CN104710273A - Preparation method of trifluoroethylene - Google Patents
Preparation method of trifluoroethylene Download PDFInfo
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- CN104710273A CN104710273A CN201310681502.0A CN201310681502A CN104710273A CN 104710273 A CN104710273 A CN 104710273A CN 201310681502 A CN201310681502 A CN 201310681502A CN 104710273 A CN104710273 A CN 104710273A
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Abstract
The invention discloses a method for preparing trifluoroethylene by a vapor phase method. The method comprises that 1,1,1,2-tetrafluoroethane as a raw material undergoes a one-step vapor phase reaction in the presence of a fluorination cracking catalyst at a temperature of 380-500 DEG C so that trifluoroethylene is obtained after hydrogen fluoride removal. A preparation method of the fluorination cracking catalyst comprises the following steps of preparing an Al-Fe-Mg compound from Al, Fe and Mg soluble salts by a certain method, carrying out equivalent-volume impregnation on the compound with a La<3+> or Ce<3+> assistant, carrying out drying and roasting to obtain a catalyst precursor and carrying out HF fluorination. The preparation method realizes a 1,1,1,2-tetrafluoroethane conversion rate greater than 50% and even reaching to 65.1% and the highest product trifluoroethylene selectivity of 99.3%.
Description
Technical field
The present invention relates to a kind of preparation method of trifluoro-ethylene, with HFA 134a be particularly raw material under the existence of fluoridizing catalyst for cracking, gas phase catalysis dehydrofluorination prepares the method for trifluoro-ethylene.
Background technology
Trifluoro-ethylene is not only a kind of important high polymer monomer, but also is the important intermediate of other chemical compound lot of synthesis.Be that the functional polymer fluoropolymer that main body and vinylidene fluoride copolymerization obtain has unusual piezoelectric property with trifluoro-ethylene, in synthesized human organ, have purposes widely; Trifluoro-ethylene and ethanol polycondensation can obtain environment-friendly cleaning agent hydrogen fluorine ether; Trifluoro-ethylene and bromine addition, and then dehydrobromination just can obtain bromotrifluoroethylene, it is also an important high polymer monomer; Trifluoro-ethylene is also the important source material of high-grade pure cotton fabric finishing agent simultaneously.But trifluoro-ethylene boiling point is lower, easy autohemagglutination blast, has higher danger and is difficult to transport and long-term preservation.The research of Present Domestic in prepared by trifluoro-ethylene is considerably less, fails to produce ripe production technology and technique.
US Patent No. 5053377, JP2178238 etc. patent discloses and containing under the metal composite catalysts such as Pd and Au, by 1,1, fluoro-2,2, the 1-trichloroethane catalysis dechlorination hydrogenolysis of 2-tri-produce trifluoro-ethylene, this route is mainly used to produce trifluorochloroethylene, the selectivity of trifluoro-ethylene is poor, abstraction and purification difficulty, the rare trifluoro-ethylene to high-quality.
US Patent No. 5089454, US2802887 etc. adopt trifluorochloroethylene to be that catalytic material Hydrogenation is for trifluoro-ethylene, group VIII metal is adopted to be catalyzer main active component, although make the yield of trifluoro-ethylene be greatly improved, but it is short to there is catalyst life, product is difficult to the problem of collection and separating-purifying.
French Patent FR2710054, FR2729136 and US Patent No. 5856593A report with HFA 134a (HFC-134a) as catalytic material dehydrofluorination prepares the operational path of trifluoro-ethylene.This technique mainly adopts AlF
3lewis acid catalyst, nitrogen makes thinner, the temperature that reaction needed is higher, and 600 DEG C time, the transformation efficiency of HFA 134a only has 34%, and catalyst activity is not high, product separation and purification difficult.
Chinese patent CN103044190A disclose a kind of with, HFA 134a is raw material, and Perfluorocyclobutane is thinner, at Al
2o
3trifluoro-ethylene is prepared with under the compound catalyst for cracking effect of metal phosphate composition.400 ~ 450 DEG C of reactions, HFA 134a transformation efficiency is up to 56.3%; Trifluoro-ethylene selectivity is up to 97.5%.
Above-mentioned operational path also exists, and trifluoro-ethylene yield is lower, severe reaction conditions, and catalyst life is short, reaction needed diluent gas, increases the problem of later stage separation costs, therefore needs a kind of preparation method of new trifluoro-ethylene.
