CN103861579B - A kind of trifluoro-ethylene catalyst for preparing - Google Patents
A kind of trifluoro-ethylene catalyst for preparing Download PDFInfo
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- CN103861579B CN103861579B CN201410102866.3A CN201410102866A CN103861579B CN 103861579 B CN103861579 B CN 103861579B CN 201410102866 A CN201410102866 A CN 201410102866A CN 103861579 B CN103861579 B CN 103861579B
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Abstract
The invention discloses a kind of trifluoro-ethylene catalyst for preparing, particularly a kind of take HFA 134a as the preparation method that the catalyst of trifluoro-ethylene prepared by raw material.The preparation method of this catalyst is: adopt coprecipitation to prepare the carrier of magnesium fluoride and aluminum fluoride, cesium nitrate or potassium nitrate is flooded after roasting, after roasting, adopt the one in equivalent impregnation method load cerous nitrate, yttrium nitrate, nickel nitrate and zirconium nitrate, make catalyst.The present invention can make HFA 134a obtain conversion ratio can reach 62.7%, and the selective of product trifluoro-ethylene is up to 99.2%.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, relate to a kind of catalyst and the preparation thereof of preparing trifluoro-ethylene with HFA 134a.
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.But trifluoro-ethylene boiling point is lower, easy autohemagglutination blast, have higher danger and be difficult to transport and long-term preservation, the research at present in prepared by trifluoro-ethylene is considerably less, fails to produce ripe production technology and technique.
French Patent (FRP) FR2710054, FR2729136 and US Patent No. 5856593A report with HFA 134a (HFC-134a) as catalytic material dehydrofluorination prepares the process route of trifluoro-ethylene.This technique mainly adopts AlF3 to make catalyst, and nitrogen is diluent, the temperature that reaction needed is higher, and 600 DEG C time, the conversion ratio of HFA 134a only has 34%, and catalyst activity is not high, separation of products and purification difficult.
Above-mentioned process route also exists that trifluoro-ethylene yield is lower, severe reaction conditions, catalyst life are short, reaction needed diluent gas, increase the problem of later stage separation costs.
Summary of the invention
The present invention overcomes the deficiency existed in background technology, adopt method of fractional steps Kaolinite Preparation of Catalyst, the carrier of magnesium fluoride and aluminum fluoride is prepared by coprecipitation, cesium nitrate or potassium nitrate is flooded after roasting, equivalent impregnation method load cerous nitrate, yttrium nitrate, nickel nitrate or zirconium nitrate is adopted again after roasting, make multicomponent catalyst, this catalyst has the advantage of high, selective good, the long service life of catalytic activity.
In order to realize object of the present invention, the invention provides a kind of trifluoro-ethylene catalyst for preparing, preparation method's step of described catalyst is as follows: by the soluble-salt of magnesium and aluminium, 0.1-0.5:1 adds polytetrafluoroethylene (PTFE) reaction bulb in molar ratio, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is between 2-5, filter, washing leaching cake is to neutral, filter cake is risen to 450-550 DEG C of roasting 1-4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, one in potassium nitrate, the total mol ratio of soluble-salt of the addition of cesium nitrate or potassium nitrate and magnesium and aluminium is 0.005-0.01:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 450-550 DEG C of roasting 1-4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping cerous nitrate, yttrium nitrate, nickel nitrate or zirconium nitrate, cerium, yttrium, the total mol ratio 0.01-0.05:1 of soluble-salt of the load capacity of nickel or zirconium and magnesium and aluminium, after evaporating water, solid is risen to 450-550 DEG C of roasting 1-4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.
The analysis of product: obtained catalyst is measured 30mL and load in reaction tube, until temperature stabilization after 420 DEG C, pass into 1, 1, 1, 2-HFC-134a, start timing, the time of keeping in touch is 6s, run 20h, product is through washing, after alkali cleaning absorbs HF, drying again, gas-chromatography is analyzed, use GC-2014C type gas chromatograph, chromatographic column is GS-GasPro post, nitrogen does carrier gas, before post, pressure is 60kPa, split ratio is 20:1, adopt fid detector, detector temperature is 220 DEG C, post case 140 DEG C of constant temperature sample introductions, adopt peak area normalization quantitative, obtain the selective data of feed stock conversion and trifluoro-ethylene.
