CN101269323A - Catalyst for producing tetrafluoromethane with gas-phase fluoridation and production method - Google Patents
Catalyst for producing tetrafluoromethane with gas-phase fluoridation and production method Download PDFInfo
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- CN101269323A CN101269323A CNA2008100613448A CN200810061344A CN101269323A CN 101269323 A CN101269323 A CN 101269323A CN A2008100613448 A CNA2008100613448 A CN A2008100613448A CN 200810061344 A CN200810061344 A CN 200810061344A CN 101269323 A CN101269323 A CN 101269323A
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Abstract
The invention relates to a catalyst used for making tetrafluoromethane through gas-phase fluorination and a preparation method thereof, and aims at providing a catalyst used for making tetrafluoromethane through gas-phase fluorination characterized by high activity and high stability and a preparation method thereof in consideration of poor activity and low stability existing in the existing gas-phase fluorination catalyst. The preparation method of the catalyst of the invention is as follows: one or more than one compound of Y, compound of Cr, compound of magnesium, aluminum, indium, gallium, zinc, scandium, strontium, iron, cobalt, nickel and cadmium are measured according to a certain proportion; the precipitator adopts one among ammonia, sodium hydroxide, ammonium carbonate, sodium carbonate and potassium hydroxide, and sediments are obtained by a coprecipitation method, and the precursor of the catalyst is obtained by baking and roasting the sediments then the catalyst is obtained after being treated with anhydrous hydrogen fluoride.
Description
Technical field
The present invention relates to a kind of catalyst that is used for gas phase fluorination, particularly a kind of catalyst and preparation method who is used for producing tetrafluoromethane by gas-phase fluorination.
Background technology
Tetrafluoromethane (below can be described as FC-14) can be used as for example microelectronics industry and semiconductor manufacturing industry ionic medium body etching gas and clean air, in addition application is also arranged, but that the production cost of FC-14 has limited is commercial to using the extensive interest of this compound at aspects such as cryogenic refrigerations.
In order to produce FC-14, following several method is disclosed up to now: the method for (1) carbon and fluorine gas reaction; (2) method of hydrogen fluoromethane and fluorine gas reaction; (3) method of thermal decomposition tetrafluoroethene; (4) fluorochloromethane and anhydrous hydrogen fluoride gaseous fluoridizing method.Above-mentioned (1) has been to use reactive extremely strong, expensive fluorine gas as the fluorine source with the weak point of the method for (2), reacts wayward, and the danger of blast is arranged, and equipment is required height, and the danger of corrosion is arranged; In addition, the method pyrolysis temperature of (3) is up to 1100 ℃, and process energy consumption is big, and product purity and yield are low.
The synthetic more promising a kind of method of FC-14 of industrialization at present is exactly above-mentioned (4) fluorochloromethane and anhydrous hydrogen fluoride gaseous fluoridizing method.Typical gaseous fluoridizing method is to make anhydrous hydrogen fluoride and halogenated hydrocarbons that displacement reaction take place in gas phase, and the halogen atom except that F is replaced into the F atom.But under most of situations, with the anhydrous hydrogen fluoride fluorination of halogenated hydrocarbon carry out not smooth, this and selection of catalysts are closely bound up, so far, existing a large amount of catalyst is proposed to be used in gas phase fluorination, is with Al about this class reaction catalyst commonly used at present
2O
3Or AlF
3Perhaps MgF
2Deng Al source and Mg source or activated carbon is that the Cr of carrier is catalyst based.And, also advised being doped in the catalyst as cobalt, manganese, nickel, zinc etc., to improve the activity of these chromium-containing catalysts by auxiliary agent.At present numerous by the disclosed catalyst amounts that is used for gas phase fluorination of domestic and international patent documentation, for example:
Japanese documentation JP-B-62-10211 discloses a kind of based on CrO
2F
2Fluorination catalyst make monochlorotrifluoromethane (CClF
3) technology of producing FC-14 through multistage gas phase catalytic fluorination reaction.
