CN103143344A - Chromium-based fluorination catalyst with high specific surface, and preparation method thereof - Google Patents
Chromium-based fluorination catalyst with high specific surface, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a chromium-based fluorination catalyst with high specific surface, high activity, and high stability, and a preparation method thereof. The chromium-based fluorination catalyst provided by the invention comprises a first active ingredient and a second active ingredient, wherein, the first active ingredient is Cr; the second active ingredient is one or more selected from Mg, Zn, Al, Co, Y, Ga or Pr; the molar ratio of the second active ingredient to the first active ingredient is 0.001-0.5:1; and the fluorination catalyst has a surface area of 320-500m<2>/g. The chromium-based fluorination catalyst provided by the invention is realized by adding an organic compound additive in the preparation process, wherein the organic compound additive is formed by compounding polyethylene glycol with an ionic liquid. The chromium-based fluorination catalyst provided by the invention is particularly suitable for the preparation of HFC-125 and HFC-134a.
Description
Technical field
The present invention relates to a kind of for fluorination reaction, especially for the height of halogenated hydrocarbons gas phase fluorination than table chromium-based fluorination catalyst and preparation method thereof.
Background technology
In gas phase fluorination, the catalyst that uses is generally with the catalyst of chromium element as main active component.Up to now, improve the method for catalyst performance normally by increasing specific surface area of catalyst or adding assistant metal and carry out.
Be used at present vapor phase method and produce the chromium-based catalysts precursor Cr of freon substitute hydrogen fluorohydrocarbon
2O
3NH
2The preparation method that O (0＜n＜3) is commonly used is the precipitation method.With NaOH, (NH
4)
2CO
3, the solubility chromic salts such as the precipitating reagent such as ammoniacal liquor precipitation chromic nitrate hydrate, chromium trichloride, chrome alum generate chromium hydroxide attitude catalyst, filter, washing, become Cr after 100～200 ℃ of dryings
2O
3NH
2O (0＜n＜3) further can be used as the catalyst of synthetic hydrogen fluorohydrocarbon through overmolding, roasting, activation, but the specific area of catalyst is usually at 100～200m
2/ g, although that this preparation method and infusion process are compared step is various, activity is higher.
For example, EP295885A1 has reported the method for preparing R134a, and its catalyst is with commodity γ-Al
2O
3Be carrier (specific area＞100m
2/ g), after the dipping active metallic compound, fluoridize the γ-Al after fluoridizing with HF in reaction tube
2O
3All change AlF into
3
EP408004 has introduced and has been stated from specific area 25m at least
2The AlF of/g
3On the existence of chromic salts catalyst under, in 220 ℃～280 ℃, make tetrachloro-ethylene carry out hydrofluorination reaction in gas phase and HF, make 1,2-, two chloro-1,1,2-HFC-143a (HCFC-123).The conversion ratio of the method tetrachloro-ethylene is very low.
By above report as can be known, at γ-Al
2O
3In fluorination process, fluoridize meeting and produce a large amount of water, make the loss of active component of dipping, in addition, fluoridize excess Temperature and can cause AlF
3Crystalline substance become.And use AlF
3The specific surface area of catalyst that direct impregnation obtains is very little, makes the conversion ratio of raw material very low.
Chinese patent CN95115476.1 discloses a kind of SiO of containing
2γ-Al
2O
3The active A lF that makes
3, its specific area 〉=40m
2/ g, pore volume 〉=0.18m
2/ g, average pore size≤9nm, AlF
3Content 〉=90%, then flood Cr
3+, Co
2+, Mg
2+Soluble-salt, drying, roasting, fluoridize with nitrogen and hydrofluoric mist and make fluorination catalyst.In order to obtain the AlF of high-specific surface area
3, generally at Al
2O
3Middle interpolation SiO
2, utilize hydrogen fluoride and SiO
2Reaction generates the volatility fluorosilicone compound and improves AlF
3The specific area of carrier, but due to easy cooling the condensing of volatility fluorosilicone compound, cause pipeline blockage makes that the preparation process of catalyst is more difficult carries out continuously; Simultaneously, need strict control to fluoridize temperature, can't guarantee the reappearance of catalyst.
