
3, Al
2O
3, MgO, fluoridize Al
2O
3, based on Cr (III) oxide and/or oxygen fluoride, be used for the regeneration of the fluorination reaction fluorination catalyst of halogenated hydrocarbons being handled at gas phase hydrogen fluoride.
The inventive method is applicable to that fluorination catalyst is by being stated from AlF
3, Al
2O
3, MgO, MgF
2, CaF
2, fluoridize Al
2O
3On Cr (III) oxide and/or oxygen fluoride and Co
2+, Mg
2+, In
3+, Zn
2+, Cd
2+One or more metals wherein constitute the regeneration of catalyst to be handled.
The inventive method is applicable to that fluorination catalyst is made of Cr (III) oxide and/or oxygen fluoride or by Cr (III) oxide and/or oxygen fluoride and Co
2+, Mg
2+In
3+, Zn
2+, Cd
2+One or more metals wherein constitute the regeneration of catalyst to be handled.
The present invention compared with prior art has following beneficial effect:
(1), be in reducing atmosphere, to carry out through fluoridizing of the catalyst after the oxidation processes, catalyst is activated, do not produce the loss of crome metal again, the service life that helps improving hardware again.
(2), the regeneration chromium-based fluorination catalyst recovers original catalytic activity, even further raising is arranged.
The specific embodiment
To assay method used among the embodiment:
1, the content of gas chromatography determination carbon dioxide.
Gas chromatography well known in the art by gathering the tail gas that regenerated catalyst is handled, is used gas chromatographic analysis, the content of carbon dioxide in the tail gas that the mensuration regenerated catalyst is handled.
2, pass through the content of oxidimetric titration assay determination Cr (VI) compound.
The oxidimetric titration analytical method of wet method well known in the art by the tail gas with acidifying water absorption and regeneration catalyst treatment, is used KI/Na then
2S
2O
3The solution titration, the content of mensuration Cr (VI) compound.
Embodiment 1
50mlCr with precipitation method preparation
2O
3After catalyst is used the HF fluorination treatment, for being used in 350 ℃ of HF to CF
2CH
2Cl fluoridizes synthetic CF
3CH
2Use catalyst in the F gas-phase reaction, lose catalytic activity until this catalyst.HF: CF wherein
2CH
2The Cl mol ratio is 10: 1.
Handled 8 hours with the mixture (volume ratio is 1: 2) of air/nitrogen at 350 ℃ of catalyst, do not detect carbon dioxide through gas chromatographic analysis to inactivation.Being cooled to 300 ℃ of carbon hydrogen fluoride mixture with the hydrogen that contains 1% volume handled 1 hour.Absorption reaction tail gas is measured through the oxidimetric titration analytical method with wet method, does not detect Cr (VI) compound.Feed pure hydrogen fluoride, be warming up to 350 ℃ gradually simultaneously, continue to feed pure hydrogen fluoride 6 hours.Catalytic activity test result before and after the catalyst regeneration is listed in table 1.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 8%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 10%.
Embodiment 2
Implement with reference to embodiment 1, different is to handle 0.5 hour 300 ℃ of carbon hydrogen fluoride mixture with the hydrogen that contains 5% volume with embodiment 1.Absorption reaction tail gas is measured through the oxidimetric titration analytical method with wet method, does not detect Cr (VI) compound.Catalytic activity test result before and after the catalyst regeneration is listed in table 1.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 7%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 10%.
Embodiment 3
Implement with reference to embodiment 1, different is to handle 0.5 hour with the carbon hydrogen fluoride mixture that contains 10% volume hydrogen at 300 ℃ with embodiment 1.Absorption reaction tail gas is measured through the oxidimetric titration analytical method with wet method, does not detect Cr (VI) compound.The catalyst activity test result is listed in table 1 before and after the catalyst regeneration.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 8%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 10%.
