CN103691430A - Catalyst for tetrafluorodichloroethane hydrodechlorination and preparation method thereof - Google Patents
Catalyst for tetrafluorodichloroethane hydrodechlorination and preparation method thereof Download PDFInfo
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- CN103691430A CN103691430A CN201210366952.6A CN201210366952A CN103691430A CN 103691430 A CN103691430 A CN 103691430A CN 201210366952 A CN201210366952 A CN 201210366952A CN 103691430 A CN103691430 A CN 103691430A
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Abstract
The invention discloses a catalyst for a tetrafluorodichloroethane hydrodechlorination reaction and a preparation method thereof. The catalyst contains a first metal component Pd, a second metal component and a rest component being an active carbon carrier; the second metal component is selected from a combination of one, two or more than three of La, K, Bi and Ni. The catalyst disclosed by the invention can obviously improve the tetrafluorodichloroethane conversion rate and stability. Chlorotetrafluoroethane and tetrafluoroethane and the like are prepared after carrying out the hydrodechlorination reaction of tetrafluorodichloroethane.
Description
Technical field
[0001] the present invention relates to a kind of Hydrodechlorinating catalyst and preparation method thereof.
Background technology
Tetrafluorodichloroethane (CFC-114 and CFC-114a) can be used as the solvent that cleans textile machinery part, can be as the dielectric of electric apparatus, detect the medium of air leakage instrument, be used for preparing the catalyst of alkane isomerisation or hydrocarbon compound hydrocracking, be again artificial plasm's initial compounds, purposes is very extensive.
Yet because tetrafluorodichloroethane belongs to ozone consuming substances (ODS), China stipulated to completely forbid the consumption of the Ozone depletion materials such as freon with on July 1st, 2007.Traditional high temperature incineration treatment process, easily causes serious secondary environmental pollution.But; tetrafluorodichloroethane can carry out catalytic hydrogenation and dechlorination reaction under catalyst action; the green harmless treatment process that belongs to CFCs material; this technique has been protected earth environment on the one hand; eliminate the negative effect of CFCs to global environment; be translated on the other hand the product that economic worth is higher, turn waste into wealth.This technique is also that the synthetic HFCs generally acknowledging is at present most economical, the easiest, the most promising method.
In hydrogenation-dechlorination course of reaction, the preparation of catalyst is the most key, patent CN200910162615.3 discloses the palladium carbon catalyst of a kind of Au of adding and Ce, this catalyst operation is after 1000 hours, CFC114a conversion ratio still keeps more than 97%, HCFC124 and HFC134a are selective and be more than 97%, its weak point is, use Pd, Au, Ce trimetallic catalyst on the one hand, and noble metal Au co-catalyst obviously improves catalyst cost; On the other hand, catalyst preparation process is complicated, is not suitable for directly applying to industrial production.
The HCl that hydrogenation-dechlorination process produces and a small amount of HF, with carrier and the effect of Pd activated centre, improve Pd activated centre mobility, thereby make catalyst because of sintering inactivation.Therefore under the prerequisite that improves catalyst stability, reduce the emphasis that catalyst cost is Hydrodechlorinating catalyst research as far as possible.
Summary of the invention
The most scabrous problem of hydrogenation-dechlorination reaction is that catalyst activity is low, poor stability, easily inactivation and cost high, the present invention is mainly by the method for selecting suitable Pd source, interpolation or not adding the second active metal component, use acid treatment absorbent charcoal carrier, guaranteeing high activity of catalyst, high selectivity, under the prerequisite of life-span length, simplify catalyst preparation process, avoided using second noble metals such as Au, reduced catalyst cost.
Catalyst provided by the invention can be used for tetrafluorodichloroethane (CFC-114 and CFC-114a) continuous catalytic hydrogenation dechlorination reaction, and the product of preparation comprises HCFC-124, HCFC-124a, HFC-134, HFC-134a, HFC-143 and HFC-143a.Reaction equation is as follows:
The technical solution used in the present invention is:
For a catalyst for tetrafluorodichloroethane hydrogenation-dechlorination reaction, described catalyst contains the first metal component, contains or do not contain the second metal component, and all the other are absorbent charcoal carrier; Described the first metal component is Pd, and the quality proportioning that the first metal component accounts for catalyst is 0.5%～5%; Described the second metal component is selected from a kind of, more than two or three combination in La, K, Bi and Ni, and the quality proportioning that the second metal component accounts for catalyst is 0.05%～5%.