Chinese patent literature CN1464872A discloses a kind of carrier bearing type catalyst or bulk catalyst with trivalent chromium oxide as major constituent, and this catalyst is applicable to fluoridizes monochlorotrifluoromethane (CClF in the gas phase
3) production FC-14.
Japanese documentation JP-B-42-3004 discloses a kind of gas phase fluorination dicholorodifluoromethane (CCl that is applicable to
2F
2) produce the catalyst of FC-14.In the instantiation, select spherical Al for use
2O
3As catalyst carrier, dipping nickel, chromium isoreactivity component, catalyst is made in back drying, calcining, activation.
Chinese patent literature CN 1091651C discloses a kind of at carrier A lF
3Or Al
2O
3The catalyst of last load C r, this catalyst are applicable in the gas phase and carry out fluorination of halogenated hydrocarbon with HF.
Chinese patent literature CN 1064628A discloses a kind of catalyst that is applicable to that vapor phase method is fluoridized halogenated hydrocarbons with hydrogen fluoride.This catalyst as the basic composition element, adds auxiliary agent nickel, zinc, cadmium etc. with chromium, gallium, oxygen, fluorine.
It is compound loaded in as the chromium-free fluorination catalyst on the carriers such as halogenated compound of aluminium oxide or aluminium oxide that Chinese patent literature CN 1078172A discloses a kind of In.But this catalyst activity is too poor, does not have actual using value.
This shows that the Cr that adds auxiliary agent is generally adopted in gas phase catalytic fluorination halogenated hydrocarbons field
2O
3Or Cr (OH)
3Or CrO
2F
2For catalyst or with Al
2O
3, AlF
3Deng material is that the Cr of carrier is catalyst based.Yet such is based on Cr (III) compound, the promoter metal of only mixing atom and do not adopt the catalyst of carrier easily to produce the unwanted difficult accessory substance that separates in the production, and the phenomenon of carbon deposition is very serious on catalyst, so that the activity of accelerator activator descends possibly; Such catalyst may generate Cr (VI) compound in roasting and activation process simultaneously, causes chromium species leakage serious, and this understands the inactivation of accelerator activator equally; There is the some shortcomings part equally and be that the Cr of carrier is catalyst based based on Al (III) compound, for example, Al at a certain temperature
2O
3Or AlF
3Be difficult to the meeting generation crystal phase transition avoided, cause catalysqt deactivation, make the service life of catalyst restricted; While Al
2O
3Change AlF into
3In time, can produce a large amount of water and makes the solubility loss of active component of load.
Summary of the invention
The objective of the invention is the weak point relatively poor at the existing existing activity of catalyst that is used for gas phase fluorination, that stability is not high, a kind of have high activity, high selectivity, stability is high, regeneration is easy to be used for producing tetrafluoromethane by gas-phase fluorination catalyst and preparation method are provided.
The present invention finishes by following technical scheme: a kind of catalyst and preparation method who is used for producing tetrafluoromethane by gas-phase fluorination, this catalyst comprises carrier and active component, wherein carrier adopts the compound of Y, in the compound of active component employing chromium and the compound of A one or more, the compound of A is the compound of magnesium, aluminium, indium, gallium, zinc, scandium, strontium, iron, cobalt, nickel and cadmium, and wherein the mol ratio between A, Cr and the Y is 0.01～0.5: 1: 0.05～20.
Above-mentioned a kind of Preparation of catalysts method that is used for producing tetrafluoromethane by gas-phase fluorination is: adopt Y (NO
3)
3Or YCl
3Or Y
2O
3Or Y (OH)
3Or YF
3Or Y (C
2H
3O
2)
3Or Y
2(SO
4)
3Or their mixture is as the Y presoma, Cr (NO
3)
3Or CrCl
3Or Cr
2O
3Or Cr (OH)
3Or CrF
3Or Cr (C
2H
3O
2)
3Or Cr (OH) SO
4Or their mixture is as the Cr presoma, the compound of A is selected from one or more in nitrate, halide, sulfate, acetate, silicate or the acylate etc., precipitating reagent adopts a kind of in ammoniacal liquor, NaOH, ammonium carbonate, sodium carbonate, the potassium hydroxide, prepare sediment with coprecipitation, sediment drying, roasting obtain this catalyst precarsor, handle the catalyst that obtains being used for producing tetrafluoromethane by gas-phase fluorination through anhydrous hydrogen fluoride again.
