CN101337187A - Catalyst for producing tetrafluoromethane by gas-phase fluorination and preparation method thereof - Google Patents
Catalyst for producing tetrafluoromethane by gas-phase fluorination and preparation method thereof Download PDFInfo
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- CN101337187A CN101337187A CNA2008101202043A CN200810120204A CN101337187A CN 101337187 A CN101337187 A CN 101337187A CN A2008101202043 A CNA2008101202043 A CN A2008101202043A CN 200810120204 A CN200810120204 A CN 200810120204A CN 101337187 A CN101337187 A CN 101337187A
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Abstract
The invention relates to a catalyst used for fluoridation. Aiming at the deficiencies that the activity is worse and the stability is not high in the prior catalyst used for producing FC-14 through gas phase fluorination, the invention provides a catalyst used for producing tetrafluoromethane through the gas phase fluorination and possessed of high activity, high selectivity, high stability and low application temperature, as well as the preparation method thereof. The catalyst of the invention comprises a carrier and an active ingredient, wherein, the carrier adopts the compound of aluminum; and the active ingredient adopt the compound of chromium. The catalyst of the invention comprises the following preparation process: firstly, the compound of Al and the compound of Cr are weighed out according to a certain proportion, after water is added and the compounds are uniformly mixed, a precipitating agent is added until the compounds are completely precipitated, then separation and washing are carried out until the filtrate is neutral, and the precipitate is dried; secondly, the dried precipitate is calcined after being shaped, so as to obtain a fluorination catalyst precursor; and thirdly, the fluorination catalyst precursor is processed by HF, so as to obtain the catalyst of the invention.
Description
Technical field
The present invention relates to a kind of catalyst that is used for fluorination reaction, be particularly useful for gaseous fluoridizing method and produce tetrafluoromethane (FC-14).
Background technology
Known tetrafluoromethane (below can be described as FC-14) is a compound very useful in the industry, for example, it is the plasma etch gases of consumption maximum in the present microelectronics industry, its high-purity gas and the high-purity gas of tetrafluoromethane are joined the gaseous mixture of high purity oxygen gas, can be widely used in the etching of thin-film materials such as silicon, silica, silicon nitride, phosphorosilicate glass and tungsten; Also there are a large amount of uses aspects such as its production at electronic device surface clean, solar cell, laser technology, gas phase insulation, super low temperature refrigeration agent, leak check agent, detergent, metal smelt and plastic industry, but that the production cost of FC-14 has limited is commercial to using the extensive interest of this compound.
In order to produce FC-14, the whole bag of tricks has been proposed up to now.The at present industrial method that is used to prepare FC-14 mainly contains following several:
(1) method of carbon and fluorine gas reaction;
(2) method of methane and fluorine gas reaction;
(3) method of hydrogen fluoromethane and fluorine gas reaction;
(4) method of thermal decomposition tetrafluoroethene;
(5) electrochemical fluorination method;
(6) fluorochloromethane and anhydrous hydrogen fluoride gaseous fluoridizing method.
In the method for above-mentioned (1), (2) and (3), exist following weak point: used reactive extremely strong, expensive fluorine gas as the fluorine source, its reaction is to carry out in violent condition, wayward, the danger of blast is arranged, and directly add the reactor that fluorine gas needs special construction, equipment is required height, the danger of corrosion is arranged, thus the generation problem relevant with operation with industrial production.In addition, prevent blast and carbon distribution as Explosion suppressant although can adopt inert gas dilution fluorine gas or employing to fluoridize halogen, when being causes an important problem---the purifying difficulty is increased, produce a large amount of losses, so this process is uneconomic.Particularly when preparing FC-14 as the fluorine source,, use excessive fluorine gas usually, can cause like this containing remaining fluorine gas in the final products, thereby bring difficulty to refining step equally in order to improve product yield with fluorine gas.In addition the method for (3) except that the fluorine gas of costliness as the fluorine source, its price as the hydrogen fluoromethane of raw material is also higher relatively, has all limited the scale of industrialized unit.
Exist following weak point in the method for above-mentioned (4): its pyrolysis temperature is up to 1100 ℃, and process energy consumption is big, and product purity and yield are low.
In the method for above-mentioned (5),, therefore can not supply raw materials with the finite quantity relevant with the finite length of electrode because electrochemical fluorination occurs in electrode surface.So electrochemical fluorination has the problem that yields poorly.Other has Russ P to adopt the anode gas that contains HF that electrolysis KF2HF generates as the fluorine source, make it 700 ~ 1200 ℃ down and charcoal react and prepare FC-14.Obviously, this method needs high temperature, and energy consumption is excessive.
