CN1044095C - Method for regenerating fluorination catalysts - Google Patents
Method for regenerating fluorination catalysts Download PDFInfo
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- CN1044095C CN1044095C CN 91109551 CN91109551A CN1044095C CN 1044095 C CN1044095 C CN 1044095C CN 91109551 CN91109551 CN 91109551 CN 91109551 A CN91109551 A CN 91109551A CN 1044095 C CN1044095 C CN 1044095C
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Abstract
The present invention discloses a method for regenerating a used fluorating catalyst, such as a chromium-containing compound, which comprises: the used catalyst is in contact with a mixture of an oxidizing agent (particularly air), hydrogen fluoride and a selectively added inert diluted agent (such as nitrogen), and the mixture comprises an oxidizing agent less than 30% in mole percentage. The method eliminates the loss of chromium in the process of waste catalyst regeneration and re-fluorination, and thermal hydrogen fluoride which can be directly used for a fluorination reaction is provided.
Description
The present invention relates to a kind of chemical method, or rather, relate to a kind of method of regeneration of fluorination catalyst.
As everyone knows, hydrogen fluoride and various organic compound reaction are in order to introduce one or more fluorine atoms.For example, known hydrogen fluoride and trichloro-ethylene or 1,1, the purpose of 1-three fluoro-2-chloroethanes reaction is preparation 1,1,1,2-HFC-134a (HFA 134a).
In these reactions, be to use a kind of fluorination catalyst traditionally; Introduced the such catalyst of several classes in the prior art.Regrettably, these catalyst are active variation in fluorination process, and this useless or used catalyst is handled through regeneration.This processing generally will relate to used catalyst is contacted with air, to burn organic impurities.This operation height heat release, and, supply air through diluent control commonly used for sending out the cooling system of avoiding costliness and can using the heat-insulating catalyst bed; Nitrogen is commonly used for this diluent.After this method use, nitrogen is discharged in the atmosphere, but the organic impurities that exists can cause problem of environmental pollution.
Have now found that, use air or other oxidant and the hydrofluoric mixture useless fluorination catalyst of can regenerating easily, and the gas after the regeneration of fluorinated hydrogen still can be used for the fluorine reaction.
For for simplicity, below only the present invention is described, but should be noted that the oxygen containing oxidant of any bag all can be used to replaces air with air oxidant.
The invention provides a kind of renovation process that is used for fluorination reaction fluorination catalyst afterwards, described method comprises: at 300-500 ℃, the mixture of described used catalyst and a kind of air and hydrogen fluoride and optional inert diluent is contacted, contain the air of as many as 30% (in mole) in the described mixture.
Specifically, the catalyst for reaction that can use the fluorination catalyst of the inventive method regeneration to comprise to be used for catalytic fluorination hydrogen to be carried out for hydrocarbon, especially chloro-alkenes (as trichloro-ethylene) or chloralkane (as 1,1,1-three fluoro-2-chloroethanes) with fontanel.Suitable fluorination catalyst is fully introduced in the prior art, and they comprise various inorganic compounds, for example especially the metal oxide and the fontanelle compound of chromium and so on of aluminium, cobalt, manganese, iron.Suitable chromium-containing catalyst comprises its oxide, hydroxide, fontanelle compound, fontanel oxide, inorganic acid salt, alkali formula charomic fluoride, and the catalyst of introducing in the applicant's BP 1,307,224.
Whether the composition that is used for the mixture of regenerated catalyst comprises diluent (as nitrogen) according to mixture to a great extent and changes in wide region.If there is not the diluent of nitrogen and so in the mixture, then hydrogen fluoride accounts for 70% (in mole) of mixture at least, and hydrofluoric content is preferably 70%-99.9% (in mole).If have diluent in the mixture, then hydrogen fluoride and diluent summation account for 70% (in mole) of mixture at least, and hydrofluoric content preferably makes the mol ratio of hydrogen fluoride and air be at least 0.1: 1.So the contained hydrogen fluoride and the mol ratio of air were at least 0.1: 1 in the mixture, preferably were at least 1: 1, the best was at least 2: 1, for example 2-100: 1.In general, the mol ratio of hydrogen fluoride and air reduces with the raising of amount of diluent.
The preferred type that also depends on the catalyst system therefor bed to a certain extent of forming.For adiabatic reactor, preferably contain the air/HF mixture of the following air of 10% (in mole), typical mixture contains 2% air approximately.For the pipe cooling reactor, can bear air up to the high level of 30% (in mole).