The present invention is a kind of, and to be used for the concrete operations step of Preparation of catalysts method of producing tetrafluoromethane by gas-phase fluorination as follows:
(1) take by weighing the compound of a certain amount of Y, the compound of Cr and the compound of A in proportion, after adding water and mixing, add precipitating reagent to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70～140 ℃ of oven dry down;
(2) sediment after will drying obtains the fluorination catalyst precursor through roasting 2～48 hours in 250～650 ℃ of temperature after the moulding, and wherein the sediment after moulding can be at air or H in roasting process
2Or N
2Carry out in the atmosphere.
(3) the logical anhydrous HF of above-mentioned fluorination catalyst precursor was handled 2～48 hours under 200～600 ℃ of temperature, obtained being used for the catalyst of producing tetrafluoromethane by gas-phase fluorination.
A kind ofly use above-mentioned catalyst and fluoridize the method for producing tetrafluoromethane, this method may further comprise the steps:
(1) 1: 4 in molar ratio～20 ratio is contacting the mixture of one or more halogenated hydrocarbons in a certain amount of tetrachloromethane, F-11, dicholorodifluoromethane, the monochlorotrifluoromethane and anhydrous HF under 340～450 ℃ with described catalyst in first reactor, and be 2～30sec time of contact;
(2) all gas that first reactor is come out through washing, 1: 4 in molar ratio～20 ratio is mixed with anhydrous HF after the drying, then mixture is being contacted in second reactor under 340～450 ℃ with described catalyst, be 2～30sec time of contact;
(3) product of step (2) is handled, isolated tetrafluoromethane and other admixture of gas, reclaim tetrafluoromethane;
(4) will deliver to first reactor from other admixture of gas and additional anhydrous HF that step (3) obtain.
Catalyst of the present invention is compared with existing catalysts for gas phase fluorination, in the very low scope of material ratio, have advantages of high catalytic activity or characteristics optionally, and have advantages such as method of operating is simple and easy, quick and cheap, catalyst of the present invention has higher using value, especially shows high economic worth in by tetrachloromethane, F-11, dicholorodifluoromethane, monochlorotrifluoromethane producing tetrafluoromethane by gas-phase fluorination.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy after the catalyst activation.
Fig. 2 is the N before and after the catalyst precarsor activation
2The adsorption desorption thermoisopleth.
The specific embodiment
Further specify the new and effective fluorination catalyst of invention below by embodiment, but the present invention is not limited to following examples.
Embodiment 1
At first the load capacity according to Cr is that 70wt% takes by weighing CrCl
3And Y (OH)
3, mix with an amount of water, add the Na that a certain amount of concentration is 2mol/L
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 90 ℃.With the oven dry after sediment after moulding at 400 ℃, N
2Roasting is 12 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 2 hours down at 600 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 2
Be that the doping of 20wt%, Fe is that 2wt% takes by weighing Cr at first according to the load capacity of Cr
2O
3, FeCl
3And Y
2O
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 140 ℃ of oven dry down.With the oven dry after sediment after moulding at 650 ℃, N
2Roasting is 2 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 3
Be that the doping of 50wt%, Ga is that 3wt% takes by weighing Cr (OH) at first according to the load capacity of Cr
3, Ga
2O
3And Y (NO
3)
3, mix with an amount of water, add (the NH that a certain amount of concentration is 2mol/L
4)
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 120 ℃.With the oven dry after sediment after moulding at 250 ℃, H
2Roasting is 48 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 8 hours down at 500 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 4
Be that the doping of 30wt%, Cd is that 1wt% takes by weighing Cr (C at first according to the load capacity of Cr
2H
3O
2)
3, Cd (NO
3)
2And YF
3, mix with an amount of water, the KOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70 ℃ of oven dry down.With the oven dry after sediment after moulding at 400 ℃, H
2Roasting is 12 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 200 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 5