Embodiment 4
Contain Cr with what coprecipitation made
3+, and
Co2+, In
3+, Ni
2+, Mg
2+, Zn
2+, Cd
2+After wherein a kind of 50ml catalyst is used the HF fluorination treatment, for being used in 3 30 ℃ of HF to CF
3CHCl
2Fluoridize synthetic CF
3CHF
2Catalyst in the gas-phase reaction loses catalytic activity until this catalyst.HF: CF wherein
3CHCl
2Mol ratio is 6: 1.
The catalyst regeneration process process is with catalyst regeneration process among the embodiment 1.Activity of such catalysts is listed in table 2 before and after the catalyst regeneration.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 5%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 12%.
Embodiment 5
Implement with reference to embodiment 4, different was with the HF mixture that contains 5% volume hydrogen 300 ℃ of fluorination treatment 0.5 hour with embodiment 4.Catalyst regeneration rear catalyst active testing the results are shown in table 2.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 8%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 12%.
Embodiment 6
Implement with reference to embodiment 4, different was with the HF mixture that contains 10% volume hydrogen 300 ℃ of fluorination treatment 0.5 hour with embodiment 4.Catalyst regeneration rear catalyst active testing the results are shown in table 2.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 8%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 12%.
Embodiment 7
Implement with reference to embodiment 5, different is that catalyst system therefor is that coprecipitation makes contains Cr with embodiment 5
3+And Co
2+, In
3+, Ni
2+, Mg
2+, Zn
2+, Cd
2+Two kinds 50ml catalyst wherein.Catalyst regeneration rear catalyst active testing the results are shown in table 3.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 4%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 15%.
Embodiment 8
The AlF that infusion process is made
3Load contains Cr
3+, and Co
2+, In
3+, Ni
2+, Mg
2+, Zn
2+, Cd
2+After wherein a kind of 50ml catalyst is used the HF fluorination treatment, for being used in 260 ℃ of HF to CH
2Cl
2Fluoridize synthetic CF
2Cl
2Catalyst in the gas-phase reaction loses catalytic activity until this catalyst.HF: CH wherein
2Cl
2Mol ratio is 6: 1.
Catalyst regeneration process is with catalyst regeneration process among the embodiment 1.Activity of such catalysts is listed in table 4 before and after the catalyst regeneration.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 10%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 20%.
Embodiment 9
Implement with reference to embodiment 8, different was with the HF mixture that contains 5% volume hydrogen 300 ℃ of fluorination treatment 0.5 hour with embodiment 8.Catalyst regeneration rear catalyst active testing the results are shown in table 4.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 9%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 20%.
Embodiment 10
Implement with reference to embodiment 8, different was with the HF mixture that contains 10% volume hydrogen 300 ℃ of fluorination treatment 0.5 hour with embodiment 8.Catalyst regeneration rear catalyst active testing the results are shown in table 4.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 8%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 20%.
Embodiment 11
The AlF that infusion process is made
3Load contains Cr
3+, and Co
2+, In
3+, Ni
2+, Mg
2+, Zn
2+, Cd
2+After wherein two kinds 50ml catalyst is used the HF fluorination treatment, for being used in 260 ℃ of HF to CH
2Cl
2Fluoridize synthetic CF
2Cl
2Catalyst in the gas-phase reaction loses catalytic activity until this catalyst.HF: CH wherein
2Cl
2Mol ratio is 6: 1.
Catalyst regeneration process is with catalyst regeneration process among the embodiment 8.Activity of such catalysts is listed in table 5 before and after the catalyst regeneration.Adopt renovation process regeneration of fluorination catalyst of the present invention to use continuously after 40 days, its conversion ratio descends 8%, and regenerates the continuous use of above-mentioned same fluorination catalyst after 20 days according to Chinese patent 97111149.9 renovation process, and its conversion ratio descends 10%.