At present, the synthetic more promising a kind of method of FC-14 of industrialization is exactly above-mentioned (6) fluorochloromethane and anhydrous hydrogen fluoride gaseous fluoridizing method.Typical gaseous fluoridizing method is to make 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 hydrogen fluoride fluorination of halogenated hydrocarbon carry out not smooth, this and selection of catalysts are closely bound up.When particularly fluoridizing fluorochloromethane with hydrogen fluoride, because the influence (electronegative influence) of adjacent fluorine atom makes the key between carbon and the last chlorine atom seem very firm, therefore the chlorine atom in the fluorochloromethane is difficult to be replaced by fluorine atom, need just can carry out under catalyst and high temperature.Owing to need at high temperature carry out the catalytic fluorination reaction, therefore improve activity of such catalysts and stability, reduce the key that reaction temperature becomes this technology.
Although existing so far catalyst openly is used to the synthetic FC-14 reaction of gas phase fluorination by 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.
American documentation literature US 4474895 discloses a kind of CrO with immersion process for preparing
3Bearing type catalyst for active component.
Yet existing catalyst all show in varying degrees active relatively poor, stability is not high.In the case, obtain satisfied productive rate in order to use chromium-based fluorination catalyst of the prior art, just this synthetic FC-14 reaction needed can be carried out under high temperature, low-speed.As adopting reaction temperature among the Japanese documentation JP-B-62-10211 is that 380 ~ 420 ℃, air speed are 10 ~ 150h
-1, can synthesize FC-14 through the multistage gas phase catalytic fluorination again; Its reaction temperature then needs up to 450 ℃ among the american documentation literature US 4474895.Owing to the speed of catalyst activity reduction along with the rising of reaction temperature is accelerated, therefore, use high temperature, not only energy consumption is big, inactivation that simultaneously can accelerator activator, and low-speed is also very big to production cost and productivity ratio influence.
Therefore, use highly active catalyst to react at low temperatures, not only help saving heat energy, also highly beneficial to prolonging life of catalyst.Its building-up process of FC-14 just requires to develop catalyst active and that stability is higher, serviceability temperature is lower, and in order to produce FC-14 efficiently, needs catalytic activity and is better than the catalyst of fluorination catalyst of the prior art on the life-span.
Summary of the invention
The objective of the invention is to be used for the weak point that the existing activity of catalyst is relatively poor, stability is not high that gas phase fluorination is produced FC-14, a kind of have high activity, high selectivity, high stability, the Catalysts and its preparation method that is used for producing tetrafluoromethane by gas-phase fluorination that serviceability temperature is low are provided at existing.
The present invention finishes by following technical scheme: a kind of Catalysts and its preparation method of producing tetrafluoromethane by gas-phase fluorination, this catalyst comprises carrier and active component, wherein carrier adopts the compound of Al, active component adopts the compound of chromium, and the mol ratio between Cr and the Al is 1: 1～19.
The Preparation of catalysts method of above-mentioned a kind of producing tetrafluoromethane by gas-phase fluorination is: adopt Al (NO
3)
3, AlCl
3Or Al
2O
3, Al (OH)
3, AlF
3, Al
2(SO
4)
3, γ-Al
2O
3In one or more as the Al presoma; Adopt Cr (NO
3)
3, CrCl
3, Cr
2O
3, Cr (OH)
3, CrF
3, Cr (C
2H
3O
2)
3, Cr (OH) SO
4In one or more as the Cr presoma; Prepare sediment with the precipitation method, precipitating reagent adopts a kind of in ammoniacal liquor, ammonium carbonate, sodium carbonate, NaOH, the potassium hydroxide, sediment drying, roasting obtain this catalyst precarsor, obtain the catalyst of producing tetrafluoromethane by gas-phase fluorination again through hydrogen fluoride trealment.
The Preparation of catalysts process of a kind of producing tetrafluoromethane by gas-phase fluorination of the present invention is as follows:
(1) take by weighing the compound of a certain amount of Al and the compound of Cr 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 300～750 ℃ of temperature after the moulding, and wherein roasting process can be at air or N
2Carry out in the atmosphere;
(3) above-mentioned fluorination catalyst precursor was handled 2～48 hours under 250～700 ℃ of temperature through HF, obtained being used for the catalyst of producing tetrafluoromethane by gas-phase fluorination.