Summary of the invention
Technical problem to be solved by this invention be to overcome in background information that trifluoro-ethylene yield in existing trifluoro-ethylene preparation method is lower, severe reaction conditions, catalyzer work-ing life are short etc. deficiency, provide a kind of with 1,1,1,2-Tetrafluoroethane is raw material, a kind of newly fluoridize catalyst for cracking effect under, a step gas-phase reaction dehydrofluorination prepares the method for trifluoro-ethylene.It is simple that fluorination catalyst of the present invention has preparation method, has highly selective and stability, environment amenable feature.
In order to realize object of the present invention, the invention provides a kind of preparation method of trifluoro-ethylene, with 1,1,1,2-Tetrafluoroethane is raw material, fluoridizing under catalyst for cracking effect, temperature of reaction is 380 DEG C ~ 500 DEG C, one step gas-phase reaction dehydrofluorination prepares trifluoro-ethylene, this preparation method fluoridizing catalyst for cracking is: the soluble salt of incipient impregnation lanthanum or cerium on Al-Fe-Mg mixture, obtained catalyst precursor after drying, roasting, then fluoridizes catalyst for cracking by obtained after HF fluoridizes for catalyst precursor.
The preparation method of described Al-Fe-Mg mixture is: with the soluble salt of the soluble salt of the soluble salt of magnesium, iron and aluminium, water-solublely according to a certain percentage be mixed with mixing solutions, a certain amount of urea is added in mixing solutions, 40 DEG C, stir under, add precipitation agent, control solution pH value between 8.5 ~ 9.5, aging 1 ~ 2h, raised temperature to 90 DEG C, continue aging 8 ~ 12h, filter, by the washing of gained gelatinous precipitate product to neutral, dry at 120 DEG C, obtain Al-Fe-Mg mixture.
In Al-Fe-Mg mixture preparation process, Mg
2+content be Al
3+, Fe
3+, Mg
2+total mole 50%, Fe
3+and Al
3+mol ratio between 1:0.5 ~ 3, Mg
2+, Fe
3+, Al
3+preferred molar ratio be 3:1:2; The content of urea is Al
3+, Fe
3+, Mg
2+3 ~ 5 times of integral molar quantity, preferably 4 times; The content of auxiliary agent is 1% ~ 3% of Al-Fe-Mg mixture quality, is preferably 2%.
On Al-Fe-Mg mixture incipient impregnation La or Ce soluble salt after, through 50 ~ 80 DEG C of dryings, after 400 ~ 500 DEG C of roastings, make catalyst precursor, then make after being fluoridized at 300 ~ 500 DEG C by HF and fluoridize catalyst for cracking.
The concrete preparation process of fluoridizing catalyst for cracking is:
La element or Ce element are auxiliary agent in the preparation process of catalyzer, by the soluble salt of La or Ce, water-solublely be mixed with steeping fluid, equi-volume impregnating is adopted to be uniformly impregnated within Al-Fe-Mg mixture by this steeping fluid, then through 50 ~ 80 DEG C of dryings, compression moulding, after 400 ~ 500 DEG C of roastings, make catalyst precursor, catalyst precursor to be fluoridized with hydrogen fluoride gas at 300 ~ 500 DEG C and obtained fluoridizes catalyst for cracking.
The soluble salt of above-mentioned magnesium, iron, aluminium, lanthanum, cerium can be the soluble salt of the arbitrary forms such as nitrate, vitriol, muriate, and preferred soluble salt is nitrate; Precipitation agent can be ammoniacal liquor or sodium hydroxide, preferred ammoniacal liquor.
Catalyst precursor after the high-temperature roasting temperature preferably 500 DEG C of hydrogen fluoride fluoridation, more preferably initially fluoridizing temperature is 300 DEG C, is warming up to 500 DEG C gradually and continues to fluoridize.
Under the existence of fluorination catalyst of the present invention, the temperature of reaction that HFA 134a takes off HF is 380 DEG C ~ 500 DEG C, preferably 440 DEG C ~ 460 DEG C.
The duration of contact of reaction can be selected in scope widely, is generally 5 seconds ~ 60 seconds, preferably 10 seconds ~ 40 seconds, more preferably 20 seconds ~ 30 seconds.
In reaction process, unreacted HFA 134a can recycle.
Type of reactor for this reaction is not crucial, can use tubular reactor, fluidized-bed reactor etc.In addition, adiabatic reactor or isothermal reactor also can be used to the present invention.
