CN1460547A - Catalyst for preparing trifluorochloroethylene by using CFC-113 catalytic hydro-dechlorination and its preparation method - Google Patents
Catalyst for preparing trifluorochloroethylene by using CFC-113 catalytic hydro-dechlorination and its preparation method Download PDFInfo
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- CN1460547A CN1460547A CN 03146226 CN03146226A CN1460547A CN 1460547 A CN1460547 A CN 1460547A CN 03146226 CN03146226 CN 03146226 CN 03146226 A CN03146226 A CN 03146226A CN 1460547 A CN1460547 A CN 1460547A
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Abstract
The present invention relates to a catalyst for preparing trifluorochloroethylene by using CFC-113 catalystic hydrogenation dechlorination process and its preparation method. Said invention adopts metal rhenium and metal copper as main active component, uses the metal lanthanum as upgrading adjuvant component and uses the coconut active carbon as carrier to prepare said invented catalyst with high activity and selectivity. Said invention also provides its formula.
Description
Technical field
The present invention prepares catalyzer, specifically, relates to 1,1,2-three fluoro-1,2, and 2-trichloroethane (being commonly called as CFC-113) is produced the trifluorochloroethylene catalyst system therefor for raw material, and preparation method thereof.
Background technology
Trifluorochloroethylene is an important monomer raw material of producing many fluorine-containing chlorine high molecular polymers (homopolymer or copolymer).Especially it still is that (trifluorochloroethylene-alkyl vinyl ether-hydroxyl vinyl ether copolymer resins, crucial raw material monomer FEVE) can further be made the fluorocarbon coating of having many uses and at room temperature can film-forming by this FEVE resin to a kind of ternary fluorocarbon resin.Tradition is produced the monomeric industrial process of trifluorochloroethylene, is by the stoichiometric chemistry reaction process process of Freon 113 (CFC-113) with the metal zinc reduction dechlorination.Though the reaction conditions of this technology is gentle (about 100 ℃ of temperature of reaction, about working pressure 1.0Mpa), but technological process can only be the operation of batch still formula, efficient is lower, except that consuming much larger than the metal zinc of theoretical amount, also to use a large amount of solvent methanols, thereby make that the production cost of fluorine vinylchlorid is higher, especially this technological process is also wanted a large amount of zinc chloride residue of by-product (1 ton of trifluorochloroethylene of every production, generate about 1.36 tons of zinc chloride waste residue liquids), and be difficult to handle, cause than the serious environmental pollution problem.
Yet, produce the method for trifluorochloroethylene if adopt the CFC-113 catalytic hydrogenation and dechlorination, not only can realize serialization production, not generate (because of having replaced metal zinc) with hydrogen but also do not have the zinc chloride waste residue, and by-product trifluoro-ethylene and hydrochloric acid (forming by the water absorbing hydrogen chloride).Trifluoro-ethylene then is the starting monomer of a kind of functional polymer fluoropolymer (multipolymer of trifluoro-ethylene and vinylidene fluoride), environment-friendly type cooling agent HCF-134a and environment-friendly cleaning agent fluorine hydrogen ether (trifluoro-ethylene and ethanol polycondensate).
Get in the trifluorochloroethylene work in the past in the catalytic hydrogenation and dechlorination legal system, the mixture of metal oxides such as the employing base metal copper, chromium, nickel, barium and the calcium that have is that active ingredient is made catalyzer (for example USP.3.333.011 (1967) and the clear 64-29328 of JP. (1989)); Perhaps support in silica gel (SiO by metallic nickel
2), aluminum oxide (Al
2O
3) or gac on make catalyzer (for example flat 5-9138 of JP. and E.P.0416,015Al (1990)).The temperature of reaction higher (400～500 ℃) that this two classes catalyzer is required, catalyzer operation lifetime are short and purpose product trifluorochloroethylene selectivity is not high; Also there are employing precious metal palladium, platinum and ruthenium etc. to be supported on gac, SiO
2Or Al
2O
3On make catalyzer (for example E.P.0459,463 (1991)), CN065261A (1992) and CN1351903A (2002)).This type of activity of such catalysts height (temperature of reaction only needs about 200～300 ℃) and the selectivity of trifluorochloroethylene are also higher.Yet these catalyzer cost an arm and a leg because of used precious metal, and the cost of the trifluorochloroethylene of producing is still higher.Learn by document, make supported catalyst with rhenium metal (Rhenium) and have good dehydrochlorination performance, be mainly used in alkyl halide (for example 1,1-ethylene dichloride or CFC-114a etc.) produce the corresponding alkyl halide that mainly removes a chlorine atom, and generate halogenated olefins (USP.2 for example, 765,352 (1956) and USP.5 hardly, 068,473 (1991)).Therefore, seek a kind of better method and prepare trifluorochloroethylene, become the task of top priority.