The diluent mixture that air/hydrogen fluoride/choosing adds also can contain organic matters, for example accounts for (in the mole) below 1% of the product of initial substance and/or intermediate and/or flaorination process.For example, hydrogen fluoride and/or diluent thus can be from the product recirculation of fluorination reaction.
Handle useless sustainable as required a period of time of catalyst with air/HF/ diluent mixture, so that the regeneration of catalyst reaches satisfied degree; Preferred treatment temperature is 330-450 ℃.Then, the gas of having regenerated preferably needn't cool off and be recycled in the fluorination reactor, or is used for another fluorination reaction.
In the method for prior art, generally to make the catalyst of regeneration before it reenters fluorination reaction, carry out pre-fluorination treatment.An advantage of catalyst recovery process of the present invention is because renovation process uses hydrogen fluoride, to need not to carry out extra pre-fluorination treatment.Another advantage of the inventive method is, owing to avoided these needs of catalyst of pre-fluorination treatment regeneration at least in part, in the regeneration of catalyst and introduce in the operation and Cr (III) compound oxidation becomes in volatile poisonous Cr (VI) compound process, the remarkable loss occurrence of Chrome-free, so the shortcoming of the catalyst regeneration method of many prior aries has been eliminated, and has perhaps reduced at least to greatest extent.
In a preferred embodiment of the invention, but the mixture of hydrogen fluoride and fluoride alternately be added in two catalyst beds that are arranged in parallel, untapped that bed carries out method of reproduction of the present invention.
Below further specify the present invention with non-limiting embodiment.
Embodiment 1
Be used for by fluoridizing 1,1,1-three fluoro-2-chloroethanes make 1,1,1, and the chromium oxide fluorination catalyst after the method for 2-HFC-134a is heated to 400 ℃ under hydrofluoric atmosphere, last 2 hours.Under 400 ℃, with 50: 1 molar mixtures of hydrogen fluoride and air on catalyst by 6 hours.In catalyst bed, observe about 50 ℃ of temperature rise.
When regenerative response is finished, end air stream, and with catalyst with being cooled to the suitable temperature of fluoridizing in 2 hours.
Embodiment 2
200 gram chromium oxide-based catalyst samples are added in the Inconel reactor that is contained in 2 inch diameters in the stove.Catalyst is heated to 350 ℃, and be exposed to mol ratio be 1: 3.5 1,1-two chloro-2,2, in 2-HFC-143a (133a) and the HF charging 16 hours.Come the gas of autoreactor to feed in the moisture washer in batches, and the chromium layer in the washer is carried out the analysis of total chrome content with atomic absorption analysis.After 16 hours, do not detect chromium in the scrubber, see Table 1 sample 1.
Termination 133a and HF are reinforced after 16 hours, the reactor nitrogen purge, and be heated to 400 ℃.Change the water of washer, add 20: 1 molar mixtures of HF and air then in the reactor.Come the product of autoreactor to feed water scrubber, and press preceding method and analyze the interior chromium content of washer.Measure in preceding 16 hours regenerative processes the total chrome content of accumulation in the washer, find not detect chromium, see Table 1 sample 2.In further studying, pressed the preceding method regenerated catalyst 72 hours rather than 16 hours, in washer, do not detect chromium yet, see sample 3.
Afterwards, make method of the present invention and traditional regeneration and fluoridize series again and compare.This regeneration series at first is included in heatable catalyst in the air, then with HF fluorination treatment more separately.Find that the catalyst exposure of air regenesis can make chromium loss reach high level down to HF, see sample 5 and 6 and comparative studies usefulness sample 7 and 8, sample 6 and 8 has adopted different HF flow rate (representing time of contact with catalyst).
After reaction a period of time (seeing sample 9), carry out two examples of the air regenesis of nitrogen dilution, their typical example is sample 10 and 11 and 12 and 13.Lose sizable chromium amount from catalyst charge.
Final reaction (is seen sample 14) after the stage, carries out one group of HF under high flow rate and short contacting time condition: the regenerative response of air.It is very low again to observe the chromium loss amount, and both having made under the highest flow velocity also is (seeing sample 15-18) like this.
At last, 1: 1 low HF: air ratio shows that chromium is lost in low HF: hand over very significantly under the air ratio condition (seeing sample 19).