Find through experiment, in with HF gas phase fluorination tetrachloromethane, F-11, dicholorodifluoromethane, monochlorotrifluoromethane producing tetrafluoromethane by gas-phase fluorination, be that catalyst based its catalytic performance of Cr of carrier is better than separately the catalytic performance with the Cr acquisition with aluminium oxide.
The present invention has overcome the problem that the catalyst activity that exists in the prior art is low, the life-span is short.Catalyst of the present invention is compared with existing catalysts for gas phase fluorination, has advantages of high catalytic activity or characteristics optionally in the very low scope of material ratio, and it is high to have stability, the advantage that serviceability temperature is low.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.
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
Be to take by weighing Cr at 1: 4 at first according to the mol ratio between Cr and the Al
2O
3And Al (OH)
3, mix with an amount of water, add certain amount of ammonia water to precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 70 ℃.With the oven dry after sediment after moulding at 300 ℃, N
2Roasting is 48 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 250 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 2
Be to take by weighing Cr (OH) at 1: 19 at first according to the mol ratio between Cr and the Al
3And Al (NO
3)
3, mix with an amount of water, add a certain amount of Na
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 600 ℃, N
2Roasting is 24 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 30 hours down at 400 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 3
Be to take by weighing CrCl at 1: 3 at first according to the mol ratio between Cr and the Al
3And Al
2O
3, mix with an amount of water, add a certain amount of KOH to precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 90 ℃.Sediment after the oven dry through roasting 36 hours in 400 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 35 hours down at 350 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 4
Be to take by weighing CrF at 1: 1.5 at first according to the mol ratio between Cr and the Al
3And AlCl
3, mix with an amount of water, add a certain amount of (NH
4)
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 140 ℃.With the oven dry after sediment after moulding at 750 ℃, N
2Roasting is 2 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 2 hours down at 700 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 5
Be to take by weighing Cr (C at 1: 1 at first according to the mol ratio between Cr and the Al
2H
3O
2)
3And Al
2(SO
4)
3, mix with an amount of water, add a certain amount of NaOH to precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 110 ℃.Sediment after the oven dry through roasting 12 hours in 600 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 25 hours down at 450 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 6
Be to take by weighing Cr (NO at 1: 9 at first according to the mol ratio between Cr and the Al
3)
3And AlF
3, mix with an amount of water, add certain amount of ammonia water to precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 130 ℃.Sediment after the oven dry through roasting 8 hours in 650 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 12 hours down at 600 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 7
Be to take by weighing Cr (OH) SO at 1: 15 at first according to the mol ratio between Cr and the Al
4And AlCl
3, mix with an amount of water, add a certain amount of Na
2CO
3To precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 100 ℃.With the oven dry after sediment after moulding at 500 ℃, N
2Roasting is 16 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 32 hours down at 380 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 8
Be to take by weighing Cr (NO at 1: 2 at first according to the mol ratio between Cr and the Al
3)
3And γ-Al
2O
3, mix with an amount of water, add a certain amount of NaOH to precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 70 ℃.With the oven dry after sediment after moulding at 300 ℃, N
2Roasting is 48 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 48 hours down at 250 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 9
Be to take by weighing Cr (NO at 1: 12 at first according to the mol ratio between Cr and the Al
3)
3And AlCl
3, mix with an amount of water, add a certain amount of (NH
4)
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 ℃, H
2Roasting is 36 hours in the atmosphere, obtains the fluorination catalyst precursor.The fluorination catalyst precursor was handled 16 hours down at 550 ℃ with HF, obtained fluorination catalyst.Its reactivity or selectivity see Table 1, table 2, table 3, table 4.
Embodiment 10
Be to take by weighing CrCl at 1: 6 at first according to the mol ratio between Cr and the Al
3And Al (OH)
3, mix with an amount of water, add certain amount of ammonia water to precipitating fully, be neutral through separating, wash then to filtrate, again sediment is dried down at 140 ℃.Sediment after the oven dry through roasting 12 hours in 600 ℃, air atmosphere after the moulding, is obtained the fluorination catalyst precursor.The fluorination catalyst precursor was handled 2 hours down at 700 ℃ with 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=8: 1, air speed: 660h
-1)
Table 2. embodiment 1-12 catalyst is to CCl
3The activity of F and the selectivity of FC-14
(HF: CCl
3F=8: 1, air speed: 660h
-1)
Table 3. embodiment 1-12 catalyst is to CCl
2F
2Activity and the selectivity of FC-14
(HF: CCl
2F
2=8: 1, air speed: 660h
-1)
Table 4. embodiment 1-12 catalyst is to CClF
3Activity and the selectivity of FC-14
(HF: CClF
3=8: 1, air speed: 660h
-1)
Claims (4)
1, a kind of Catalysts and its preparation method of producing tetrafluoromethane by gas-phase fluorination, this catalyst comprises carrier and active component, it is characterized in that carrier adopts the compound of Al, active component adopts the compound of chromium.