Summary of the invention
The objective of the invention is to solve existing problem in the above-mentioned prior art, and a kind of used catalyzer of trifluorochloroethylene (and by-product trifluoro-ethylene) of producing is provided, and preparation method thereof.
The object of the invention can realize by following measure:
Catalyzer of the present invention is to be main active constituent with VIIB family rhenium metal element and copper in the periodic table of elements, and lanthanoid metal is the upgrading auxiliary agent, and coconut husk activated carbon (being called for short the coconut husk charcoal) is a carrier.
The present invention adopts that VIIB family rhenium metal element is crucial active constituent in the periodic table of elements, its consumption be total catalyst weight 0.05% to 10% between, preferable amount is 0.5%～5% rhenium metal.
It is metallic copper that the present invention adopts another reactive metal component, its consumption be generally total catalyst weight 0.5～20% between, preferable amount is 2%～15%.
The 3rd upgrading auxiliary agent component that the present invention adopts is a lanthanoid metal, its role is to further improve catalyst performance (mainly being to improve the transformation efficiency of CFC-113).Its consumption is generally 0.05%～4% of total catalyst weight, and preferable amount is 0.1%～2%.
It is the coconut husk charcoal that catalyzer of the present invention carries (load) body, and its specific surface area is generally 1200～1300m
2/ g, pore volume 0.5～0.8cm
3/ g and mean pore size are between 7～10 .This coconut husk charcoal should be in advance before using with 10% aqueous nitric acid processing, so that some metal-salt (the being ash content) content that makes wherein to be contained is reduced to the ppm level.Carrier of the present invention is the commercial goods, belongs to known technology.
Method for preparing catalyst involved in the present invention is to adopt the aqueous chloride solution of perrhenic acid and copper and lanthanum to flood coconut husk charcoal carrier.Can be with the incipient impregnation liquid dipping method under the vacuum condition, also can be in vacuum rotary evaporator with excess volume steeping fluid (but metal component content measures) dipping and be evaporated to dried method and prepare catalyzer.The mode that reactive metal or upgrading metal component can adopt substep adding (sequencing of adding is not limit) or all metal components once to add.Oven dry and roasting (400～500 ℃) under the nitrogen gas stream protection places in the room temperature container standby subsequently.
Temperature of reaction of the present invention is 150～350 ℃, but preferred 180～300 ℃ temperature range; The height of reaction pressure is not the key operation parameter, under normal pressure or the pressure all can, but preferred normal pressure～0.3MPa; It is necessary introducing hydrogen in reaction process, and hydrogen usage is too small or excessively all reaction result is had a negative impact, and adopts H usually
2/ CFC-113 molecular ratio is 1 to 6, but preferably adopts 1.5 to 3.0; The charging space velocity of raw material Freon 113 (CFC-113) is generally 0.1h
-1To 6h
-1, but for making operation steady, even reach the longest the work-ing life of catalyzer, preferred 0.4h
-1To 2.0h
-1And, in time withdraw from for ease of reaction heat, also should add inert gas dilution in the reaction raw materials hydrogen, adopt nitrogen or argon gas as carrier gas all can, carrier gas/hydrogen molecule ratio is generally 0.5～1.5, but is the best with 1.
The present invention has following advantage compared to existing technology: the three-way catalyst of rhenium-copper of the present invention-lanthanum not only has good CFC-113 reactive behavior and generates the trifluorochloroethylene selectivity, and also has good operational stability.Catalyzer raw material cost is also lower than the precious metal simultaneously.
Specific implementation method
Enumerate three embodiment below, the present invention is further specified, but these embodiment do not mean to the present invention's any restriction in addition.
