CN103288589A - Method for co-production of trifluoroethylene and hydrogen fluoride - Google Patents
Method for co-production of trifluoroethylene and hydrogen fluoride Download PDFInfo
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- CN103288589A CN103288589A CN2013102171471A CN201310217147A CN103288589A CN 103288589 A CN103288589 A CN 103288589A CN 2013102171471 A CN2013102171471 A CN 2013102171471A CN 201310217147 A CN201310217147 A CN 201310217147A CN 103288589 A CN103288589 A CN 103288589A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for the co-production of trifluoroethylene and hydrogen fluoride, and is used for producing the trifluoroethylene in a hydrogen fluoride removing manner by taking 1,1,1,3-tetrafluoroethane as a main raw material as well as co-producing the hydrogen fluoride. The method comprises the following steps: mixing HFC-134a (1,1,1,2-tetrafluoroethane) and an inert gas at a molar ratio f 1:(1-20); performing a reaction of removing HF (Hydrogen Fluoride) from the HFC-134a in a fixed bed reactor through an acid catalyst under the conditions that the temperature ranges from 300 to 650 DEG C, the air speed ranges from 300 to 2000h<-1> and the pressure ranges from 0.1 to 0.8Mp; separating tail gas in a first separation tower; pretreating the catalyst and producing an anhydrous hydrogen fluoride product through the cyclic utilization of the separated hydrogen fluoride; realizing the cyclic utilization of the HFC-134a and the inert gas after separating the HFC-134a with a low boiling point, the inert gas and the trifluoroethylene in a second separation tower; performing alkaline cleaning, drying, compression and condensation liquefaction on the trifluoroethylene; then enabling the trifluoroethylene to enter a first rectifying tower; finally drying and packaging the trifluoroethylene treated in the first rectifying tower. The method is suitable for the production of the trifluoroethylene, and belongs to an atomic economic reaction. The two reaction products have important economic values; the conversion rate of the HFC-134a is high; the selectivity and yield of the trifluoroethylene as a main product are high.
Description
Technical field
The present invention relates to a kind of chemical preparation process, particularly the hydrofluoric method of a kind of production trifluoro-ethylene coproduction.
Background technology
Trifluoro-ethylene (TrFE) is mainly used in synthetic fluoropolymer at present as a kind of important Fluorine containing olefine.This class fluoropolymer had both had heat-resistant stability, chemicals-resistant stability and stable ultraviolet resistance, the resolvability and the melt-processible that also have conventional polymer, also have unique electrical property such as ferroelectricity, piezoelectricity, pyroelectricity, high dielectric property simultaneously, be with a wide range of applications in industries such as electronics, military affairs, medical treatment.
The main synthetic method of document and patent report trifluoro-ethylene monomer has at present:
(1) CFC-113 hydrodechlorination method: 2CF
2ClCFCl+H
2→ 2CF
2=CHF+6HCl
(2) CFC-1123 hydrodechlorination method: 2CF
2=CFCl+H
2→ 2CF
2=CHF+2HCl
(3) CFC-114 hydrodechlorination method: CF
3CCl
2F+2H
2→ CF
2=CHF+2HCl+HF
(4) zinc powder dehalogenation method: CF
3CFX
2+ 2Zn+H
2O → 2CF
2=CHF+ZnX
2+ ZnCl
2+ Zn (OH)
2(X=Cl, Br)
(5) synthetic trifluoro-ethylene: the CCl of CFC-12 and HFC-134a high temperature
2F
2+ 2CF
3CH
2F → 2CF
2=CHF+CF
4+ 2HCl
(6) HFC-134a dehydrofluorination method: CF
3CHF
2→ CF
3=CHF+HF
Industrial application is relative with bibliographical information more at present with (2) for technology (1), being prepared by the method for corresponding fluorohaloparaffin dehalogenation is more valued method at present, technology (1) is by 1,1,2-three chloro-1,2,2-Halothane (CFC-113) hydrogenolysis dechlorination on noble metal catalyst prepares trifluoro-ethylene, its product mainly contains trifluorochloroethylene and trifluoro-ethylene, and this method is not high to the selectivity of trifluoro-ethylene.Technology (2) is to obtain by trifluorochloroethylene (CFC-1113) hydrogenolysis dechlorination under the effect of palladium or platinum catalyst, and this method as raw material, does not have advantage with trifluorochloroethylene economically.Aforesaid method exists that catalyst life is short, product is difficult to collect and separates problem such as purification, the having relatively high expectations of conversion unit, and the cost that this has increased the production trifluoro-ethylene undoubtedly causes that the market value of trifluoro-ethylene is higher.
