CN103894219B - The renovation process of fluorination catalyst - Google Patents
The renovation process of fluorination catalyst Download PDFInfo
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- CN103894219B CN103894219B CN201410144067.2A CN201410144067A CN103894219B CN 103894219 B CN103894219 B CN 103894219B CN 201410144067 A CN201410144067 A CN 201410144067A CN 103894219 B CN103894219 B CN 103894219B
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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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- Y02P20/584—Recycling of catalysts
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Abstract
The present invention relates to a kind of renovation process of fluorination catalyst, it comprises high-temperature blowing operation, high temperature regeneration operation, no-load voltage ratio step for regeneration and high-pressure regeneration operation, wherein high-temperature process purges high temperature catalyst by high temperature nitrogen, and high temperature regeneration operation is regenerated catalyst by the mist of the gas that can react with carbon containing small amount; No-load voltage ratio step for regeneration be constantly increase reacting gas in mist at ambient pressure content to regenerate catalyst; High-pressure regeneration operation is that mist is regenerated catalyst under ever-increasing regenerating system environmental pressure.Can by the activation recovering of catalyst to initial activity according to the inventive method.
Description
Technical field
The present invention relates to the renovation process of the fluorination catalyst for fluoric ether preparation technology.
Background technology
HFA 134a (HFC-134a) and pentafluoroethane (HFC-125) belong to ODS(ODS) substitute, belong to environmental protection novel refrigerant.HFA 134a (HFC-134a) and pentafluoroethane (HFC-125) by HF and alkenyl halide under catalysis of solid catalyst effect, can carry out reacting and obtain under certain temperature, pressure and the condition of time of contact.Chinese invention patent ZL01141970.9 discloses a kind of fluorination catalyst that can be used for HFA 134a and prepare, and this fluorination catalyst structural formula is CrX
0.005-0.5y
0.005-0.3o
0.1-1.0f
1.0-3.0, wherein X is Mn, Co or Zn, and Y is Mg or Ni.This catalyst has active high, good stability, the advantages such as long service life.But because of the reason such as alkane, chloralkane compounds high temperature cabonization generated after alkenyl halide or reaction, this catalyst in use for some time catalytic efficiency reduces even inactivation.The conventional regeneration method of metallic catalyst is that catalyst is contacted certain hour at a certain temperature with regeneration gas such as air or oxygen etc.This renovation process is better for the regeneration effect of most metals catalyst, but for having the fluorination catalyst of described structure, regeneration effect is unsatisfactory, and the activity of the catalyst after regeneration only can reach 50% ~ 60% of fresh catalyst.In addition, also also exist and make fluorination catalyst specific area on the low side and cause the catalytic activity of catalyst to decay fast, the problem such as target product selectivity is low.Therefore, be necessary to provide a kind of renovation process being suitable for above-mentioned fluorination catalyst.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of renovation process of fluorination catalyst.
For solving above technical problem, the present invention takes following technical scheme:
A renovation process for fluorination catalyst, the structural formula of described fluorination catalyst is CrX
0.005-0.5y
0.005-0.3o
0.1-1.0f
1.0-3.0, wherein X is Mn, Co or Zn, and Y is Mg or Ni, and described renovation process comprises the steps:
(1) high-temperature blowing operation: fluorination catalyst is added in fixed bed reactors, be heated to 250 ~ 400 DEG C, continue to pass into the nitrogen that pressure is 0.1 ~ 0.9MPa, temperature is 250 ~ 400 DEG C to purge fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 0.01 second to 1 hour;
(2) high temperature regeneration operation: after completing high-temperature blowing operation, continues under normal pressure to pass into the first regeneration gas that temperature is 250 ~ 400 DEG C, and this first regeneration gas contains nitrogen and is selected from O
2, O
3, N
2at least one in O, wherein O
2, O
3, N
2the volume ratio sum of O is 2% ~ 12%, and the time of contact controlling the first regeneration gas and fluorination catalyst is 0.01 second to 1 hour;
(3) no-load voltage ratio step for regeneration: controlling fluorination catalyst temperature is 250 ~ 400 DEG C, continues to pass into the second regeneration gas that temperature is 250 ~ 400 DEG C under normal pressure, the second regeneration gas contains nitrogen and is selected from O
2, O
3, N
2at least one in O, the time of contact controlling the second regeneration gas and fluorination catalyst is 0.01 second to 1 hour, O in described second regeneration gas
2, O
3, N
2o volume ratio sum progressively increases with the increase passing into the time, starts O in the second regeneration gas passed into most
2, O
3, N
2o volume ratio sum is 2% ~ 12%, O in the second regeneration gas finally passed into
2, O
3, N
2o volume ratio sum is 5% ~ 25%;
(4) high-pressure regeneration operation: controlling fluorination catalyst temperature is 250 ~ 400 DEG C, continues to pass into the 3rd regeneration gas that temperature is 250 ~ 400 DEG C, O in the 3rd regeneration gas
2, O
3, N
2o volume ratio sum is 2% ~ 25%, the time of contact controlling the 3rd regeneration gas and fluorination catalyst is 0.01 second to 1 hour, initial pressure in fixed bed reactors is normal pressure, passes into the increase of time progressively rise to 0.15 ~ 0.5MPa with the 3rd regeneration gas, then maintains more than 20 hours.