As preferred mode, above-mentioned the second metal component is selected from a kind of, more than two or three combination in La, Bi or K; The quality proportioning that the second metal component accounts for catalyst is 0.1%～2%.
As preferred mode, the quality proportioning that above-mentioned the first metal component accounts for catalyst is 1%～3%.
The present invention is not particularly limited the absorbent charcoal carrier using, but is preferably coconut husk granular active carbon, and particle diameter is 20～40 orders.
The present invention also provides a kind of preparation method of above-mentioned catalyst, comprises the following steps:
(1) carrier pretreatment: active carbon is joined in acid solution, water-bath reflow treatment 2～4h at 60～90 ℃, washing, dry;
(2) source metal dipping: will be mixed with Pd source maceration extract containing Pd compound, or will be mixed with mixed impregnant liquor containing Pd compound and the second metallic compound, the active carbon after step (1) is processed becomes catalyst precarsor after being placed into and flooding 10～24 h in maceration extract;
(3) by the dry 4～6h of catalyst precarsor, then after roasting, obtain catalyst.
As preferred mode, the acid of using in above-mentioned steps (1) is selected from nitric acid and/or hydrochloric acid, and the concentration of acid is 5～20%; Nitric acid more preferably, concentration is 5～10%.
As preferred mode, in catalyst of the present invention preparation, use containing Pd compound be selected from halide, acetate, nitrate, the acid of chlorine palladium of Pd, the complex compound of palladium ammonia and organic palladium a kind of, more than two or three combine; More preferably palladium bichloride and/or palladium nitrate.
As preferred mode, the second metallic compound using in catalyst preparation of the present invention is selected from bimetallic nitrate or halide; Bimetallic nitrate more preferably.As an example, can be La (NO
3)
3nH
2o, KNO
3, Bi (NO
3)
35H
2o and Ni (NO
3)
26H
2o.
The preferred mode of doing, in above-mentioned steps (3), the baking temperature of catalyst precarsor is 80～150 ℃, sintering temperature is 300～400 ℃.
Catalyst prepared by the present invention, before for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination, is preferably processed through reduction, and catalyst is at V
h2: V
n2in=10:10～10:60 atmosphere, overall flow rate is at 20～70ml/min and 200～400 ℃, reduction 1～10h.
When catalyst of the present invention is reacted for tetrafluorodichloroethane hydrogenation-dechlorination, reaction temperature is preferably 100～200 ℃, and reaction pressure is preferably normal pressure, H
2with mole proportion optimization of tetrafluorodichloroethane be 2～4:1, combined feed speed is 6～100ml/min.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does 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 within the scope of claims, may comprise.