US5892135 has reported CF
3CFCl
2(CFC-114) hydrodechlorination prepares trifluoro-ethylene, as above-mentioned technology (3).The by product of this reaction is more, as CF
2=CH
2, CF
3CH
2F and CF
2=CHCl etc., the easy inactivation of catalyzer, and exist product to be difficult to collect and the separation and purification problem equally.
The method of patent JP57026629A, CN101851146A and CN102372593 adopting process (4), the shortcoming of this method are that reaction raw materials is difficult for obtaining, and hydrogen halide solution is to the seriously corroded of equipment in the product, and three wastes treatment capacity is big.The route of patent CN102267866A adopting process (5), this method with methyl chlorofluoride and HFC-134a as raw material, with the chromic oxide that adds auxiliary agent as catalyzer, the temperature height of this reaction, the side reaction of methyl chlorofluoride disproportionation is more, exist product to be difficult to problems such as collection, separation and purification, this method is not suitable for carrying out industrialization.
The patent of adopting process (6) is respectively: FR2710054A has reported a kind of preparation method of trifluoro-ethylene, uses aluminum fluoride as catalyzer; US5856593A adopts the chromated oxide of other metal that mixes as the catalyzer of preparation trifluoro-ethylene; FR2729136A feeds BF when the preparation trifluoro-ethylene
3Improve activity of such catalysts.All there is the problem that the transformation efficiency of HFC-134a is not high, life of catalyst is short in aforesaid method, and BF
3Belong to hazardous product inflammable, explosive, hypertoxic and chance water vigorous reaction, in use can bring potential safety hazard.In addition, producing a large amount of anhydrous hydrogen fluorides in this technology is not fully utilized and does not produce economic benefit.
The present invention selects for use with γ-Al
2O
3And α-Al
2O
3Come catalysis HFC-134a dehydrofluorination to produce trifluoro-ethylene, and the coproduction anhydrous hydrogen fluoride.This method belongs to atomic economy reaction, and product all has important economic value, and no side reaction takes place, and the transformation efficiency height of HFC-134a, trifluoro-ethylene selectivity height, catalyst life height.
Summary of the invention
The objective of the invention is to overcome existing weak point of producing trifluoro-ethylene technology, low etc. as raw materials for production and catalyzer cost, product collection and the performance of separating purification, catalyzer, by product utilization ratio, a kind of method of producing trifluoro-ethylene coproduction anhydrous hydrogen fluoride is provided.Adopt this processing method, can reduce the cost of raw materials for production and catalyzer, product is easy to purify and separate, and takes full advantage of by product, and the performance height of catalyzer, produces trifluoro-ethylene coproduction anhydrous hydrogen fluoride especially for the HFC-134a dehydrofluorination.
In order to solve these technical problems, the technical scheme of employing of the present invention is as follows:
The hydrofluoric method of a kind of production trifluoro-ethylene coproduction, concrete steps are as follows:
(1), the catalyzer of in fixed-bed reactor, packing into, earlier 200 ℃ of dryings under rare gas element feed HF gas (hydrogen fluoride) then, with rare gas element catalyzer are carried out activation treatment after the vaporizing chamber vaporization;
(2), with 1,1,1,3-Tetrafluoroethane (HFC-134a) and the described rare gas element of step (1) 1:1～1:20 in molar ratio mix, enter in the fixed bedreactor of step (1) gained after heating, the control temperature of reaction is that 300～650 ℃, air speed are 300～2000 h
-1, pressure is 0.1～0.8 Mp;
(3), step (2) reacted tail gas is separated through first knockout tower, isolated hydrogen fluoride is capable of circulation for pretreatment catalyst, in addition can also be through second rectifying tower, be packaged into the HF product after dry;
(4), low-boiling-point substance HFC-134a, rare gas element and trifluoro-ethylene after first knockout tower in the step (2) separated, proceed to separate at second knockout tower, HFC-134a and rare gas element enter recycle in separately the raw material storage equipment; Wherein: the weight ratio that trifluoro-ethylene, HF and HFC-134a press 1:1:1 generates;
(5), with the trifluoro-ethylene that separates in the step (4), behind alkali cleaning, drying, compression, condensation liquefaction, enter first rectifying tower, the trifluoro-ethylene that will handle from first rectifying tower is packed after drying at last.