Table 1
* in order to compare
| Sample | Charging | Time of contact (second) | Temperature ℃ | Time (hour) | Chromium loss (gram) |
| 1 2 3 4 * 5 * 6 * 7 * 8 9 *10 *11 *12 *13 14 15 16 17 18 19 | 133a: HF1: 3.5 HF: 20: 1 HF of air: 20: 1 133a of air: HF1: 3.5 air HF air HF 133a: HF1: 3.5 N2: 10: 1 HF N2 of air: 10: 1 HF 133a: HF1 of air: 3.5 HF: 20: 1 HF of air: 20: 1 HF of air: 20: 1 HF of air: 20: 1 HF of air: air 1: 1 | 159 181 181 159 410 205 410 20 173 37 20 35 20 173 181 90 45 30 90 | 350 400 400 350 350 350 350 350 300 350 350 400 350 300 400 400 400 400 400 | 16 16 72 16 18 16 18 4 8 16 2 16 2 16 16 23 23 23 23 | 0.000 0.000 0.000 0.000 0.000 0.187 0.002 0.321 0.000 0.005 0.465 0.006 0.220 0.000 0.000 0.001 0.000 0.000 0.010 |
Embodiment 3
10kg chromium oxide fluorination catalyst is added in the salt cooling reactor of 2 inch diameters.By at 300 ℃ of logical 5kg HF finishing catalyst, then in the HF charging, add 133a, obtain 3.0: 1HF: the molar feed ratio of 133a.Pressing with regard to reactor is 13 Barks, catalyst temperature is brought up to 320 ℃, to reach the 12% purpose conversion ratio to 134a by 133a.Under reaction condition, be about 10 seconds time of contact in the reactor.Along with the catalyst deactivation, improve the reactor temperature, to keep the reaction yield of 12%134a.After operating 90 hours, catalyst is deactivation, turns off the 133a charging.Reactor is heated to 380 ℃, and catalyst cleans in the HF charging simultaneously.
Then, air is added in the HF charging, so that the HF that mixes: the air molar feed ratio is 40: 1.Stop air feed and reactor drop to 300 ℃ before regenerated catalyst 16 hours with this understanding.Restart the 133a charging, to obtain 3: 1 original HF: the molar feed ratio of 13a.In the time must keeping the 12%134a productive rate, improve catalyst temperature again.HF: the operating time is 92 hours behind the air regenesis.Repeat this reaction and HF/ air regenesis operation 3 times again.
Then, make according to the long HF that records of the postorder stage of reaction: the efficient of air regenesis method and nitrogen: the comparing of air regenesis method.In the 5th after operating period, regenerate in 380 ℃ again, but substitute HF stream to form 40: 1 N with the nitrogen that waits molar flow
2: Air mixing.Regenerate after 16 hours, make the temperature of catalyst be reduced to 300 ℃, fluoridize again with HF, and add 133a as stated above.From the result of table 2 as seen, cycle operating time of observing catalyst is being adopted N
2: descend gradually during the air regenesis method.
Table 2
Cycle operating time
(hour) new catalyst 90HF: method of reproduction 1 92HF after the air: method of reproduction 2 100HF after the air: method of reproduction 3 100HF after the air: method of reproduction 4 100 compares N after the air
2: method of reproduction 5 93N after the air
2: method of reproduction 6 54N after the air
2: method of reproduction 7 66N after the air
2: method of reproduction 8 47N after the air
2: method of reproduction 9 36N after the air
2: method of reproduction 10 22N after the air
2: method of reproduction 11 21 after the air
Embodiment 4
The 10kg catalyst is added to adiabatic reactor.Adopt the nitrogen that supplies preheating so that the temperature of adiabatic reactor inner catalyst is brought up to 250 ℃.Press the method for embodiment 3 then, with 5kg HF fluorination catalyst.Fluoridize in advance toward HF and to add nitrogen in the charging, with the temperature rise of limiting catalyst below 100 ℃.Remove the nitrogen dilution agent, and with the HF charging with the adjustment to 300 of catalyst ℃.Add 133a to form HF then in the HF charging: the 133a molar feed ratio is 3: 1 a reactant mixture.Regulate the charging aperture temperature and improve catalyst temperature, till obtaining purpose value 12%134a productive rate.When being about 330 ℃, the charging aperture temperature obtains the purpose conversion ratio.Owing to for the compensate for catalyst deactivation improves catalyst temperature, the reaction selectivity of 98-99%134a was kept 100 hours.
Then according to the present invention with reactivation of catalyst.This comprises that stopping 350 ℃ of preheated feed of 133a charging and use is convenient to regeneration to regulate catalyst temperature.Air is incorporated in the HF charging gradually.In regenerative process, adiabatic temperature rise make the temperature of catalyst bring up to 380-400 by 350 ℃ (HF of employing: the air molar feed ratio is 20-50: 1).By from the downstream water scrubber system, taking a sample, measure the release conditions of chromium in the catalyst regeneration process.