Patent documentation US5849658 has reported that also the catalytic activity of catalyst and its specific area have sizable relation, improves Cr
2O
3NH
2The specific area of O (0＜n＜3) helps to improve its catalytic activity
Chinese patent CN1068521A discloses a kind of ammonia precipitation process chromic salts (chromic nitrate hydrate, chromium trichloride, chrome alum etc.) solution and has prepared the method for high specific surface chrome catalysts, the method adopts the chromium nitrate aqueous solution of ammonia precipitation process, and the factors such as the concentration by controlling chromic salts and ammoniacal liquor in preparation process, reaction temperature, ammoniacal liquor rate of addition are come increasing specific surface area.
Chinese patent CN1408476 has described high active long-acting fluorating catalyst and manufacture method thereof, it adopts the precipitation method that active component soluble-salt (but nitrate, sulfate, chloride) is configured to certain density solution, react with precipitating reagent (ammoniacal liquor, NaOH, KOH etc.) under 20～100 ℃, control final pH value 6.5～9.5 to, obtain the catalyst precursor by filtration, washing, drying, roasting after precipitation, the catalyst precursor specific area that obtains is greater than 200m
2/ g.But the specific surface area of catalyst of these preparation method's preparations can not be entirely satisfactory, and therefore need to seek a kind of raising Cr
2O
3NH
2The method of the specific area of O (0＜n＜3).
In order to overcome the undesirable shortcoming of specific surface area of catalyst of the prior art, the inventor has designed the preparation method of the precursor of high-ratio surface chromium-based catalysts.
Summary of the invention
The object of the present invention is to provide the preparation method of chromium-based fluorination catalyst and the precursor thereof of a kind of high activity, high stable, bigger serface, this precursor can be used for the catalyst of gas phase fluorination halogenated hydrocarbons after super-dry, roasting, activation.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of for by C
1-C
4Halogenated hydrocarbons prepare the chromium-based fluorination catalyst of corresponding hydrogen fluorohydrocarbon, comprise the first active component and the second active component, wherein:
The first active component is Cr;
The second active component is selected from one or more combinations in Mg, Zn, Al, Co, Y, Ga or Pr;
Mole proportioning of the second active component and the first active component is 0.001～0.5: 1;
The specific area of described fluorination catalyst is 320～500m
2/ g is preferably 380～500m
2/ g.
Mole proportion optimization of above-mentioned the second active component and the first active component is 0.01～0.1: 1.
The present invention also provides a kind of preparation method of above-mentioned chromium-based fluorination catalyst, comprises the steps:
(1) be that 400～6000 polyethylene glycol and the organic composite additive of the composite formation of ionic liquid join in the alcohols solvent of chromic salts with molecular weight, the salt of interpolation the second active component in the alcohol solution of chromic salts simultaneously, the mass ratio of described organic composite additive and chromic salts is 0.1: 1～0.8: 1;
(2) add precipitating reagent to precipitate under stirring condition, control the PH of solution 6.5～10.0, after filtration, wash, be drying to obtain the catalyst precursor;
(3) use the fluorization agent fluorating catalyst former body, namely get chromium-based fluorination catalyst.
Form colloidal sol after having added each component in the alcohol solution of chromic salts in above-mentioned steps (1), in described step (2), catalyst precursor is preferably dimensioned to be 20～250nm.
Chromic salts can provide with the form of the salt of any suitable trivalent chromic ion in above-mentioned steps (1), and the salt of trivalent chromic ion is preferably: chromic nitrate (Cr (NO
3)
3) or its crystalline hydrate compound, chromium chloride (CrCl
3) or its crystalline hydrate compound.