Preferably, in step (1), the time of contact controlling nitrogen and catalyst is 15 ~ 40 minutes.
Preferably, described first regeneration gas is mixed by nitrogen and air or oxygen,
Preferably, in step (2), the time of contact controlling the first regeneration gas and fluorination catalyst is 15 ~ 40 minutes.
Preferably, in step (3), described second regeneration gas is mixed by nitrogen and air or oxygen.
Preferably, in step (3), in the process passing into the second regeneration gas, the temperature of fluorination catalyst is tested, control O in described second regeneration gas
2, O
3, N
2gathering way of O volume ratio sum, ensures that the fluctuation of the temperature of fluorination catalyst is no more than 10 DEG C.
According to the present invention, step (3) and step (4) are carried out after step (2), carry out or carry out simultaneously between step (3) and step (4) after an elder generation one.
Preferably, step (3) is carried out after step (2), before step (4).
Preferably, in step (3), O in the second regeneration gas passed into is started most
2, O
3, N
2o volume ratio sum is 5% ~ 10%, O in the second regeneration gas finally passed into
2, O
3, N
2o volume ratio sum is 15% ~ 25%.
Preferably, in step (4), O in described 3rd regeneration gas
2, O
3, N
2o volume ratio sum is 15% ~ 25%.
Preferably, in step (4), the 3rd regeneration gas is mixed by nitrogen and air or oxygen.
Preferably, in step (4), the pressure in fixed bed reactors progressively rises to 0.2 ~ 0.4MPa from normal pressure.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Adopt the inventive method successfully can realize the regeneration of fluorination catalyst, fluorination catalyst after regeneration is the active level that can return to fresh catalyst not only, and in catalyst activation process, prevent sintering phenomenon to occur, increasing specific surface area and pore volume greatly, thus catalyst activity is high, good stability, other character such as mechanical performance is kept all very well.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.The implementation condition adopted in embodiment can require to do further adjustment according to the concrete difference used, and not marked implementation condition is the condition in normal experiment.
The old fluorination catalyst used in following examples prepares according to ZL01141970.9 method and is used in the fluorination catalyst after producing 134a a period of time, and its structural formula is CrMn
0.3mg
0.1o
0.5f
2.0.
Embodiment 1
Quantitative old fluorination catalyst is loaded fixed bed reactors, then carries out the regeneration of catalyst successively as follows:
(1) high-temperature blowing operation: fluorination catalyst is heated to 300 DEG C, continue to pass into the nitrogen that pressure is 0.5MPa, temperature is 300 DEG C to purge fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 0.5 hour, and duration of ventilation is 30 hours;
(2) high temperature regeneration operation: after completing high-temperature blowing operation, continue under normal pressure to pass into the first regeneration gas that temperature is 300 DEG C, this first regeneration gas by nitrogen and air in mass ratio 1:1 mix, control 1 hour time of contact of the first regeneration gas and fluorination catalyst, duration of ventilation is 40 hours;
(3) no-load voltage ratio step for regeneration: controlling fluorination catalyst temperature is 300 DEG C, continue under normal pressure to pass into the second regeneration gas that temperature is 300 DEG C, the time of contact controlling the second regeneration gas and catalyst is 1 hour, second regeneration gas is mixed by nitrogen and air, and the mixed proportion both progressively changing, the ratio starting most nitrogen and air in the second regeneration gas passed into is 1:1, progressively improve the ratio of air, be extremely finally all air, in the process, the temperature of catalyst is detected, control gathering way of AIR Proportional, ensure that the temperature fluctuation of catalyst is no more than 10 DEG C,
(4) high-pressure regeneration operation: controlling fluorination catalyst temperature is 300 DEG C, continue to pass into the 3rd regeneration gas that temperature is 300 DEG C, 3rd regeneration gas is all air, the time of contact controlling the 3rd regeneration gas and fluorination catalyst is 1 hour, initial pressure in fixed bed reactors is normal pressure, pass into the increase of time with the 3rd regeneration gas and progressively rise to 0.4MPa, maintain 20 hours, complete the regeneration of fluorination catalyst.