Embodiment 1: rhenium-copper-lanthanum supports (Sample A) on the coconut husk charcoal
Take by weighing the perrhenic acid solution 7.82g (be dissolved in concentrated nitric acid make by rhenium metal) of rhenium-containing 2.68% (wt) respectively, cupric chloride (CuCl
22H
2O) 4.91g; And lanthanum nitrate (La (NO
3)
3NH
2O) 0.54g; Be dissolved in jointly in the 40g deionized water, making the mother liquor that contains the reactive metal component, and this mother liquor placed in the vacuum rotary evaporator, put into 20g coconut husk charcoal (28～42 order) again; Under 40 ℃ of the holding temperatures conditions that constantly rotation is stirred and vacuumized, be evaporated to dried, again 150 ℃ of oven dry 4 hours down.The weight composition of making catalyzer (Sample A) thus is roughly: Re 1%-Cu 9%-La 1%.
Comparative example 1: rhenium is supported on (sample B) on the coconut husk charcoal
The perrhenic acid solution 3.98g of rhenium-containing 2.68% (wt) (be dissolved in concentrated nitric acid make by rhenium metal) is dissolved in the 20g deionized water and makes mother liquor; Again 10g coconut husk charcoal (28～42 order) is placed the 50ml round-bottomed flask; And this flask that fills the coconut husk charcoal given earlier the degassing processing 3 hours of finding time under the condition of 130 ℃ and about 500Pa; Be chilled to room temperature and keeping under the condition of vacuum, the rhenium-containing mother liquor prepared of injection rapidly, and under the condition of slowly rocking, be evaporated to dried, and then oven dry 5 hours under 130 ℃ and normal pressure.The about 1%wt of catalyst samples B rhenium-containing that makes thus.
Comparative example 2: copper is supported on (sample C) on the coconut husk charcoal
According to the method for comparative example 1,2.50g cupric chloride (CuCl22H2O) is dissolved in the 0.1N aqueous hydrochloric acid of 20ml and makes the cupric mother liquor, impregnated in (28～42 order) on the 10g coconut husk charcoal.The about 9%wt of catalyst samples C cupric that makes thus.
Comparative example 3: rhenium and copper are supported on (sample D) on the coconut husk charcoal
According to the method for embodiment 1, with the perrhenic acid solution 3.99g of rhenium-containing 2.68% (wt) (be dissolved in concentrated nitric acid make by rhenium metal) and with 2.48g cupric chloride (CuCl
22H
2O) be dissolved in the 20g deionized water and make mother liquor; And place in the vacuum rotary evaporator, put into 10g coconut husk charcoal (28～42 order) again, about 1%wt of catalyst samples D rhenium-containing that makes thus and the about 9%wt of cupric.
Comparative example 4: ruthenium and copper are supported on (sample E) on the coconut husk charcoal
According to the method for embodiment 1, with 0.53g ruthenium chloride (RuCl
23H
2O) and with 2.15g cupric chloride (CuCl
22H
2O) be dissolved in successively in the aqueous hydrochloric acid that 20ml concentration is 0.1N and make the mother liquor that contains ruthenium and copper; And place in the vacuum rotary evaporator, put 10g coconut husk charcoal (28～42 order) again, the catalyst samples E that makes thus contains about 1%wt of ruthenium and the about 8%wt of cupric.
Embodiment 2: the reaction test of Freon 113 (CFC-113) hydrodechlorination
(reactor size φ in the fixed-bed reactor of making by stainless steel
In10mm and the height 400mm) in be respectively charged into the catalyst samples (A that makes by aforesaid method (embodiment 1 or comparative example 1,2,3 and 4), B, C, D, E) 5ml earlier carries out under thermal treatment under the nitrogen gas stream and the hydrogen stream reduction reaction to these catalyzer and handles, promptly under nitrogen gas stream (40ml/min), handled 3 hours in 450 ℃, and under nitrogen gas stream, being cooled to 100 ℃, swap-in hydrogen reduced 5 hours under hydrogen flowing quantity 40ml/min and 300～350 ℃ of conditions.After restoring operation is finished; under the hydrogen stream protection, be cooled to 150 ℃; carry out Freon 113 hydrodechlorination reaction evaluating rating test; used reaction evaluating condition is: working pressure is a normal pressure; CFC-113: H2: N2=1: 2: 2 (molecular ratio), and CFC-113 feed volume space velocity is for pressing used differential responses temperature by 0.4h
-1～1.6h
-1Between change.Reaction product adopts online gas chromatography analysis method assay determination (with PorapaK-Q chromatogram carrier).The reaction result that obtains is listed in the table 1.