At first the load capacity according to Cr is 30wt%, and the doping of Zn is that 5wt% takes by weighing CrF
3, Zn (CH
3COO)
2And Y
2(SO
4)
3, mix with an amount of water, the NaOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 110 ℃ of oven dry down.Sediment after the oven dry through roasting 8 hours in 500 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 6
Be that the doping of 10wt%, Ni is that 1wt% takes by weighing Cr at first according to the load capacity of Cr
2O
3, NiSO
4And YCl
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 120 ℃ of oven dry down.Sediment after the oven dry through roasting 30 hours in 300 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 7
Be that the doping of 20wt%, In is that 0.8wt% takes by weighing Cr (NO at first according to the load capacity of Cr
3)
3, In (NO
3)
3And Y (C
2H
3O
2)
3, mix with an amount of water, the NaOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 140 ℃ of oven dry down.With the oven dry after sediment after moulding at 400 ℃, N
2Roasting is 12 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 2 hours down at 600 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 8
Be that the doping of 50wt%, Co is that 2.5wt% takes by weighing Cr at first according to the load capacity of Cr
2O
3, Co (NO
3)
2And YF
3, mix with an amount of water, add the Na that a certain amount of concentration is 2mol/L
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 80 ℃.With the oven dry after sediment after moulding at 500 ℃, H
2Roasting is 8 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 10 hours down at 420 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 9
Be that the doping of 8wt%, M g is that 1wt% takes by weighing Cr (OH) SO at first according to the load capacity of Cr
4, Mg
2Si
3O
8And Y (C
2H
3O
2)
3, mix with an amount of water, the KOH that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 90 ℃ of oven dry down.With the oven dry after sediment after moulding at 250 ℃, H
2Roasting is 48 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 10
Be that the doping of 30wt%, Sr is that 4.5wt% takes by weighing Cr (OH) SO at first according to the load capacity of Cr
4, SrCl
2And Y (OH)
3, mix with an amount of water, add the Na that a certain amount of concentration is 2mol/L
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 120 ℃.Sediment after the oven dry through roasting 8 hours in 500 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 11
Be that the doping of 10wt%, Al is that 3.5wt% takes by weighing Cr (C at first according to the load capacity of Cr
2H
3O
2)
3, Al (OH)
3And Y
2(SO
4)
3, mix with an amount of water, add the Na that a certain amount of concentration is 2mol/L
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 140 ℃.Sediment after the oven dry through roasting 2 hours in 650 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 200 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 12
Be that the doping of 50wt%, Sc is that 2.5wt% takes by weighing CrF at first according to the load capacity of Cr
3, Sc (NO
3)
3And Y (NO
3)
3, mix with an amount of water, the ammoniacal liquor that adds a certain amount of concentration and be 2mol/L to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70 ℃ of oven dry down.With the oven dry after sediment after moulding at 400 ℃, N
2Roasting is 12 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 24 hours down at 380 ℃ with anhydrous HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Table 1. embodiment 1-12 catalyst is to CCl
4Activity and the selectivity of FC-14
(HF: CCl
4=20: 1, time of contact: 30sec)
Table 2. embodiment 1-12 catalyst is to CCl
3The activity of F and the selectivity of FC-14
(HF: CCl
3F=20: 1, time of contact: 20sec)
Table 3. embodiment 1-12 catalyst is to CCl
2F
2Activity and the selectivity of FC-14
(HF: CCl
2F
2=10: 1, time of contact: 10sec)
Table 4. embodiment 1-12 catalyst is to CClF
3Activity and the selectivity of FC-14
(HF: CClF
3=4: 1, time of contact: 2sec)
Claims (4)
1, a kind of catalyst that is used for producing tetrafluoromethane by gas-phase fluorination, this catalyst comprises carrier and active component, wherein carrier adopts the compound of Y, it is characterized in that active component adopts one or more in the compound of the compound of chromium and A, the compound of A is the compound of magnesium, aluminium, indium, gallium, zinc, scandium, strontium, iron, cobalt, nickel and cadmium, and wherein the mol ratio between A, Cr and the Y is 0.01～0.5: 1: 0.05～20.
