CN101637732B - Dehydrofluorination catalyst - Google Patents
Dehydrofluorination catalyst Download PDFInfo
- Publication number
- CN101637732B CN101637732B CN2009101626187A CN200910162618A CN101637732B CN 101637732 B CN101637732 B CN 101637732B CN 2009101626187 A CN2009101626187 A CN 2009101626187A CN 200910162618 A CN200910162618 A CN 200910162618A CN 101637732 B CN101637732 B CN 101637732B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ammonium
- fluoride
- dehydrofluorination
- acid ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a dehydrofluorination catalyst aiming at solving the problems of low activity of the catalyst and low selectivity to Z-type fluoroolefin. The precursor of the catalyst consists of 40-80 percent of trivalent chromium compound and 20-60 percent of fluoride of metal ammonium by mass percent, wherein the trivalent chromium compound is chromic oxide or chromium hydroxide, and the fluoride of metal ammonium is hexafluoro ammonium metatitanic, hexafluoro ammonium antimonite or hexafluoro ammonium stannate. The catalyst is prepared by the following method: evenly mixing the trivalent chromium compound and the fluoride of metal ammonium by mass percent, pressing and shaping the mixture, and then baking and activating hydrogen fluoride. The dehydrofluorination catalyst has high activity and selectivity to the Z-type fluoroolefin, and is mainly used for preparing corresponding Z-type fluoroolefin by dehydrofluorination using hydrofluorocarbon as the material under the condition of gaseous phase reaction.
Description
Technical field
The present invention relates to a kind of Dehydrofluorination catalyst, especially relate to and be used for the Dehydrofluorination catalyst that hydrogen fluorohydrocarbon dehydrofluorination under the gas phase condition prepares Z type fluoroolefin.
Background technology
1,1,1,3-tetrafluoeopropene (HFO-1234ze) and 1,2,3,3,3-five fluorine propylene (HFO-1225ye) have latent value (GWP) of lower greenhouse effects and the latent value (ODP) of zero ozone depletion, are considered to the most potential and substitute 1,1,1, the third generation ODS substitute of 2-HFC-134a (HFC-134a) is widely used as cold-producing medium, blowing agent, aerosol propellant, solvent etc.Above-mentioned fluoroolefin is made by hydrogen fluorohydrocarbon dehydrofluorination usually.At present, the Dehydrofluorination catalyst of hydrogen fluorohydrocarbon chrome catalysts normally.
World patent WO2008008350A2 has reported a kind of CrF
3Catalyst is in 348 ℃ of catalysis 1,1,1,2,2,3-HFC-236fa (HFC-236cb) dehydrofluorination is made HFO-1225ye, operation is after 26 hours continuously, and the HFC-236cb conversion ratio is 23.8%, Z-1,2,3,3,3-five fluorine propylene (Z-HFO-1225ye) selectivity are 82.8%, E-1,2,3,3,3-five fluorine propylene (E-HFO-1225ye) selectivity are 10.9%.This catalyst exists active and to the low problem of selectivity of Z type fluoroolefin.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that exists in the background technology, provide a kind of active high, to the high Dehydrofluorination catalyst of selectivity of Z type fluoroolefin.
In order to solve the problems of the technologies described above, the present invention is with the proportionally mixed catalyst precursor that gets of the fluoride of trivalent chromium compound and metal acid ammonium, when presoma during in high-temperature roasting, the metal acid ammonium fluoride, comprise ammonium hexa-fluorotitanate, hexafluoro-antimonic acid ammonium or hexafluoro stannic acid ammonium, decomposes has a large amount of volatile matters to produce, make catalyst have characteristics such as specific area height, pore volume are big, micropore ratio height, improved the catalytic activity of catalyst.The decomposition of metal acid ammonium fluoride has produced metal fluoride,, discovers that above-mentioned metal fluoride can effectively improve the selectivity of Z type fluoroolefin as titanium tetrafluoride, antimony pentafluoride, tin tetrafluoride.