Intermediate ion liquid of the present invention add the surface acidity that can change catalyst, the difference of its addition can change it and adapt to different fluorine halogen substitution reactions, and can increase the adsorption desorption ability to material in fluorination reaction process, thereby improve greatly catalytic activity.Above-mentioned ionic liquid is preferably glyoxaline ion liquid, i.e. 1-alkyl-3-methyl tetrafluoroborate, and wherein the carbon chain lengths of alkyl is 2～10, has following (I) structural formula:
[C
nmin]BF
4 (I)
Wherein: n is integer and 2≤n≤10,
In glyoxaline ion liquid, the carbon chain lengths of alkyl is preferably 4≤n≤8.
The present invention is by adding organic composite additive to control specific area and the surface acidity of chromium-based fluorination catalyst presoma in the preparation process of chromium-based fluorination catalyst presoma.The quality proportion optimization of above-mentioned polyethylene glycol and ionic liquid is 0.5～3: 1, more preferably 1～1.5: 1.
The molecular weight of above-mentioned polyethylene glycol is preferably 400～2000, and more preferably 600～1000.
Above-mentioned alcohols solvent is preferably≤positive alcohol or the different alcohols of 3 carbon, more preferably methyl alcohol and/or ethanol.
It is 2～15% ammoniacal liquor that above-mentioned precipitating reagent is preferably concentration.
In the preparation method of above-mentioned chromium-based fluorination catalyst, the second active component and the first active component mole proportion optimization are 0.001～0.5: 1, more preferably 0.01～0.1: 1.
In the present invention, chromium-based fluorination catalyst obtains by catalyst precursor materials is fluoridized, the common fluorization agent that is used for activating catalyst all can be used for fluorating catalyst former body of the present invention, from the angle that is easy to get, preferably use the mist of hydrogen fluoride or hydrogen fluoride and inert gas.Preferred activity methods is the presoma roasting in the nitrogen of 350 ℃～550 ℃ with chromium-based fluorination catalyst, then passes into nitrogen and hydrofluoric mist is fluoridized under 200～400 ℃, makes chromium-based fluorination catalyst.
In above-mentioned steps (2), drying is preferably in two steps and carries out, and first carries out vacuum freeze drying, and vacuum is not less than 0.09Mpa; And then carry out drying at the temperature of 80～110 ℃; Be 0.5～5 hour drying time.
In the present invention, gas phase fluorination refers to that the fluorine chlorine exchange reaction of carrying out, the essential condition of impact reaction have the proportioning of temperature, pressure, two kinds of raw materials (halogenated hydrocarbons and fluoride) and the material air speed (wherein air speed is mass flow/catalyst volume) by beds etc. under chromium-based fluorination catalyst exists.
The invention provides the application of described chromium-based fluorination catalyst in preparation HFC-125, take HCFC-123 as raw material, under chromium-based fluorination catalyst exists, prepare HFC-125 with the HF gas-phase reaction, mole proportion optimization of described HF and HCFC-123 is 3～10: 1, be preferably 2～10 seconds time of contact, reaction temperature is preferably 280～350 ℃.
The present invention also provides the application of described chromium-based fluorination catalyst in preparation HFC-134a, take HCFC-133a as raw material, under chromium-based fluorination catalyst exists, prepare HFC-134a with the HF gas-phase reaction, mole proportion optimization of described HF and HCFC-133a is 2～10: 1, be preferably 2～10 seconds time of contact, reaction temperature is preferably 300～360 ℃.
the present invention has overcome the deficiencies in the prior art, on the one hand by adding organic composite additive, improve greatly the specific area of catalyst precursor, improved significantly the activity of catalyst, ionic liquid in organic composite additive can change the surface acidity of catalyst according to demand, control catalyst particle by form colloidal sol in the chromic salts alcoholic solution on the other hand, Particle size control is at 20～250nm, thereby make catalyst have great specific area, thereby solve the undesirable problem of catalyst activity, make chromium-based fluorination catalyst of the present invention have high conversion, high selectivity and good stability.