Among the present invention, the rare gas element in the step (1) is He, Ar or N
2One or both.
Among the present invention, the AHF gas after the vaporizer vaporization and the mol ratio of rare gas element are 1:1～1:8.
Among the present invention, catalyzer is γ-Al described in the step (1)
2O
3Or α-Al
2O
3
Among the present invention, the tail gas in step (2) and (3) after reactor reaction is rare gas element, TrFE, HF and HFC-134a, and wherein product TrFE and HF and HFC-134a raw material generate in the ratio of 1:1:1.
Among the present invention, the HF purity in the step (3) after the separation of second rectifying tower, drying reaches more than 99.9 %.
The present invention proposes a kind of method of producing trifluoro-ethylene coproduction anhydrous hydrogen fluoride, selects γ-Al for use
2O
3And α-Al
2O
3Be catalyzer, HFC-134a is had higher transformation efficiency and stability.HF through the first knockout tower after separating can be used for deactivated catalyst, also can pack sale.HFC-134a and rare gas element through the second knockout tower after separating carry out recycle, and TrFE sells through alkali cleaning, drying, condensation, rectifying, dry packaging final prod afterwards.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
The specific examples mode
Be further described below by a kind of method of producing trifluoro-ethylene coproduction anhydrous hydrogen fluoride of the present invention of some embodiment, but the present invention is not limited to these embodiment.
Embodiment 1
With reference to Fig. 1: with a certain amount of α-Al
2O
3In the reactor bed of packing into.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 450 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 2
With reference to Fig. 1: with a certain amount of α-Al
2O
3In the reactor bed of packing into, AHF after the vaporizing chamber vaporization, is fluoridized 2 and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and N
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 480 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 3
With reference to Fig. 1: with a certain amount of γ-Al
2O
3In the reactor bed of packing into.Press HFC-134a and CO
2Mol ratio be 1:9, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 4
With reference to Fig. 1: with γ-Al
2O
3And α-Al
2O
3Mix in the reactor bed of packing into by the molar weight of 1:1, HF after the vaporizing chamber vaporization, is fluoridized 2 and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 5
Molar weight by 1:20 takes by weighing glucose and γ-Al
2O
3, then glucose solution is impregnated into γ-Al
2O
3In, roasting forms C@ γ-Al under super-dry, nitrogen atmosphere then
2O
3Catalyzer.
With reference to Fig. 1: catalyzer is packed in the reactor bed, and HF fluoridizes 2 h and 4 h to catalyzer respectively under 260 ℃ and 400 ℃ after the vaporizing chamber vaporization then.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and N
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 6
With reference to Fig. 1: with γ-Al
2O
3Mix in the reactor bed of packing into by the molar weight of 15:1 with ZnO, HF after the vaporizing chamber vaporization, is fluoridized 2 h and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 7
With reference to Fig. 1: with γ-Al
2O
3Mix in the reactor bed of packing into by the molar weight of 15:1 with MgO, HF after the vaporizing chamber vaporization, is fluoridized 2 h and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 450 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 8
With reference to Fig. 1: with γ-Al
2O
3Mix in the reactor bed of packing into by the molar weight of 10:1 with NiO, HF after the vaporizing chamber vaporization, is fluoridized 2 h and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 9
With reference to Fig. 1: with γ-Al
2O
3And Cr
2O
3Mix in the reactor bed of packing into by the molar weight of 10:1, HF after the vaporizing chamber vaporization, is fluoridized 2 h and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 10
With reference to Fig. 1: with γ-Al
2O
3, NiO and Co
2O
3Mix in the reactor bed of packing into by the molar weight of 18:1:1, HF after the vaporizing chamber vaporization, is fluoridized 2 h and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Embodiment 11
With reference to Fig. 1: with γ-Al
2O
3, Co
2O
3And La
2O
3Mix in the reactor bed of packing into by the molar weight of 18:1:1, HF after the vaporizing chamber vaporization, is fluoridized 2 h and 4 h respectively under 260 ℃ and 400 ℃.Press HFC-134a and CO
2Mol ratio be 1:5, feed HFC-134a and CO
2Gas forms mixed gas, behind heat exchanger in reactor, at 400 ℃, normal pressure, 675 h
-1Air speed under react; Reacted gas utilizes through the isolated HF gas circulation of first knockout tower, HF gas can also be separated through second rectifying tower, then the dry HF gas that obtains the above purity of 99.9 %.Isolated tail gas further separates TrFE, HFC-134a, CO through knockout tower
2Gas and other micro-component enter second knockout tower and further separate HFC-134a and CO
2Gas circulation is utilized, isolated TrFE and other minor component are through alkali cleaning and drying, carry out condensation liquefaction after the compressed machine compression then, enter rectifying tower again and carry out rectifying, the directly emptying of trace noncondensable gas, the purity of main rectifying product TrFE can reach more than 99.9 %, at last TrFE is carried out finished product packing after drying.