Embodiment 2
Quantitative old fluorination catalyst is loaded fixed bed reactors, then carries out the regeneration of catalyst successively as follows:
(1) high-temperature blowing operation: fluorination catalyst is heated to 300 DEG C, continue to pass into the nitrogen that pressure is 0.1MPa, temperature is 300 DEG C to purge fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 0.5 hour, and duration of ventilation is 30 hours;
(2) high temperature regeneration operation: after completing high-temperature blowing operation, continue under normal pressure to pass into the first regeneration gas that temperature is 300 DEG C, this first regeneration gas by nitrogen and air in mass ratio 1:1 mix, control 0.5 hour time of contact of the first regeneration gas and fluorination catalyst, duration of ventilation is 20 hours;
(3) no-load voltage ratio step for regeneration: controlling fluorination catalyst temperature is 300 DEG C, continue under normal pressure to pass into the second regeneration gas that temperature is 300 DEG C, the time of contact controlling the second regeneration gas and catalyst is 0.5 hour, second regeneration gas is formed by nitrogen and oxygen mix, and the mixed proportion both progressively changing, the ratio starting most nitrogen and oxygen in the second regeneration gas passed into is 10:1, progressively improve the ratio of oxygen, ratio to last nitrogen and oxygen is 3:1, in the process, the temperature of catalyst is detected, control gathering way of AIR Proportional, ensure that the temperature fluctuation of catalyst is no more than 10 DEG C,
(4) high-pressure regeneration operation: controlling fluorination catalyst temperature is 300 DEG C, continue to pass into the 3rd regeneration gas that temperature is 300 DEG C, 3rd regeneration gas is all air, the time of contact controlling the 3rd regeneration gas and fluorination catalyst is 1 hour, initial pressure in fixed bed reactors is normal pressure, pass into the increase of time with the 3rd regeneration gas and progressively rise to 0.4MPa, maintain 20 hours, complete the regeneration of fluorination catalyst.
Embodiment 3
Quantitative old fluorination catalyst is loaded fixed bed reactors, then carries out the regeneration of catalyst successively as follows:
(1) high-temperature blowing operation: fluorination catalyst is heated to 200 DEG C, continue to pass into the nitrogen that pressure is 0.1MPa, temperature is 200 DEG C to purge fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 15 minutes, and duration of ventilation is 30 hours;
(2) high temperature regeneration operation: after completing high-temperature blowing operation, continue under normal pressure to pass into the first regeneration gas that temperature is 200 DEG C, this first regeneration gas by nitrogen and air in mass ratio 1:1 mix, control 15 minutes times of contact of the first regeneration gas and fluorination catalyst, duration of ventilation is 10 hours;
(3) no-load voltage ratio step for regeneration: controlling fluorination catalyst temperature is 200 DEG C, continue under normal pressure to pass into the second regeneration gas that temperature is 200 DEG C, the time of contact controlling the second regeneration gas and catalyst is 40 minutes, second regeneration gas is formed by nitrogen and oxygen mix, and the mixed proportion both progressively changing, the ratio starting most nitrogen and oxygen in the second regeneration gas passed into is 10:1, progressively improve the ratio of oxygen, ratio to last nitrogen and oxygen is 3:1, in the process, the temperature of catalyst is detected, control gathering way of AIR Proportional, ensure that the temperature fluctuation of catalyst is no more than 10 DEG C,
(4) high-pressure regeneration operation: controlling fluorination catalyst temperature is 200 DEG C, continue to pass into the 3rd regeneration gas that temperature is 200 DEG C, 3rd regeneration gas is all air, the time of contact controlling the 3rd regeneration gas and fluorination catalyst is 0.5 hour, initial pressure in fixed bed reactors is normal pressure, pass into the increase of time with the 3rd regeneration gas and progressively rise to 0.3MPa, maintain 20 hours, complete the regeneration of fluorination catalyst.