Figure of description
The described catalyst test collection of illustrative plates of Fig. 1 catalyst Preparation Example 1
The described catalyst test collection of illustrative plates of Fig. 2 catalyst comparative example 1
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but do not limit the invention to these specific embodiment.One skilled in the art would recognize that the present invention contained all alternatives, improvement project and the equivalents that may comprise in claims scope.
Catalyst Preparation Example 1
Take 120g CrCl
36H
2O is dissolved in the 480ml ethanolic solution, then adds 24gPEG-600 and [C in mentioned solution
4Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 450m
2/ g.And adopt Micromeritics AutoChem II 2920 type auto-programming intensification chemical adsorption instruments to carry out temperature programmed desorption (TPD) test spectrogram and see Figure of description 1 fluoridizing rear catalyst.
Catalyst Preparation Example 2
Take 120g CrCl
36H
2O and 0.05g magnesium nitrate are dissolved in 480ml ethanol, then add 36g PEG-1000 and [C in mentioned solution
4Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 480m
2/ g.
Catalyst Preparation Example 3
Take 120g CrCl
36H
2O and 0.06g zinc nitrate are dissolved in 480ml ethanol, then add 12g PEG-1000 and [C in mentioned solution
2Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 410m
2/ g.
Catalyst Preparation Example 4
Take 120g CrCl
36H
2O and 0.06g zinc nitrate are dissolved in 600ml ethanol, then add 12g PEG-1000 and [C in mentioned solution
2Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 370m
2/ g.
Catalyst Preparation Example 5
Take 120g CrCl
36H
2O and 0.06g zinc nitrate are dissolved in 600ml ethanol, then add 36g PEG-1000 and [C in mentioned solution
2Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 500m
2/ g.
Catalyst Preparation Example 6
Take 120g CrCl
36H
2O and 0.06g zinc nitrate are dissolved in 300ml ethanol, then add 24g PEG-600 and [C in mentioned solution
6Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 370m
2/ g.
Catalyst Preparation Example 7
Take 120g CrCl
36H
2O and 0.06g zinc nitrate are dissolved in 300ml ethanol, then add 12g PEG-1000 and [C in mentioned solution
2Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 320m
2/ g.
Catalyst Preparation Example 8
Take 120g CrCl
36H
2O and 0.06g magnesium nitrate are dissolved in 480ml ethanol, then add 36g PEG-2000 and [C in mentioned solution
10Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 460m
2/ g.
Catalyst Preparation Example 9
Take 120g CrCl
36H
2O and 0.06g cobalt nitrate are dissolved in 600ml ethanol, then add 36g PEG-400 and [C in mentioned solution
8Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 430m
2/ g.
Catalyst Preparation Example 10
Take 120g CrCl
36H
2O and 0.05g aluminum nitrate are dissolved in 300ml ethanol, then add 36g PEG-5000 and [C in mentioned solution
6Min] BF
41: 1 compound even solvent in mass ratio, add again the ammonia spirit of 10% concentration of 150g in the mentioned solution, control solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, when reaching 0.09Mpa ,-40 ℃ of vacuums put into material, the first step is warming up to 0 ℃, keeps 4 hours, and second step is warming up to 90 ℃, after dry 2h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
The specific area that adopts BET to analyze its presoma is 380m
2/ g.
Catalyst comparative example 1
Take 120g CrCl
36H
2O is dissolved in the 480ml deionized water, then adds the 10% concentration ammonia spirit of 150g in the mentioned solution, controls solution final pH value between 6.5-10.0, filter described solution, sediment is extremely neutral with the deionized water washing, after 110 ℃ of dry 16h, make catalyst precursor.
Then with described catalyst precursor compression molding, in the reactor of then packing into, 400 ℃ of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized under 200-400 ℃, make chromium-based fluorination catalyst.