The present invention, adopts 1,1,1,2-Tetrafluoroethane is raw material, under the existence of fluoridizing catalyst for cracking, 350 DEG C ~ 500 DEG C there is gas phase fluorination, high yield pulp1 or highly selective can prepare trifluoro-ethylene, the present invention can make 1, and 1,1,2-Tetrafluoroethane obtains transformation efficiency and is greater than 55%, even reaches 65.1%, and the selectivity of product trifluoro-ethylene is up to 99.3%.
The present invention compared with prior art, has advantage as follows:
(1) preparation technology of catalyzer is simple, and three industrial wastes are few, and Catalyst Production is with low cost, use safety environmental protection.
(2) do not use N2 or other organic and inorganic diluent gass in reaction process, reduce the difficulty of later stage separating-purifying.
(3) the present invention compared with prior art, and temperature of reaction decreases, and decreases the loss of energy, and the reduction of simultaneous temperature makes the kind of by product and quantity reduce, and improves the selectivity of product, reduces the difficulty of later stage separating-purifying.
(4) precursor of catalyzer of the present invention uses the form of Al-Fe-Mg mixture dipping thulium to be prepared, the modulation lewis acidity of catalyzer, improve the degree of scatter of active ingredient simultaneously, make the activity of catalyzer, selectivity, be compared with prior art obtained for and greatly improve.
Figure of description
Fig. 1 is the thermogravimetric analysis figure of catalyzer prepared by embodiment 1;
Embodiment
Provide specific embodiments of the invention below, but do not limit the scope of the invention.
Embodiment 1
By the Mg (NO of 148g
3)
2, 80.7g Fe (NO
3)
3with the Al (NO of 142g
3)
3be dissolved in 500ml water, by Mg
3+: Fe
3+: Al
3+mol ratio 3:1:2 is made into mixing solutions, adds 480g urea (Mg wherein
3+, Fe
3+, Al
3+4 times of integral molar quantity), be heated to 40 DEG C, add a certain amount of ammoniacal liquor, regulate pH value about 8.5, aging 2h, raised temperature to 90 DEG C, continues aging 10h, filters, by the washing of gained gelatinous precipitate product to neutral, dry at 120 DEG C, obtain Al-Fe-Mg mixture.
By the La (NO of 6.25g
3)
36H
2o(La content is 2% of Al-Fe-Mg mixture quality), be dissolved in 100ml water and be mixed with steeping fluid, equi-volume impregnating is adopted to be uniformly impregnated within by this steeping fluid on this Al-Fe-Mg mixture of 100g, then through 50 DEG C of dryings, compression moulding, in retort furnace, 450 DEG C of roastings are after 8 hours, make catalyst precursor.
The catalyst precursor made is loaded tubular reactor, be warming up to 300 DEG C, pass into hydrogen fluoride gas, control exothermic heat of reaction intensification and be less than 20 DEG C, gradually HF flow is increased to 500ml/min, treats that temperature is down to 300 DEG C, continue to fluoridize 1 hour, then be warming up to 500 DEG C with 1 DEG C/min temperature rise rate, continue to fluoridize 8 hours, obtain and fluoridize catalyst for cracking.
Be add 60 milliliters in the carbon steel pipe of 38mm to fluoridize catalyst for cracking at internal diameter, pass into 1,1,1,2-Tetrafluoroethane, 380 DEG C are reacted, and duration of contact is 30 seconds, after reaction 20h, reaction product through washing, alkali cleaning removing HF after, with gas chromatographic analysis 1,1, the transformation efficiency of 1,2-Tetrafluoroethane be 50.8% and the selectivity of trifluoro-ethylene be 99.3%.
Embodiment 2
The present embodiment carries out according to the step identical with embodiment 1, and difference is that the temperature of reaction of HFA 134a changes 420 DEG C into by 380 DEG C, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 53.7% and the selectivity of trifluoro-ethylene be 99.1%.
Embodiment 3
The present embodiment carries out according to the step identical with embodiment 1, and difference is that the temperature of reaction of HFA 134a changes 440 DEG C into by 380 DEG C, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 59.2% and the selectivity of trifluoro-ethylene be 98.9%.
Embodiment 4
The present embodiment carries out according to the step identical with embodiment 1, and difference is that the temperature of reaction of HFA 134a changes 460 DEG C into by 380 DEG C, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 63.4% and the selectivity of trifluoro-ethylene be 98.5%.
Embodiment 5
The present embodiment carries out according to the step identical with embodiment 1, and difference is that the temperature of reaction of HFA 134a changes 500 DEG C into by 380 DEG C, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 65.1% and the selectivity of trifluoro-ethylene be 96.3%.