Table 1
| Catalyst | Test condition | Conversion ratio/% | Selectivity/% | |
| Temperature/℃ | HF/CF 3CH 2Cl | |||
| Initial | ????350 | ????10/1 | ????18.5 | ????97.0 |
| Inactivation | ????350 | ????10/1 | ????10.2 | ????95.0 |
| Example 1 regeneration | ????350 | ????10/1 | ????19.0 | ????97.0 |
| Example 2 regeneration | ????350 | ????10/1 | ????20.2 | ????97.0 |
| Example 3 regeneration | ????350 | ????10/1 | ????19.3 | ????96.0 |
Table 2
| Catalyst | Test condition | Conversion ratio/% | Selectivity/% | |
| Temperature/℃ | HF/CF 3CHCl 2 | |||
| Initial | ????330 | ????6/1 | ????75.6 | ????99.5 |
| With what cross | ????330 | ????6/1 | ????35.0 | ????99.5 |
| Example 4 regeneration | ????330 | ????6/1 | ????78.0 | ????99.6 |
| Example 5 regeneration | ????330 | ????6/1 | ????81.5 | ????99.5 |
| Example 6 regeneration | ????330 | ????6/1 | ????82.0 | ????99.5 |
Selectivity is meant and generates CF
3CHFCl and CF
3CHF
2Summation.
Table 3
| Catalyst | Test condition | Conversion ratio/% | Selectivity/% | |
| Temperature/℃ | HF/CF 3CHCl 2 | |||
| Initial | ????330 | ????6/1 | ????75.6 | ????99.5 |
| With what cross | ????330 | ????6/1 | ????35.0 | ????99.5 |
| Example 7 regeneration | ????330 | ????6/1 | ????79.0 | ????99.4 |
Selectivity is meant and generates CF
3CHFCl and CF
3CHF
2Summation.
Table 4
| Catalyst | Test condition | Conversion ratio/% | Selectivity/% | |
| Temperature/℃ | ??HF/CH 2Cl 2 | |||
| Initial | ????260 | ????8/1 | ????85.0 | ????88.0 |
| With what cross | ????260 | ????8/1 | ????52.0 | ????80.0 |
| Example 8 regeneration | ????260 | ????8/1 | ????84.0 | ????87.0 |
| Example 9 regeneration | ????260 | ????8/1 | ????88.0 | ????89.0 |
| Example 10 regeneration | ????260 | ????8/1 | ????86.0 | ????89.0 |
Table 5
| Catalyst | Test condition | Conversion ratio/% | Selectivity/% | |
| Temperature/℃ | ??HF/CH 2Cl 2 | |||
| Initial | ????260 | ????8/1 | ????85.0 | ????88.0 |
| With what cross | ????260 | ????8/1 | ????52.0 | ????80.0 |
| Example 11 regeneration | ????260 | ????8/1 | ????85.5 | ????89.0 |
Claims (4)
1, a kind of method of regeneration of chromium-based fluorination catalyst, comprising following steps:
(1), deactivated chromium-based fluorination catalyst is handled, disappear until organic pollution at 300 ℃～500 ℃ mists with air and nitrogen;
(2), at 250 ℃～350 ℃ mists with the hydrogen of hydrogen fluoride and 1%～12% percent by volume, handle the catalyst of handling through step (1), absorption tail gas, detection is less than Cr (VI) compound;
(3), at 300 ℃～350 ℃ catalyst of handling by step (2) with hydrogen fluoride trealment.
2, method according to claim 1, wherein the chromium base is Cr (III) oxide and/or oxygen fluoride, is to be made by infusion process, carrier is selected from AlF
3, Al
2O
3, MgO, MgF
2, fluoridize Al
2O
3
3, method according to claim 1, wherein catalyst is by being stated from AlF
3, Al
2O
3, MgO, fluoridize Al
2O
3On Cr (III) oxide and/or oxygen fluoride and Co
2+, Mg
2+In
3+, Zn
2+, Ni
2+, Cd
2+One or more metals are wherein formed.