Detailed description of the invention
Provide specific embodiments of the invention below, but do not limit the scope of the invention.
Embodiment 1
The magnesium nitrate of 0.1mol is added in polytetrafluoroethylene (PTFE) reaction bulb, the aluminum nitrate of 1mol, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is 2, filter, washing leaching cake is to neutral, filter cake is risen to 450 DEG C of roasting 1h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, the addition of cesium nitrate and magnesium nitrate, the ratio of aluminum nitrate total mole is 0.005:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 450 DEG C of roasting 4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping cerous nitrate, cerous nitrate addition and magnesium nitrate, the total mol ratio of aluminum nitrate is 0.01:1, after evaporating water, solid is risen to 450 DEG C of roasting 4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.Feed stock conversion is 56.8%, and trifluoro-ethylene is selective reaches 98.7%.
Embodiment 2
Identical with embodiment 1 method of operating, the mol ratio adding magnesium sulfate and aluminum sulfate is 0.1:1, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is 3, filter, washing leaching cake is to neutral, filter cake is risen to 470 DEG C of roasting 3h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, the addition of cesium nitrate and magnesium sulfate, the total mol ratio of aluminum sulfate is 0.007:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 470 DEG C of roasting 3h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping yttrium nitrate, the total mol ratio 0.02:1 of soluble-salt of yttrium nitrate addition and magnesium and aluminium, after evaporating water, solid is risen to 470 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.Feed stock conversion is 55.9%, and trifluoro-ethylene is selective reaches 98.2%.
Embodiment 3
Identical with embodiment 1 method of operating, the mol ratio adding magnesium chloride and aluminium chloride is 0.1:1, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is 4, filter, washing leaching cake is to neutral, filter cake is risen to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, the total mol ratio of soluble-salt of the addition of cesium nitrate and magnesium and aluminium is 0.009:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping nickel nitrate, the total mol ratio 0.04:1 of soluble-salt of nickel nitrate addition and magnesium and aluminium, after evaporating water, solid is risen to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.Feed stock conversion is 60.4%, and trifluoro-ethylene is selective reaches 98.3%.
Embodiment 4
Identical with embodiment 1 method of operating, the mol ratio adding magnesium nitrate and aluminum nitrate is 0.1:1, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is 5, filter, washing leaching cake is to neutral, filter cake is risen to 550 DEG C of roasting 1h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, the total mol ratio of soluble-salt of the addition of cesium nitrate and magnesium and aluminium is 0.01:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 550 DEG C of roasting 1h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping zirconium nitrate, the total mol ratio 0.05:1 of soluble-salt of zirconium nitrate addition and magnesium and aluminium, after evaporating water, solid is risen to 550 DEG C of roasting 1h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.Feed stock conversion is 55.3%, and trifluoro-ethylene is selective reaches 99.1%.
Embodiment 5
Identical with embodiment 3 method of operating, the total mol ratio 0.02:1 of soluble-salt of nickel nitrate addition and magnesium and aluminium.Feed stock conversion is 57.6%, and trifluoro-ethylene is selective reaches 98.9%.
Embodiment 6
The operation identical with embodiment 1, the mol ratio adding magnesium nitrate and aluminum nitrate is 0.2:1, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is 4, filter, washing leaching cake is to neutral, filter cake is risen to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, the total mol ratio of soluble-salt of the addition of potassium nitrate and magnesium and aluminium is 0.009:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping nickel nitrate, the total mol ratio 0.04:1 of soluble-salt of nickel nitrate addition and magnesium and aluminium, after evaporating water, solid is risen to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.Feed stock conversion is 62.7%, and trifluoro-ethylene is selective reaches 98.5%.
Carry out life test to the catalyst of embodiment 6, evaluation result is in table 1.
Table 1
Embodiment 7
Substantially identical with the method for operating of embodiment 6, the mol ratio that difference is to add magnesium nitrate and aluminum nitrate is 0.3:1.Feed stock conversion is 61.3%, and trifluoro-ethylene is selective reaches 98.7%.
Embodiment 8
Substantially identical with the method for operating of embodiment 6, the mol ratio that difference is to add magnesium nitrate and aluminum nitrate is 0.5:1.Feed stock conversion is 58.9%, and trifluoro-ethylene is selective reaches 99.2%.