Embodiment 6
The present embodiment carries out according to the step identical with embodiment 4, and difference is Fe (NO
3)
3change the FeCl of 108.4g into
3, Al (NO
3)
3amount change 71g into, Fe
3+and Al
3+mol ratio be 1:0.5, the amount of urea changes 360g(Mg into
3+, Fe
3+, Al
3+3 times of integral molar quantity), ammoniacal liquor changes sodium hydroxide into, and pH value changes 9.5 into, makes Al-Fe-Mg mixture.La (NO
3)
36H
2o changes Ce (NO into
3)
36H
2o, mass conservation (Ce content is 2% of Al-Fe-Mg mixture quality), all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 55.3% and the selectivity of trifluoro-ethylene be 98.6%.
Embodiment 7
The present embodiment carries out according to the step identical with embodiment 4, and difference is Fe (NO
3)
3amount change 60.5g into, Al (NO
3)
3change the Al of 133.7g into
2(SO
4)
3, Fe
3+and Al
3+mol ratio change 1:3 into, the amount of urea changes 600g(Mg into
3+, Fe
3+, Al
3+5 times of integral molar quantity), make Al-Fe-Mg mixture, all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 62.6% and the selectivity of trifluoro-ethylene be 96.8%.
Embodiment 8
The present embodiment carries out according to the step identical with embodiment 1, and difference is La (NO
3)
36H
2o changes the LaCl of 1.8g into
3(La content is 1% of Al-Fe-Mg mixture quality), all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 61.8% and the selectivity of trifluoro-ethylene be 96.4%.
Embodiment 9
The present embodiment carries out according to the step identical with embodiment 1, and difference adds La (NO
3)
36H
2o changes the La of 6g into
2(SO
4)
3(La content is 3% of Al-Fe-Mg mixture quality), all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 60.2% and the selectivity of trifluoro-ethylene be 98.0%.
Embodiment 10
The present embodiment carries out according to the step identical with embodiment 1, and the duration of contact of reaction is difference change 5s into, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 50.2% and the selectivity of trifluoro-ethylene be 99.3%.
Embodiment 11
The present embodiment carries out according to the step identical with embodiment 1, and the duration of contact of reaction is difference change 10s into, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 54.9% and the selectivity of trifluoro-ethylene be 99.1%.
Embodiment 12
The present embodiment carries out according to the step identical with embodiment 1, and the duration of contact of reaction is difference change 20s into, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 63.5% and the selectivity of trifluoro-ethylene be 98.8%.
Embodiment 13
The present embodiment carries out according to the step identical with embodiment 1, and the duration of contact of reaction is difference change 40s into, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 64.1% and the selectivity of trifluoro-ethylene be 97.9%.
Embodiment 14
The present embodiment carries out according to the step identical with embodiment 1, and the duration of contact of reaction is difference change 60s into, and all the other conditions are constant.After reaction 20h, reaction product after washing, alkali cleaning removing HF, with the transformation efficiency of gas chromatographic analysis HFA 134a be 64.9% and the selectivity of trifluoro-ethylene be 97.2%.
Embodiment 15
The present embodiment carries out according to the step identical with embodiment 3, and difference changes 300h into by 20h at the reaction times.Reaction product is after washing, alkali cleaning removing HF, and with gas chromatographic analysis, the transformation efficiency of HFA 134a and the selectivity of trifluoro-ethylene the results are shown in Table one.
Table one
The thermogravimetric analysis example of catalyzer:
Fluorination catalyst after embodiment 1 being activated carries out thermogravimetric analysis, sees Fig. 1.Result shows that the mass loss of catalyzer 600 DEG C time is only 0.1%, and when temperature reaches 800 DEG C, loss quality also only has 1.0%, and the better heat stability of fluorination catalyst of the present invention is described.
Claims (7)
1. the preparation method of a trifluoro-ethylene, it is characterized in that, with 1,1,1,2-Tetrafluoroethane is raw material, fluoridizing under catalyst for cracking effect, temperature of reaction is 380 DEG C ~ 500 DEG C, duration of contact is 5 seconds ~ 60 seconds, and a step gas-phase reaction dehydrofluorination prepares trifluoro-ethylene, and this preparation method fluoridizing catalyst for cracking is: the soluble salt of incipient impregnation La or Ce on Al-Fe-Mg mixture, obtained catalyst precursor after drying, roasting, then fluoridize catalyst for cracking by obtained after HF fluoridizes for catalyst precursor.