Table 1, several catalytic agent specimen reaction performance comparison result
Annotate: C in the table
CFC-113The molecule transformation efficiency of expression raw material Freon 113 (CFC-113);
| The reaction conditions sample | Temperature of reaction (℃) | ????150 | ??200 | ??250 | ??300 |
| CFC-113 air speed (h -1) | ????0.4 | ??0.8 | ??1.2 | ??1.6 | |
| Sample A | ??C CFC-113(％mol) | ????42.53 | ??56.38 | ??81.38 | ??92.89 |
| ??S CTFE(％mol) | ????95.98 | ??96.36 | ??96.43 | ??94.07 | |
| ??S TrFE(％mol) | ????3.83 | ??2.65 | ??2.49 | ??4.22 | |
| Sample B | ??C CFC-113(％mol) | ????7.16 | ??9.36 | ??14.04 | ??31.90 |
| ??S CTFE(％mol) | ????73.35 | ??84.00 | ??92.13 | ??95.89 | |
| ??S TrFE(％mol) | ????0 | ????0 | ????0 | ????0 | |
| Sample C | ??C CFC-113(％mol) | ????1.16 | ??1.28 | ??3.38 | ??14.97 |
| ??S CTFE(％mol) | ????77.84 | ??84.38 | ??68.34 | ??67.29 | |
| ??S TrFE(％mol) | ????13.07 | ??15.63 | ??17.75 | ??11.49 | |
| Sample D | ??C CFC-113(％mol) | ????8.73 | ??15.57 | ??33.47 | ??63.08 |
| ??S CTFE(％mol) | ????86.34 | ??94.11 | ??95.67 | ??95.12 | |
| ??S TrFE(％mol) | ????8.95 | ??3.20 | ??2.19 | ??2.60 | |
| Sample E | ??C CFC-113(％mol) | ????32.63 | ??61.59 | ??97.74 | ??99.61 |
| ??S CTFE(％mol) | ????67.09 | ??80.37 | ??83.60 | ??83.96 | |
| ??S TrFE(％mol) | ????0.70 | ??0.97 | ??1.24 | ??7.25 |
S
CTFEExpression generates the molecular selectivity of trifluorochloroethylene (CTFE);
S
TrFEExpression generates the molecular selectivity of trifluoro-ethylene (TrFE).
Listed reaction result shows in the table 1, no matter separately rhenium is supported on (as sample B) on the gac, or separately copper is supported on (as sample C) on the gac, their Freon 113 (CFC-113) reaction conversion ratio (C
CFC-113) numerical value is all very low, over-all properties is not good, but the selectivity (S of the trifluorochloroethylene of sample B when being higher than 250 ℃
CTFE) obviously higher.Rhenium and copper are supported on (as sample D) on the gac simultaneously, and its combined reaction performance is obviously improved, and the characteristic of rhenium has obtained reinforcement, and promptly the selectivity of trifluorochloroethylene is improved (referring in 150～200 ℃ of low-temperature ranges).If compare the trifluorochloroethylene selectivity (S of Re-Cu/C with it with by the catalyzer (being sample E) that ruthenium and copper are supported on the gac
CTFE) obviously be better than Ru-Cu/C, but its CFC-113 transformation efficiency will hang down.Introduce the ternary component Re-Cu-La/C catalyzer (as Sample A) that lanthanoid metal is made as the upgrading auxiliary agent in the Re-Cu/C system, its over-all properties further improves again, particularly Freon 113 transformation efficiency (C
CFC-113) can increase substantially.
Embodiment 3: rhenium-copper-lanthanum is supported on the long period study on the stability test of the catalyzer (being Sample A) on the coconut husk charcoal
On the used hydrogenation reaction device of embodiment 2, according to the nitrogen of embodiment 2 handle down with hydrogen under reductive condition Sample A is carried out pre-treatment, and at normal pressure, CFC-113: H
2: N
2=1: 2: 2 (molecular ratio), and Freon 113 charging air speed (volume) is 0.45h
-1Under the condition, tentatively investigated the operational stability of this Sample A, its test-results is listed in the table 2.