Adopting specific area and pore structure tester (being designated hereinafter simply as BET) to analyze its presoma specific area is 220m
2/ g.And adopt Micromeritics AutoChem II 2920 type auto-programming intensification chemical adsorption instruments to carry out temperature programmed desorption (TPD) test spectrogram and see Figure of description 2 fluoridizing rear catalyst.
Test example 1 different catalysts is to synthetic HFC-125 (CF
3CHF
2) impact
With the chromium-based fluorination catalyst of comparative example 1 and embodiment 1 be respectively charged into the nickel alloy pipe (middle part of φ 46 * 3mm) fixed bed reactors, specifically filling process is: slowly vertically add the comparative example 1 of 100mL and the chromium-based fluorination catalyst of embodiment 1-9 (noting not shaking graduated cylinder in adition process) respectively in graduated cylinder; And then respectively with vertical the joining in reactor of chromium-based fluorination catalyst of the comparative example 1 in graduated cylinder and embodiment 1-9, install reactor.
Before beginning reaction, first purge 4 hours with nitrogen under 400 ℃, then pass into HF and HCFC-123 (CF
3CHCl
2) react, the mol ratio of controlling HF and HCFC-123 is 5: 1, and be 5 seconds time of contact, and reaction temperature is 350 ℃, and the reaction time is 24 hours; After reaction finishes, product is removed HCl and HF through washing, alkali cleaning, then use the gas chromatographic analysis product composition.The results are shown in Table 1.
Table 1 different catalysts is to HFC-125 (CF
3CHF
2) impact of synthetic result
Test example 2 different catalysts are to synthetic HFC-134a (CF
3CH
2F) impact
With the chromium-based fluorination catalyst of comparative example 1 and embodiment 1 be respectively charged into the nickel alloy pipe (middle part of φ 46 * 3mm) fixed bed reactors, specifically filling process is: slowly vertically add the comparative example 1 of 100mL and the chromium-based fluorination catalyst of embodiment 1-9 (noting not shaking graduated cylinder in adition process) respectively in graduated cylinder; And then respectively with vertical the joining in reactor of chromium-based fluorination catalyst of the comparative example 1 in graduated cylinder and embodiment 1-9, install reactor.
Before beginning reaction, first purge 4 hours with nitrogen under 400 ℃, then pass into HF and HCFC-133a (CF
3CH
2Cl) react, the mol ratio of controlling HF and HCFC-133a is 5: 1, and be 5 seconds time of contact, and reaction temperature is 310 ℃, and the reaction time is 24 hours; After reaction finishes, product is removed HCl and HF through washing, alkali cleaning, then use the gas chromatographic analysis product composition.The results are shown in Table 2.
Table 2 different catalysts is to HFC-134a (CF
3CH
2F) impact of synthetic result
Claims (16)
1. one kind is used for by C
1-C
4Halogenated hydrocarbons prepare the fluorination catalyst of corresponding hydrogen fluorohydrocarbon, it is characterized in that described fluorination catalyst is chromium-based fluorination catalyst, comprise the first active component and the second active component, wherein:
The first active component is Cr;
The second active component is selected from one or more combinations in Mg, Zn, Al, Co, Y, Ga or Pr;
Mole proportioning of the second active component and the first active component is 0.001～0.5:1;
The specific area of described fluorination catalyst is 320～500m
2/ g.
According to claimed in claim 1 for by C
1-C
4Halogenated hydrocarbons prepare the fluorination catalyst of corresponding hydrogen fluorohydrocarbon, the specific area that it is characterized in that described fluorination catalyst is 380～500m
2/ g.
According to claimed in claim 1 for by C
1-C
4Halogenated hydrocarbons prepare the fluorination catalyst of corresponding hydrogen fluorohydrocarbon, mole proportioning that it is characterized in that described the second active component and the first active component is 0.01～0.1:1.