2. the preparation method of trifluoro-ethylene according to claim 1, it is characterized in that, the preparation method of described Al-Fe-Mg mixture is: by the soluble salt of magnesium, iron and aluminium, be made into mixing solutions, add urea and precipitation agent, control the pH value of solution between 8.5 ~ 9.5, obtain Al-Fe-Mg mixture through overaging, drying, roasting, the soluble salt of described magnesium, iron and aluminium is the nitrate of magnesium, iron and aluminium, vitriol or muriate.
3. the preparation method of trifluoro-ethylene according to claim 2, is characterized in that, Mg in described Al-Fe-Mg mixture
2+content be Al
3+, Fe
3+, Mg
2+50%, Fe of integral molar quantity
3+and Al
3+mol ratio between 1:0.5 ~ 3, the content of urea is Al
3+, Fe
3+, Mg
2+3 ~ 5 times of integral molar quantity; The content of La or Ce is 1% ~ 3% of Al-Fe-Mg mixture quality.
4. the preparation method of trifluoro-ethylene according to claim 3, is characterized in that, Mg in Al-Fe-Mg mixture
2+, Fe
3+, Al
3+mol ratio be 3:1:2, the content of urea is Al
3+, Fe
3+, Mg
2+4 times of integral molar quantity, the content of La or Ce is 2% of Al-Fe-Mg mixture quality.
5. the preparation method of trifluoro-ethylene as claimed in claim 1, it is characterized in that, the soluble salt of incipient impregnation La or Ce on Al-Fe-Mg mixture, through 50 ~ 80 DEG C of dryings, make catalyst precursor after 400 ~ 500 DEG C of roastings, then make after being fluoridized at 300 ~ 500 DEG C by HF and fluoridize catalyst for cracking.
6. the preparation method of trifluoro-ethylene according to claim 1, is characterized in that the soluble salt of described La or Ce is nitrate, vitriol or muriate.
7. the preparation method of the trifluoro-ethylene according to claim arbitrary in Claims 1-4, is characterized in that, is fluoridizing under catalyst for cracking effect, and duration of contact is 20 seconds ~ 30 seconds, and temperature of reaction is 440 ~ 460 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251518A (en) * | 2015-11-02 | 2016-01-20 | 西安近代化学研究所 | Catalyst for preparing trichloroethylene from 1,1,1,2-tetrafluoroethane |
| CN107243352A (en) * | 2017-07-11 | 2017-10-13 | 上海三爱富新材料股份有限公司 | Catalyst for synthesizing trifluoro-ethylene and preparation method thereof |
| CN109675572A (en) * | 2018-12-25 | 2019-04-26 | 西安近代化学研究所 | A kind of preparation method and purposes of Fluorine containing olefine cis-trans isomerization catalyst |
| CN114247445A (en) * | 2021-11-26 | 2022-03-29 | 西安近代化学研究所 | Fluorination composite catalyst, preparation method and application |
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| 蔚辰刚; 周强; 彭小波; 谢冠群; 王树华; 罗孟飞;: "HFC-134a裂解制备三氟乙烯催化剂的研究", 《第八届全国工业催化技术及应用年会论文集》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251518A (en) * | 2015-11-02 | 2016-01-20 | 西安近代化学研究所 | Catalyst for preparing trichloroethylene from 1,1,1,2-tetrafluoroethane |
| CN105251518B (en) * | 2015-11-02 | 2017-09-08 | 西安近代化学研究所 | A kind of 1,1,1,2 HFC-134as prepare trifluoro-ethylene catalyst |
| CN107243352A (en) * | 2017-07-11 | 2017-10-13 | 上海三爱富新材料股份有限公司 | Catalyst for synthesizing trifluoro-ethylene and preparation method thereof |
| CN107243352B (en) * | 2017-07-11 | 2019-12-20 | 上海三爱富新材料科技有限公司 | Catalyst for synthesizing trifluoroethylene and preparation method thereof |
| CN109675572A (en) * | 2018-12-25 | 2019-04-26 | 西安近代化学研究所 | A kind of preparation method and purposes of Fluorine containing olefine cis-trans isomerization catalyst |
| CN114247445A (en) * | 2021-11-26 | 2022-03-29 | 西安近代化学研究所 | Fluorination composite catalyst, preparation method and application |
| CN114247445B (en) * | 2021-11-26 | 2024-03-29 | 西安近代化学研究所 | Fluorinated composite catalyst, preparation method and application |
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