The stability test result of table 2, Sample A (Re-Cu-La/C)
| Reaction times accumulative total (hr) | Temperature of reaction (℃) | ??C CFC-113 ??(％mol) | ????S CTFE???(％mol) | ????S TrFE???(％mol) |
| ????50 ????100 ????200 ????300 ????400 ????500 | ????194 ????201 ????215 ????237 ????261 ????315 | ????76.68 ????76.34 ????74.67 ????73.88 ????72.35 ????71.00 | ????96.29 ????96.36 ????96.10 ????94.25 ????90.33 ????85.94 | ????2.73 ????2.49 ????3.75 ????4.08 ????4.31 ????10.98 |
The result shows: the over-all properties and the operational stability of such catalyzer (Sample A) are all good, are fit to the reaction process process by Freon 113 (CFC-113) hydrodechlorination system trifluorochloroethylene (by-product trifluoro-ethylene simultaneously) fully.
Claims (4)
1, a kind of CFC-113 of being used for catalytic hydrogenation and dechlorination is produced the catalyzer of trifluorochloroethylene, it is characterized in that with rhenium metal and metallic copper be main active constituent, and lanthanoid metal is as upgrading auxiliary agent component, and the coconut husk activated carbon is a carrier;
The rhenium metal that is adopted, its consumption be generally total catalyst weight 0.05% to 10% between;
The metallic copper that is adopted, its consumption be generally total catalyst weight 0.5% to 20% between;
The lanthanoid metal that is adopted, its consumption be generally total catalyst weight 0.05% to 4% between.
2, produce the used catalyzer of trifluorochloroethylene according to the said a kind of catalytic hydrogenation and dechlorination of claim 1, it is characterized in that the rhenium metal that adopted, its consumption is 0.5%～5% of a total catalyst weight; The metallic copper that is adopted, consumption are generally 2%～15% of total catalyst weight; The lanthanoid metal that is adopted, consumption are generally 0.1%～2% of total catalyst weight.
3, a kind of CFC-113 of being used for catalytic hydrogenation and dechlorination is produced the method for preparing catalyst of trifluorochloroethylene; it is characterized in that adopting the incipient impregnation liquid dipping of aqueous chloride solution under vacuum condition of perrhenic acid and copper and lanthanum; or in vacuum rotary evaporator with excess volume steeping fluid dipping and be evaporated to the dried coconut husk charcoal carrier that floods; oven dry and roasting are 400～500 ℃ under nitrogen protection, place in the room temperature container standby.
4, preparation method according to claim 3 is characterized in that, active constituent or upgrading auxiliary agent once add, or substep adds; Substep adds fashionable, adds active constituent or upgrading auxiliary agent order and does not limit.
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|---|---|---|---|
| CN 03146226 CN1202913C (en) | 2003-07-07 | 2003-07-07 | Catalyst for preparing trifluorochloroethylene by using CFC-113 catalytic hydro-dechlorination and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03146226 CN1202913C (en) | 2003-07-07 | 2003-07-07 | Catalyst for preparing trifluorochloroethylene by using CFC-113 catalytic hydro-dechlorination and its preparation method |
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| CN1202913C CN1202913C (en) | 2005-05-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140356A (en) * | 2014-07-16 | 2014-11-12 | 常熟三爱富氟化工有限责任公司 | Novel preparation method for green CTFE |
| CN109967101A (en) * | 2019-05-08 | 2019-07-05 | 西安近代化学研究所 | A kind of selection hydrogenation-dechlorination preparation chlorotrifluoroethylene catalyst |
-
2003
- 2003-07-07 CN CN 03146226 patent/CN1202913C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140356A (en) * | 2014-07-16 | 2014-11-12 | 常熟三爱富氟化工有限责任公司 | Novel preparation method for green CTFE |
| CN109967101A (en) * | 2019-05-08 | 2019-07-05 | 西安近代化学研究所 | A kind of selection hydrogenation-dechlorination preparation chlorotrifluoroethylene catalyst |
| CN109967101B (en) * | 2019-05-08 | 2021-12-21 | 西安近代化学研究所 | Catalyst for preparing chlorotrifluoroethylene by selective hydrogenation dechlorination |
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|---|---|
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