Claims (2)
1. a trifluoro-ethylene catalyst for preparing, it is characterized in that being prepared by following steps: by the soluble-salt of magnesium and aluminium, 0.1-0.5:1 adds polytetrafluoroethylene (PTFE) reaction bulb in molar ratio, add water stirring and dissolving, dropwise add the hydrofluoric acid that mass concentration is 40%, adjust ph is between 2-5, filter, washing leaching cake is to neutral, filter cake is risen to 450-550 DEG C of roasting 1-4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, filter cake after roasting is put into flask, add cesium nitrate, one in potassium nitrate, the total mol ratio of soluble-salt of the addition of cesium nitrate or potassium nitrate and magnesium and aluminium is 0.005-0.01:1, be dissolved in water, stir 3h, by water evaporate to dryness, solid rises to 450-550 DEG C of roasting 1-4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, solid is added in flask, adopt equivalent impregnation method dipping cerous nitrate, yttrium nitrate, nickel nitrate or zirconium nitrate, cerium, yttrium, the total mol ratio 0.01-0.05:1 of soluble-salt of the load capacity of nickel or zirconium and magnesium and aluminium, after evaporating water, solid is risen to 450-550 DEG C of roasting 1-4h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.
2. catalyst according to claim 1, it is characterized in that, by the soluble-salt of magnesium and aluminium, in molar ratio for 0.2:1 adds polytetrafluoroethylene (PTFE) reaction bulb, adjust ph is 4, filter cake is risen to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, the total mol ratio of soluble-salt of the addition of cesium nitrate or potassium nitrate and magnesium and aluminium is 0.008:1, solid rises to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, adopt equivalent impregnation method dipping cerous nitrate, yttrium nitrate, nickel nitrate or zirconium nitrate, cerium, yttrium, the total mol ratio 0.04:1 of soluble-salt of the load capacity of nickel or zirconium and magnesium and aluminium, solid is risen to 500 DEG C of roasting 2h with the heating rate of 10 DEG C/min in Muffle furnace, cooling, make catalyst.
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| CN104529690A (en) * | 2014-12-30 | 2015-04-22 | 内蒙古三爱富万豪氟化工有限公司 | Method for coproducing trifluoroethylene and vinyl fluoride |
| CN105597795B (en) * | 2015-11-06 | 2018-04-17 | 西安近代化学研究所 | A kind of preparation method of nanometer of Naluminum fluoride base catalyst |
| CN106000428B (en) * | 2016-05-20 | 2018-11-13 | 浙江工业大学 | A kind of HFA 134a catalytic pyrolysis generates the catalyst and in situ regeneration method of trifluoro-ethylene |
| CN106902850B (en) * | 2017-02-10 | 2019-08-27 | 西安近代化学研究所 | A kind of 1,1,1,2- tetrafluoroethane prepares trifluoro-ethylene catalyst |
| CN114560750A (en) * | 2022-01-28 | 2022-05-31 | 浙江巨化技术中心有限公司 | Preparation method of 1-chloro-2, 3, 3-trifluoropropene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468323A (en) * | 2007-12-10 | 2009-07-01 | 霍尼韦尔国际公司 | Method for making catalyst compositions of alkali metal halide-doped bivalent metal fluorides and process for making fluorinated olefins |
| US20110245549A1 (en) * | 2010-04-05 | 2011-10-06 | Honeywell International Inc. | Integrated Process to Co-Produce Trans-1-Chloro-3,3,3-Trifluoropropene and Trans-1,3,3,3-Tetrafluoropropene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101468323A (en) * | 2007-12-10 | 2009-07-01 | 霍尼韦尔国际公司 | Method for making catalyst compositions of alkali metal halide-doped bivalent metal fluorides and process for making fluorinated olefins |
| US20110245549A1 (en) * | 2010-04-05 | 2011-10-06 | Honeywell International Inc. | Integrated Process to Co-Produce Trans-1-Chloro-3,3,3-Trifluoropropene and Trans-1,3,3,3-Tetrafluoropropene |
Non-Patent Citations (1)
| Title |
|---|
| "气相催化脱氟化氢制备含氟烯烃催化剂的研究进展";白彦波等;《化工进展》;20131231;第32卷;第2387-2391，2452页 * |
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