After regeneration in about 5 hours, along with regenerative response is calmed down, catalyst in reactor is cooled to 350 ℃.Then, stop air feed, the HF feeding temperature is fixed to 330 ℃, prepares to begin 133a reaction cycle next time.Restart the 133a charging, 330 ℃ of discoveries, the catalyst of reactivation has obtained the 134a productive rate of 12-14%.
The chromium-based catalysts quilt is reactivation successfully, has not observed chromium and has been discharged into the downstream scrubber system.And regenerative response has also been avoided a large amount of nitrogen is introduced upstream device; When with the common two or more reactor of the parallel together use of gas extraction system, these characteristics are extremely valuable, because dilute from the unreacted feed operant response device, 134a and Hcl product be not used to regenerate a large amount of nitrogen of off line reactor.
Embodiment 5
Comparative example
From the catalyst operation of the regeneration of embodiment 4 92 hours.Then, stop the 133a charging, and the HF preheater is fixed to 350 ℃.Afterwards, replace the HF air-flow with identical nitrogen stream.When catalyst temperature reaches 350 ℃, in nitrogen, add air with regenerated catalyst.Use N
2: air feed is than for 20-50: 1 produces 50 ℃ of temperature rises, has fallen again in 5-6 hour time, and it is reinforced to stop air afterwards, and restarts the HF charging.The chromium content of monitoring in the scrubber system, the result shows, at catalyst regeneration with have in the fluorination process 15 to restrain chromium and lose from reactor again.
Claims (7)
1. the method for the fluorination catalyst after a regeneration is used in fluorination reaction, this method is included in 300 ℃-500 ℃ makes described used catalyst contact with hydrofluoric mixture with a kind of air that contains, and contains the air of as many as 30% (in mole) in the described mixture.
2. in accordance with the method for claim 1, wherein in the mixture mol ratio of hydrogen fluoride and air be at least 0.1: 1.
3. in accordance with the method for claim 2, wherein the mol ratio of hydrogen fluoride and air is 2-100: 1.
4. in accordance with the method for claim 3, wherein mixture contains 70%-99.9% (in mole) hydrogen fluoride.
5. according to the described method of arbitrary claim among the claim 1-4, wherein mixture also contains a kind of inert diluent.
6. according to the described method of arbitrary claim among the claim 1-4, wherein temperature is 330 ℃-450 ℃.
7. according to the described method of arbitrary claim among the claim 1-5, wherein catalyst is a chromium-containing catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109551 CN1044095C (en) | 1990-09-14 | 1991-10-05 | Method for regenerating fluorination catalysts |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909020084A GB9020084D0 (en) | 1990-09-14 | 1990-09-14 | Chemical process |
| CN 91109551 CN1044095C (en) | 1990-09-14 | 1991-10-05 | Method for regenerating fluorination catalysts |
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| Publication Number | Publication Date |
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| CN1071348A CN1071348A (en) | 1993-04-28 |
| CN1044095C true CN1044095C (en) | 1999-07-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 91109551 Expired - Lifetime CN1044095C (en) | 1990-09-14 | 1991-10-05 | Method for regenerating fluorination catalysts |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9219720D0 (en) * | 1992-09-17 | 1992-10-28 | Ici Plc | Catalyst production |
| FR2746674B1 (en) * | 1996-03-29 | 1998-04-24 | Atochem Elf Sa | REGENERATION OF GAS PHASE FLUORATION CATALYSTS |
| IT1282960B1 (en) * | 1996-05-06 | 1998-04-02 | Ausimont Spa | PROCESS FOR THE REGENERATION OF A CATALYST BASED ON TRIVALENT CHROME COMPOUNDS |
| IT1282961B1 (en) * | 1996-05-06 | 1998-04-02 | Ausimont Spa | PROCESS FOR THE REGENERATION OF A CATALYST BASED ON TRIVALENT CHROME COMPOUNDS |
| ES2216736T1 (en) * | 2001-06-28 | 2004-11-01 | Honeywell International Inc. | PROCESS TO PREPARE A CATALYST IN THE FLUORATION. |
| 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 |
| CN102156163B (en) * | 2010-08-03 | 2012-11-07 | 中国科学院地质与地球物理研究所 | Method for analyzing layered fluorination of diatom sample |
| EP3466912B1 (en) | 2011-01-21 | 2022-04-13 | Arkema France | Catalytic gas phase fluorination |
| EP2665693B1 (en) * | 2011-01-21 | 2017-07-19 | Arkema France | Catalytic gas phase fluorination |
| CN103894219B (en) * | 2014-04-11 | 2015-09-30 | 太仓中化环保化工有限公司 | The 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 |
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1991
- 1991-10-05 CN CN 91109551 patent/CN1044095C/en not_active Expired - Lifetime
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