4, method according to claim 1, wherein step (2) temperature is 300 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101015528A CN100372611C (en) | 2004-12-23 | 2004-12-23 | Regeneration method of fluorine catalyst with chromium base |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101015528A CN100372611C (en) | 2004-12-23 | 2004-12-23 | Regeneration method of fluorine catalyst with chromium base |
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| Publication Number | Publication Date |
|---|---|
| CN1651144A true CN1651144A (en) | 2005-08-10 |
| CN100372611C CN100372611C (en) | 2008-03-05 |
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ID=34869627
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894219A (en) * | 2014-04-11 | 2014-07-02 | 太仓中化环保化工有限公司 | Fluorination catalyst regeneration method |
| CN103896721A (en) * | 2014-04-11 | 2014-07-02 | 太仓中化环保化工有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane |
| CN106582729A (en) * | 2016-12-21 | 2017-04-26 | 山东华安新材料有限公司 | Treatment method of chromium-containing waste catalyst |
| CN107376953A (en) * | 2017-08-03 | 2017-11-24 | 乳源东阳光氟有限公司 | A kind of recovery method of useless chromium-based fluorination catalyst |
| CN107670701A (en) * | 2017-10-16 | 2018-02-09 | 乳源东阳光氟有限公司 | A kind of renovation process of fluorination catalyst |
| CN107899585A (en) * | 2017-10-27 | 2018-04-13 | 乳源东阳光氟有限公司 | A kind of renovation process of fluorination catalyst |
| JP2019500359A (en) * | 2015-12-14 | 2019-01-10 | アルケマ フランス | Vapor phase catalytic fluorination using chromium catalyst |
| CN109482244A (en) * | 2018-11-09 | 2019-03-19 | 三明学院 | Catalyst regeneration process is used in a kind of R125 production |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044095C (en) * | 1990-09-14 | 1999-07-14 | 帝国化学工业公司 | Process for regeneration of fluorination catalyst |
| JP3248923B2 (en) * | 1991-05-29 | 2002-01-21 | 昭和電工株式会社 | Activation regeneration method of chromium-based fluorination catalyst and method of producing halogenated hydrocarbon |
| DE4419534C1 (en) * | 1994-06-03 | 1995-10-19 | Hoechst Ag | Process for the regeneration of a chromium- and magnesium-containing fluorination catalyst |
| IT1282961B1 (en) * | 1996-05-06 | 1998-04-02 | Ausimont Spa | PROCESS FOR THE REGENERATION OF A CATALYST BASED ON TRIVALENT CHROME COMPOUNDS |
-
2004
- 2004-12-23 CN CNB2004101015528A patent/CN100372611C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894219A (en) * | 2014-04-11 | 2014-07-02 | 太仓中化环保化工有限公司 | Fluorination catalyst regeneration method |
| CN103896721A (en) * | 2014-04-11 | 2014-07-02 | 太仓中化环保化工有限公司 | Preparation method of 1,1,1,2-tetrafluoroethane |
| JP2019500359A (en) * | 2015-12-14 | 2019-01-10 | アルケマ フランス | Vapor phase catalytic fluorination using chromium catalyst |
| CN106582729A (en) * | 2016-12-21 | 2017-04-26 | 山东华安新材料有限公司 | Treatment method of chromium-containing waste catalyst |
| CN107376953A (en) * | 2017-08-03 | 2017-11-24 | 乳源东阳光氟有限公司 | A kind of recovery method of useless chromium-based fluorination catalyst |
| CN107376953B (en) * | 2017-08-03 | 2020-04-21 | 乳源东阳光氟有限公司 | Method for recovering waste chromium-based fluorination catalyst |
| CN107670701A (en) * | 2017-10-16 | 2018-02-09 | 乳源东阳光氟有限公司 | A kind of renovation process of fluorination catalyst |
| CN107670701B (en) * | 2017-10-16 | 2018-10-16 | 乳源东阳光氟有限公司 | A kind of regeneration method of fluorination catalyst |
| CN107899585A (en) * | 2017-10-27 | 2018-04-13 | 乳源东阳光氟有限公司 | A kind of renovation process of fluorination catalyst |
| CN107899585B (en) * | 2017-10-27 | 2019-10-18 | 乳源东阳光氟有限公司 | A kind of regeneration method of fluorination catalyst |
| CN109482244A (en) * | 2018-11-09 | 2019-03-19 | 三明学院 | Catalyst regeneration process is used in a kind of R125 production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100372611C (en) | 2008-03-05 |
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