2, a kind of method for preparing the catalyst of claim 1 is characterized in that this Preparation of catalysts method is: adopt Y (NO
3)
3Or YCl
3Or Y
2O
3Or Y (OH)
3Or YF
3Or Y (C
2H
3O
2)
3Or Y
2(SO
4)
3Or their mixture is as the Y presoma, Cr (NO
3)
3Or CrCl
3Or Cr
2O
3Or Cr (OH)
3Or CrF
3Or Cr (C
2H
3O
2)
3Or Cr (OH) SO
4Or their mixture is as the Cr presoma, the compound of A is selected from one or more in nitrate, halide, sulfate, acetate, silicate or the acylate etc., precipitating reagent adopts a kind of in ammoniacal liquor, NaOH, ammonium carbonate, sodium carbonate, the potassium hydroxide, prepare sediment with coprecipitation, sediment drying, roasting obtain this catalyst precarsor, handle obtaining this catalyst again through anhydrous hydrogen fluoride.
3, a kind of preparation according to claim 2 is used for the method for the catalyst of producing tetrafluoromethane by gas-phase fluorination, it is characterized in that the concrete preparation manipulation step of this catalyst is as follows:
(1) take by weighing the compound of a certain amount of Y, the compound of Cr and the compound of A in proportion, after adding water and mixing, add precipitating reagent to precipitation fully, be neutral through separating, wash then to filtrate, again with sediment 70～140 ℃ of oven dry down;
(2) sediment after will drying obtains the fluorination catalyst precursor through roasting 2～48 hours in 250～650 ℃ of temperature after the moulding, and wherein the sediment after moulding can be at air or H in roasting process
2Or N
2Carry out in the atmosphere;
(3) the logical anhydrous HF of above-mentioned fluorination catalyst precursor was handled 2～48 hours under 200～600 ℃ of temperature, obtained catalysts for gas phase fluorination.
4, a kind of catalyst of application rights requirement 1 is fluoridized the method for producing tetrafluoromethane, it is characterized in that this method may further comprise the steps:
(1) 1: 4 in molar ratio～20 ratio is contacting the mixture of one or more halogenated hydrocarbons in a certain amount of tetrachloromethane, F-11, dicholorodifluoromethane, the monochlorotrifluoromethane and anhydrous HF under 340～450 ℃ with described catalyst in first reactor, and be 2～30sec time of contact;
(2) all gas that first reactor is come out through washing, 1: 4 in molar ratio～20 ratio is mixed with anhydrous HF after the drying, then mixture is being contacted in second reactor under 340～450 ℃ with described catalyst, be 2～30sec time of contact;
(3) product of step (2) is handled, isolated tetrafluoromethane and other admixture of gas, reclaim tetrafluoromethane;
(4) will deliver to first reactor from other admixture of gas and additional anhydrous HF that step (3) obtain.
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|---|---|---|---|
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|---|---|---|---|
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| CN108863710A (en) * | 2018-06-20 | 2018-11-23 | 临海市利民化工有限公司 | A kind of preparation method of tetrafluoromethane |
| CN108863710B (en) * | 2018-06-20 | 2021-03-19 | 临海市利民化工有限公司 | Preparation method of tetrafluoromethane |
| CN111036225A (en) * | 2019-12-17 | 2020-04-21 | 山东东岳化工有限公司 | Method for preparing high-activity pentafluoroethane chromium-based catalyst through sectional roasting and sectional fluorination |
| CN116946978A (en) * | 2023-09-21 | 2023-10-27 | 山东东岳化工有限公司 | Method for preparing high-purity carbon tetrafluoride and chlorine |
| CN116946978B (en) * | 2023-09-21 | 2024-02-02 | 山东东岳绿冷科技有限公司 | Method for preparing high-purity carbon tetrafluoride and chlorine |
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