2, the Catalysts and its preparation method of producing tetrafluoromethane by gas-phase fluorination according to claim 1 is characterized in that the mol ratio between Cr and the Al is 1: 1～19.
3, the Catalysts and its preparation method of producing tetrafluoromethane by gas-phase fluorination according to claim 1 is characterized in that the Preparation of catalysts method of producing tetrafluoromethane by gas-phase fluorination is: adopt Al (NO
3)
3, AlCl
3, Al
2O
3, Al (OH)
3, AlF
3, Al
2(SO
4)
3, γ-Al
2O
3In one or more as the Al presoma; Adopt Cr (NO
3)
3, CrCl
3, Cr
2O
3, Cr (OH)
3, CrF
3, Cr (C
2H
3O
2)
3, Cr (OH) SO
4In one or more as the Cr presoma; Prepare sediment with the precipitation method, precipitating reagent adopts a kind of in ammoniacal liquor, ammonium carbonate, sodium carbonate, NaOH, the potassium hydroxide, sediment drying, roasting obtain this catalyst precarsor, obtain the catalyst of producing tetrafluoromethane by gas-phase fluorination again through hydrogen fluoride trealment.
4, the Catalysts and its preparation method of producing tetrafluoromethane by gas-phase fluorination according to claim 3 is characterized in that, this Preparation of catalysts process is as follows:
(1) take by weighing the compound of a certain amount of Al and the compound of Cr 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 300～750 ℃ of temperature after the moulding, and wherein roasting process can be at air or N
2Carry out in the atmosphere;
(3) above-mentioned fluorination catalyst precursor was handled 2～48 hours under 250～700 ℃ of temperature through HF, obtained being used for the catalyst of producing tetrafluoromethane by gas-phase fluorination.
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|---|---|---|---|
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|---|---|---|---|
| CNA2008101202043A CN101337187A (en) | 2008-08-08 | 2008-08-08 | Catalyst for producing tetrafluoromethane by gas-phase fluorination and preparation method thereof |
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ID=40211447
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151576A (en) * | 2011-03-01 | 2011-08-17 | 浙江师范大学 | Catalyst for fluoridizing chlorinated olefin and preparation method thereof |
| CN102716761A (en) * | 2012-07-03 | 2012-10-10 | 浙江师范大学 | Catalyst for producing hexafluoroisopropanol through gas phase hydrogenation of hexafluoroacetone trihydrate |
| CN102140054B (en) * | 2010-01-28 | 2013-11-20 | 中国中化股份有限公司 | Preparation method of tetrafluoromethane |
| CN108654597A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that microwave radiation technology combustion method prepares the amorphous catalyst with doped structure |
| 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 |
-
2008
- 2008-08-08 CN CNA2008101202043A patent/CN101337187A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140054B (en) * | 2010-01-28 | 2013-11-20 | 中国中化股份有限公司 | Preparation method of tetrafluoromethane |
| CN102151576A (en) * | 2011-03-01 | 2011-08-17 | 浙江师范大学 | Catalyst for fluoridizing chlorinated olefin and preparation method thereof |
| CN102151576B (en) * | 2011-03-01 | 2012-08-08 | 浙江师范大学 | Catalyst for fluoridizing chlorinated olefin and preparation method thereof |
| CN102716761A (en) * | 2012-07-03 | 2012-10-10 | 浙江师范大学 | Catalyst for producing hexafluoroisopropanol through gas phase hydrogenation of hexafluoroacetone trihydrate |
| CN102716761B (en) * | 2012-07-03 | 2013-10-23 | 浙江师范大学 | Catalyst for producing hexafluoroisopropanol through gas phase hydrogenation of hexafluoroacetone trihydrate |
| CN108654597A (en) * | 2018-04-29 | 2018-10-16 | 浙江工业大学 | A kind of method that microwave radiation technology combustion method prepares the amorphous catalyst with doped structure |
| 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 |
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Open date: 20090107 |