According to claimed in claim 1 for by C
1-C
4Halogenated hydrocarbons prepare the preparation method of the fluorination catalyst of corresponding hydrogen fluorohydrocarbon, it is characterized in that comprising the steps:
(1) be that 400～6000 polyethylene glycol and the organic composite additive of the composite formation of ionic liquid join in the alcohols solvent of chromic salts with molecular weight, the salt of interpolation the second active component in the alcohol solution of chromic salts simultaneously, the mass ratio of described organic composite additive and chromic salts is 0.1:1～0.8:1;
(2) add precipitating reagent to precipitate under stirring condition, control the PH of solution 6.5～10.0, after filtration, wash, be drying to obtain the catalyst precursor;
Use the fluorization agent fluorating catalyst former body, namely get chromium-based fluorination catalyst.
5. according to the preparation method of fluorination catalyst claimed in claim 4, it is characterized in that in described step (1), each component forms colloidal sol, in described step (2), catalyst precursor is of a size of 20～250nm.
6. according to the preparation method of fluorination catalyst claimed in claim 4, it is characterized in that described chromic salts is chromic salt, be selected from chromic nitrate or its crystalline hydrate compound, chromium chloride or its crystalline hydrate compound.
7. according to the preparation method of fluorination catalyst claimed in claim 4, it is characterized in that described ionic liquid is glyoxaline ion liquid 1-alkyl-3-methyl tetrafluoroborate, has following (I) structural formula:
[C
nmin]BF
4 (I)
Wherein: n is integer and 2≤n≤10, min=.
8. according to the preparation method of fluorination catalyst claimed in claim 7, the carbon chain lengths that it is characterized in that alkyl in described glyoxaline ion liquid is 4≤n≤8.
9. according to the preparation method of fluorination catalyst claimed in claim 4, the molecular weight that it is characterized in that described polyethylene glycol is 400～2000, and the quality proportioning of polyethylene glycol and ionic liquid is 0.5～3:1.
10. according to the preparation method of fluorination catalyst claimed in claim 9, the molecular weight that it is characterized in that described polyethylene glycol is 600～1000, and the quality proportioning of polyethylene glycol and ionic liquid is 1～1.5:1.
11. according to the preparation method of fluorination catalyst claimed in claim 4, it is characterized in that described alcohols solvent is positive alcohol or the different alcohols of≤3 carbon, described precipitating reagent is that concentration is 2～15% ammoniacal liquor.
12. according to the preparation method of the described fluorination catalyst of claim 11, it is characterized in that described alcohols solvent is methyl alcohol and/or ethanol.
13. according to the preparation method of fluorination catalyst claimed in claim 4, it is characterized in that described the second active component and the first active component mole proportioning are 0.01～0.1:1, described fluorization agent is the mist of hydrogen fluoride or hydrogen fluoride and inert gas.
14. the preparation method according to fluorination catalyst claimed in claim 4, it is characterized in that in step (2), drying is carried out in two steps, first carry out vacuum freeze drying, vacuum is not less than 0.09Mpa, and then carry out drying at the temperature of 80～110 ℃, be 0.5～5 hour drying time.
15. the application in preparation HFC-125 of an one of claim 1 to 14 described fluorination catalyst, it is characterized in that: take HCFC-123 as raw material, under chromium-based fluorination catalyst exists, prepare HFC-125 with the HF gas-phase reaction, mole proportioning of described HF and HCFC-123 is 3～10:1, be 2～10 seconds time of contact, and reaction temperature is 280～350 ℃.
16. the application in preparation HFC-134a of an one of claim 1 to 14 described fluorination catalyst, it is characterized in that: take HCFC-133a as raw material, under chromium-based fluorination catalyst exists, prepare HFC-134a with the HF gas-phase reaction, mole proportioning of described HF and HCFC-133a is 2～10:1, be 2～10 seconds time of contact, and reaction temperature is 300～360 ℃.
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