Embodiment 4
Quantitative old fluorination catalyst is loaded fixed bed reactors, then carries out the regeneration of catalyst successively as follows:
(1) high-temperature blowing operation: fluorination catalyst is heated to 300 DEG C, continue to pass into the nitrogen that pressure is 0.5MPa, temperature is 300 DEG C to purge fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 0.5 hour, and duration of ventilation is 30 hours;
(2) high temperature regeneration operation: after completing high-temperature blowing operation, continue under normal pressure to pass into the first regeneration gas that temperature is 300 DEG C, this first regeneration gas by nitrogen and air in mass ratio 1:1 mix, control 1 hour time of contact of the first regeneration gas and fluorination catalyst, duration of ventilation is 40 hours;
(3) high-pressure regeneration operation: controlling fluorination catalyst temperature is 300 DEG C, continue to pass into the 3rd regeneration gas that temperature is 300 DEG C, 3rd regeneration gas is all air, the time of contact controlling the 3rd regeneration gas and fluorination catalyst is 1 hour, initial pressure in fixed bed reactors is normal pressure, pass into the increase of time with the 3rd regeneration gas and progressively rise to 0.4MPa, maintain 20 hours;
(4) no-load voltage ratio step for regeneration: controlling fluorination catalyst temperature is 300 DEG C, continue under normal pressure to pass into the second regeneration gas that temperature is 300 DEG C, the time of contact controlling the second regeneration gas and catalyst is 1 hour, second regeneration gas is mixed by nitrogen and air, and the mixed proportion both progressively changing, the ratio starting nitrogen and air in the second regeneration gas passed into most is 1:1, progressively improves the ratio of air, to being all finally air, complete the regeneration of catalyst.
Comparative example 1
Traditionally catalyst recovery process regenerates old catalyst, specific as follows:
(1) quantitative old fluorination catalyst is loaded fixed bed reactors, be heated to 300 DEG C, continue to pass into the nitrogen that pressure is 0.1MPa, temperature is 300 DEG C to purge fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 0.5 hour, and duration of ventilation is 30 hours;
(2) continue under normal pressure to pass into the air that temperature is 300 DEG C, control 2 hours times of contact of air and fluorination catalyst, duration of ventilation is 40 hours, completes the regeneration of catalyst.
Fluorination catalyst after above-mentioned regeneration is applied to respectively and prepares HFA 134a (HFC-134a), evaluate the conversion ratio of alkenyl halide, the selective of reaction in catalytic reaction.
1. application process is as follows:
Get the fluorination catalyst 50ml after above-mentioned regeneration respectively to load in the nickel pipe bed bioreactor of the Ф 19x2 of fused salt heating, carry out following two-step reaction:
(1)3HF+CCl
2=CHCl→CF
3CH
2Cl+2HCl
(2)3HF+CF
3CH
2Cl→CF
3CH
2F+HCl
Wherein:
(1) anhydrous hydrogen fluoride (HF) and trichloro-ethylene are the ingredient proportion continuous dosing of 10:1 in molar ratio, and controlling reaction temperature is 280 ± 5 DEG C, and volume space velocity is 1320/h;
(2) anhydrous hydrogen fluoride and HCFC-133a are the ingredient proportion continuous dosing of 4.5:1 in molar ratio, and controlling reaction temperature is 350 ± 5 DEG C, and volume space velocity is 1320/h.
2. result is see table 1.