embodiment 1
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 5% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
The preparation of Pd source maceration extract: claim 3.082g PdCl
2solid, gets 11.5ml concentrated hydrochloric acid and joins PdCl
2in solid, after its solid CL, add distilled water diluting, and constant volume is standby in 100ml volumetric flask.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned PdCl of 5.5ml
2solution, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, the mass fraction of metal Pd is 2%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 2
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 10% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
The preparation of Pd source maceration extract: claim 3.082g PdCl
2solid, gets 11.5ml concentrated hydrochloric acid and joins PdCl
2in solid, after its solid CL, add distilled water diluting, and constant volume is standby in 100ml volumetric flask.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned PdCl of 5.5ml
2solution, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, the mass fraction of metal Pd is 2%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 3
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 15% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
The preparation of Pd source maceration extract: claim 3.082g PdCl
2solid, gets 11.5ml concentrated hydrochloric acid and joins PdCl
2in solid, after its solid CL, add distilled water diluting, and constant volume is standby in 100ml volumetric flask.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned PdCl of 5.5ml
2solution, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, the mass fraction of metal Pd is 2%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 4
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 20% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
The preparation of Pd source maceration extract: claim 3.082g PdCl
2solid, gets 11.5ml concentrated hydrochloric acid and joins PdCl
2in solid, after its solid CL, add distilled water diluting, and constant volume is standby in 100ml volumetric flask.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned PdCl of 5.5ml
2solution, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, the mass fraction of metal Pd is 2%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 5
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 5% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
The preparation of Pd source maceration extract: claim 3.937g Pd (NO
3)
2solid, gets 11.5ml concentrated hydrochloric acid and joins Pd (NO
3)
2in solid, after its solid CL, add distilled water diluting, and constant volume is standby in 100ml volumetric flask.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned PdCl of 5.5ml
2solution, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, the mass fraction of metal Pd is 2%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 6
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 5% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
Maceration extract preparation: claim 3.082g PdCl
2with 0.451g Ni (NO
3)
26H
2o solid, gets 11.5ml concentrated hydrochloric acid and joins in above-mentioned solid, add distilled water diluting, and constant volume is standby in 100ml volumetric flask after its solid CL.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned mixed solution of 5.5ml, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, metallized metal Pd mass fraction is that 2%, Ni mass fraction is 0.1%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 7
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 5% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
Maceration extract preparation: claim 3.082g PdCl
2with 0.2354g KNO
3solid, gets 11.5ml concentrated hydrochloric acid and joins in above-mentioned solid, add distilled water diluting, and constant volume is standby in 100ml volumetric flask after its solid CL.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned mixed solution of 5.5ml, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, metallized metal Pd mass fraction is that 2%, K mass fraction is 0.1%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 8
By 50g finished particle shape (average grain diameter approximately 20～40 orders), specific area 1000～1500m
2the nitric acid that the active carbon of/g is 5% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
Maceration extract preparation: claim 3.082g PdCl
2with 0.211g Bi (NO
3)
35H
2o solid, gets 11.5ml concentrated hydrochloric acid and joins in above-mentioned solid, add distilled water diluting, and constant volume is standby in 100ml volumetric flask after its solid CL.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned mixed solution of 5.5ml, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, metallized metal Pd mass fraction is that 2%, Bi mass fraction is 0.1%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
embodiment 9
By 50g finished particle shape (the about 20-40 order of average grain diameter), specific area 1000-1500m
2the nitric acid that the active carbon of/g is 5% by mass concentration water-bath at 90 ℃ refluxes and washs 4h, then uses distilled water cyclic washing to neutral, and at 110 ℃, forced air drying 4h is standby.
Maceration extract preparation: claim 3.082g PdCl
2with 0.4846g La (NO
3)
3nH
2o(La
2o
3content is no less than 44%) solid, get 11.5ml concentrated hydrochloric acid and join in above-mentioned solid, after its solid CL, add distilled water diluting, and constant volume is standby in 100ml volumetric flask.
Adopt equi-volume process Kaolinite Preparation of Catalyst, dipping at room temperature carries out.Get active carbon 5g, add the above-mentioned mixed solution of 5.5ml, dipping 24 h are then dried 4 h in 110 ℃ of air dry ovens, and under air atmosphere, in Muffle furnace, 400 ℃ of roasting 4 h obtain catalyst.In catalyst, metallized metal Pd mass fraction is that 2%, La mass fraction is 0.1%.Anti-applications catalyst is at V
h2: V
n2online reductase 12 h at 300 ℃ in=10:30 (overall flow rate is 40ml/min) atmosphere.
comparative example 1
Adopting the active carbon of unprocessed mistake is carrier Kaolinite Preparation of Catalyst, with PdCl
2for Pd source, all the other conditions are identical with embodiment 1.
comparative example 2
The active carbon that adopts unprocessed mistake is carrier Kaolinite Preparation of Catalyst, with Pd (NO
3)
2for Pd source, all the other conditions are identical with embodiment 1.
Catalyst prepared by embodiment 1-9 and comparative example 1-2 is for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination, catalyst amount: 1g, charge ratio: V
h2: V
tetrafluorodichloroethane (CFC-114 and CFC-114a)=50:25 (overall flow rate is 75ml/min), reaction pressure: normal pressure, reaction temperature: 150 ℃.The result data that catalyst accumulative total is reacted after 1500h is listed in table 1.