In the reaction process reactor I tail gas is analyzed, analytical results is asked for an interview table 1.
Table 1. embodiment 1-12 catalyzer is to the activity of HFC-134a and the selectivity of 1,1,2-trifluoro propene
Claims (4)
1. produce the hydrofluoric method of trifluoro-ethylene coproduction for one kind, it is characterized in that concrete steps are as follows:
(1), the catalyzer of in fixed-bed reactor, packing into, earlier 200 ℃ of dryings under rare gas element feed HF gas then, with rare gas element catalyzer are carried out activation treatment after the vaporizing chamber vaporization;
(2), with 1,1,1,3-Tetrafluoroethane (HFC-134a) and the described rare gas element of step (1) 1:1～1:20 in molar ratio mix, enter in the fixed bedreactor of step (1) gained after heating, the control temperature of reaction is that 300～650 ℃, air speed are 300～2000 h
-1, pressure is 0.1～0.8 Mp;
(3), step (2) reacted tail gas is separated through first knockout tower, isolated hydrogen fluoride is capable of circulation for pretreatment catalyst, in addition can also be through second rectifying tower, be packaged into the HF product after dry;
(4), low-boiling-point substance HFC-134a, rare gas element and trifluoro-ethylene after first knockout tower in the step (2) separated, proceed to separate at second knockout tower, HFC-134a and rare gas element enter recycle in separately the raw material storage equipment; Wherein: the weight ratio that trifluoro-ethylene, HF and HFC-134a press 1:1:1 generates;
(5), with the trifluoro-ethylene that separates in the step (4), behind alkali cleaning, drying, compression, condensation liquefaction, enter first rectifying tower, the trifluoro-ethylene that will handle from first rectifying tower is packed after drying at last.
2. method according to claim 1, it is characterized in that: the rare gas element in the step (1) is He, Ar or N
2One or both.
3. method according to claim 1 is characterized in that: the HF gas after the vaporizer vaporization and the mol ratio of rare gas element are 1:1～1:8.
4. method according to claim 1, it is characterized in that: catalyzer is γ-Al described in the step (1)
2O
3Or α-Al
2O
3
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844411A (en) * | 2015-04-03 | 2015-08-19 | 北京宇极科技发展有限公司 | Method for synthesizing hexafluoro-1,3-butadiene |
| 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 |
| JPWO2015115548A1 (en) * | 2014-01-30 | 2017-03-23 | 旭硝子株式会社 | Method for producing trifluoroethylene |
| 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 |
| WO2024057657A1 (en) * | 2022-09-16 | 2024-03-21 | Ａｇｃ株式会社 | Fluoroolefin production method |
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| US5856593A (en) * | 1994-08-08 | 1999-01-05 | Imperial Chemical Industries Plc | Process for the production of fluorine containing olefins |
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| JPWO2015115548A1 (en) * | 2014-01-30 | 2017-03-23 | 旭硝子株式会社 | Method for producing trifluoroethylene |
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| CN104844411B (en) * | 2015-04-03 | 2017-08-29 | 北京宇极科技发展有限公司 | A kind of method for synthesizing the butadiene of hexafluoro 1,3 |
| 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 |
| WO2024057657A1 (en) * | 2022-09-16 | 2024-03-21 | Ａｇｃ株式会社 | Fluoroolefin production method |
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