Table 1
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; the equivalence change that all Spirit Essences according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (10)
1. a renovation process for fluorination catalyst, the structural formula of described fluorination catalyst is CrX
0.005-0.5y
0.005-0.3o
0.1-1.0f
1.0-3.0, wherein X is Mn, Co or Zn, and Y is Mg or Ni, it is characterized in that: described renovation process comprises the steps:
(1) high-temperature blowing operation: described fluorination catalyst is added in fixed bed reactors, be heated to 250 ~ 400 DEG C, continue to pass into the nitrogen that pressure is 0.1 ~ 0.9MPa, temperature is 250 ~ 400 DEG C to purge described fluorination catalyst, the time of contact wherein controlling nitrogen and catalyst is 15 minutes to 1 hour;
(2) high temperature regeneration operation: after completing high-temperature blowing operation, continues under normal pressure to pass into the first regeneration gas that temperature is 250 ~ 400 DEG C, and this first regeneration gas contains nitrogen and is selected from O
2, O
3, N
2at least one in O, wherein O
2, O
3, N
2the volume ratio sum of O is 2% ~ 12%, and the time of contact controlling the first regeneration gas and fluorination catalyst is 15 minutes to 1 hour;
(3) no-load voltage ratio step for regeneration: controlling fluorination catalyst temperature is 250 ~ 400 DEG C, continues to pass into the second regeneration gas that temperature is 250 ~ 400 DEG C under normal pressure, described second regeneration gas contains nitrogen and is selected from O
2, O
3, N
2at least one in O, the time of contact controlling the second regeneration gas and fluorination catalyst is 0.5 little of 1 hour, O in described second regeneration gas
2, O
3, N
2o volume ratio sum progressively increases with the increase passing into the time, starts O in the second regeneration gas passed into most
2, O
3, N
2o volume ratio sum is 2% ~ 12%, O in the second regeneration gas finally passed into
2, O
3, N
2o volume ratio sum is 5% ~ 25%;
(4) high-pressure regeneration operation: controlling fluorination catalyst temperature is 250 ~ 400 DEG C, continues to pass into the 3rd regeneration gas that temperature is 250 ~ 400 DEG C, O in described 3rd regeneration gas
2, O
3, N
2o volume ratio sum is 2% ~ 25%, the time of contact controlling the 3rd regeneration gas and fluorination catalyst is 0.5 little of 1 hour, initial pressure in described fixed bed reactors is normal pressure, pass into the increase of time with the 3rd regeneration gas and progressively rise to 0.15 ~ 0.5MPa, then maintain more than 20 hours.
2. the renovation process of fluorination catalyst according to claim 1, is characterized in that: in step (1), and the time of contact controlling nitrogen and catalyst is 15 ~ 40 minutes.
3. the renovation process of fluorination catalyst according to claim 1, is characterized in that: in step (2), and described first regeneration gas is mixed by nitrogen and air or oxygen.
4. the renovation process of fluorination catalyst according to claim 1, is characterized in that: in step (2), and the time of contact controlling the first regeneration gas and fluorination catalyst is 15 ~ 40 minutes.
5. the renovation process of fluorination catalyst according to claim 1, is characterized in that: in step (3), and described second regeneration gas is mixed by nitrogen and air or oxygen.
6. the renovation process of fluorination catalyst according to claim 1, is characterized in that: in step (3), in the process passing into the second regeneration gas, test the temperature of fluorination catalyst, controls O in described second regeneration gas
2, O
3, N
2gathering way of O volume ratio sum, ensures that the fluctuation of the temperature of fluorination catalyst is no more than 10 DEG C.
7. the renovation process of fluorination catalyst according to claim 1, it is characterized in that: step (3) and step (4) are carried out after step (2), carry out after an elder generation one between step (3) and step (4).
8. the renovation process of fluorination catalyst according to claim 7, is characterized in that: step (3) is carried out after step (2), before step (4).
9. the renovation process of the fluorination catalyst according to claim 7 or 8, is characterized in that: in step (3), start O in the second regeneration gas passed into most
2, O
3, N
2o volume ratio sum is 5% ~ 12%, O in the second regeneration gas finally passed into
2, O
3, N
2o volume ratio sum is 15% ~ 25%.
10. the renovation process of fluorination catalyst according to claim 8, is characterized in that: in step (4), O in described 3rd regeneration gas
2, O
3, N
2o volume ratio sum is 15% ~ 25%.
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| CN105457688A (en) * | 2015-12-16 | 2016-04-06 | 七台河宝泰隆圣迈煤化工有限责任公司 | Catalyst regeneration method |
| 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 |
| 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 |
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| CN1044095C (en) * | 1990-09-14 | 1999-07-14 | 帝国化学工业公司 | Process for regeneration of fluorination catalyst |
| 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 |
| CN100372611C (en) * | 2004-12-23 | 2008-03-05 | 西安近代化学研究所 | Regeneration method of fluorine catalyst with chromium base |
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