From table 1 experimental result, catalyst provided by the invention and method for preparing catalyst can obviously improve tetrafluorodichloroethane conversion ratio and stability.
Table 1 tetrafluorodichloroethane hydrogenation-dechlorination catalysts and result data
Claims (12)
1. for a catalyst for tetrafluorodichloroethane hydrogenation-dechlorination reaction, it is characterized in that described catalyst contains the first metal component, contain or do not contain the second metal component, all the other are absorbent charcoal carrier; Described the first metal component is Pd, and the quality proportioning that the first metal component accounts for catalyst is 0.5%～5%; Described the second metal component is selected from a kind of, more than two or three combination in La, K, Bi and Ni, and the quality proportioning that the second metal component accounts for catalyst is 0.05% ~ 5%.
2. according to the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 1, it is characterized in that described the second metal component is selected from a kind of, more than two or three combination in La, Bi or K, the quality proportioning that the second metal component accounts for catalyst is 0.1%～2%.
3. according to the catalyst for tetrafluorodichloroethane hydrogenation-dechlorination reaction claimed in claim 1, it is characterized in that the quality proportioning that described the first metal component accounts for catalyst is 1%～3%.
4. according to the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 1, it is characterized in that described absorbent charcoal carrier is coconut husk granular active carbon, particle diameter is 20～40 orders.
5. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 1, it is characterized in that comprising the following steps:
(1) carrier pretreatment: active carbon is joined in acid solution, water-bath reflow treatment 2～4h at 60～90 ℃, washing, dry;
(2) source metal dipping: will be mixed with Pd source maceration extract containing Pd compound, or will be mixed with mixed impregnant liquor containing Pd compound and the second metallic compound, the active carbon after step (1) is processed becomes catalyst precarsor after being placed into and flooding 10～24 h in maceration extract;
(3) by the dry 4～6h of catalyst precarsor, then after roasting, obtain catalyst.
6. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 5, it is characterized in that the acid of using in described step (1) is selected from nitric acid and/or hydrochloric acid, the mass concentration of acid is 5～20%.
7. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 6, it is characterized in that the acid of using in described step (1) is nitric acid, concentration is 5～10%.
8. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 5, it is characterized in that described halide, acetate, nitrate, the acid of chlorine palladium, the complex compound of palladium ammonia and a kind of, more than two or three combination in organic palladium that is selected from Pd containing Pd compound, described the second metallic compound is selected from bimetallic nitrate or halide.
9. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 8, it is characterized in that the described Pd compound that contains is selected from palladium bichloride and/or palladium nitrate, described the second metallic compound is bimetallic nitrate.
10. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 5, it is characterized in that in described step (3), catalyst precarsor baking temperature is 80～150 ℃, sintering temperature is 300～400 ℃.
11. according to the preparation method of the catalyst for the reaction of tetrafluorodichloroethane hydrogenation-dechlorination claimed in claim 5, it is characterized in that described catalyst is at V
h2: V
n2in=10:10～10:60 atmosphere, overall flow rate is at 20～70ml/min and 200～400 ℃, reduction 1～10h.
12. application in the reaction of tetrafluorodichloroethane hydrogenation-dechlorination according to catalyst claimed in claim 1, is characterized in that reaction temperature is 100～200 ℃, and reaction pressure is normal pressure, H
2with mole proportioning of tetrafluorodichloroethane be 2～4:1, combined feed speed is 6～100ml/min.
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| CN108794334B (en) * | 2017-04-27 | 2021-05-11 | 浙江省化工研究院有限公司 | Method for preparing difluoroacetic acid ester through gas-solid phase reaction |
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| CN111135842A (en) * | 2019-12-26 | 2020-05-12 | 浙江巨化技术中心有限公司 | Catalyst for catalytic conversion of impurities in octafluorocyclobutane, and preparation method and application thereof |
| CN111135842B (en) * | 2019-12-26 | 2022-07-01 | 浙江巨化技术中心有限公司 | Catalyst for catalytic conversion of impurities in octafluorocyclobutane, and preparation method and application thereof |
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