The invention provides a kind of Dehydrofluorination catalyst, its characteristics are that the presoma of this catalyst is made up of the fluoride of trivalent chromium compound and metal acid ammonium, its quality percentage composition: trivalent chromium compound is 40%～80%, the fluoride of metal acid ammonium is 20%～60%, wherein trivalent chromium compound is chromium oxide or chromium hydroxide, the fluoride of metal acid ammonium is ammonium hexa-fluorotitanate, hexafluoro-antimonic acid ammonium or hexafluoro stannic acid ammonium, and this catalyst can obtain by the following method:
(1) fluoride with trivalent chromium compound and metal acid ammonium mixes by mass percentage, and compression moulding obtains catalyst precursor;
(2) catalyst precursor that step (1) is obtained carries out roasting after 6～15 hours at 300 ℃～450 ℃, and 250 ℃～350 ℃ with hydrogen fluoride activation 6～15 hours, makes Dehydrofluorination catalyst.
The preferred ammonium hexa-fluorotitanate of the fluoride of metal acid ammonium of the present invention.
The preferred chromium hydroxide of trivalent chromium compound of the present invention.
Cr of the present invention (OH)
3Can obtain by the following method: chromic soluble salt is dissolved in the water, adds precipitating reagents at 20 ℃～90 ℃, precipitation between the control pH value of solution 7.5～8.5, after filtration, washing, obtain Cr (OH) 100 ℃～200 ℃ dryings
3Above-mentioned chromic soluble salt can be chromic nitrate, chromium sulfate, chromium chloride or chromium+oxalic acid, preferred chromic nitrate; Precipitating reagent can be NaOH, sodium carbonate, sodium acid carbonate or ammoniacal liquor, preferred ammoniacal liquor.
The mixture of preferred chromium hydroxide of the presoma of Dehydrofluorination catalyst of the present invention and ammonium hexa-fluorotitanate, its quality percentage composition is 65% and 35%;
The preparation method of Dehydrofluorination catalyst of the present invention may further comprise the steps:
(1) fluoride with trivalent chromium compound and metal acid ammonium mixes by mass percentage, and compression moulding obtains catalyst precursor;
(2) catalyst precursor that step (1) is obtained carries out roasting after 6～15 hours at 300 ℃～450 ℃, and 250 ℃～350 ℃ with hydrogen fluoride activation 6～15 hours, makes Dehydrofluorination catalyst.
Increase the oxide of metals such as zinc, nickel, magnesium or cobalt or hydroxide as co-catalyst in the presoma of catalyst, can increase the mechanical strength or the catalytic activity of catalyst, the present invention is not further limited.
Dehydrofluorination catalyst of the present invention is applicable to that hydrogen fluorohydrocarbon catalytic dehydrofluorination prepares serial fluoroolefin under the gas phase condition, is particularly useful for dehydrofluorination, isomerization one step preparation Z type fluoroolefin, for example: 1,1,1,2,2,3-HFC-236fa (HFC-236cb) or 1,1,1,2,3,3-HFC-236fa (HFC-236ea) dehydrofluorination prepares Z-1,2,3,3,3-five fluorine propylene (Z-HFO-1225ye), 1,1,1,2,3-pentafluoropropane (HFC-245eb) or 1,1,1,3,3-pentafluoropropane (HFC-245fa) dehydrofluorination prepares Z-1,1,1,3-tetrafluoeopropene (Z-HFO-1234ze) etc.
The present invention compared with prior art, have following advantage: Dehydrofluorination catalyst of the present invention is used for the reaction of synthetic Z type fluoroolefin of one step of hydrogen fluorohydrocarbon dehydrofluorination isomerization, not only active good, and to the selectivity height of Z type fluoroolefin, the present invention moves 100 hours continuously, the HFC-236cb conversion ratio is 92% and to Z-1,2,3,3, the selectivity of 3-five fluorine propylene is 94%, and the CrF of documents
3Catalyst moves 26 hours continuously, and the HFC-236cb conversion ratio is 23.8%, to Z-1, and 2,3,3,3-five fluorine propylene (Z-HFO-1225ye) selectivity are 82.8%.
The specific embodiment
The present invention is described in more detail below by embodiment, but be not limited to given example.
Analytical instrument: Autosorp ZXF-5 type BET analyzer (Xibei Chemical Inst manufactures and designs), Tianjin, island GC-MS2010, chromatographic column is capillary column Al
2O
3/ S " 50m * 0.320mm * 0.25 μ m " (manufacturing of chromatographic technique research and development centre of Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences).
The specific area measuring method: specific surface area of catalyst adopts the BET method to measure, and used instrument is an AutosorpZXF-5 type BET analyzer, and sample is handled in 50 ℃ of oven dry, at 180 ℃, and 1.33 * 10
-6Low temperature N is carried out in Pa vacuum outgas 5 hours then
2Absorption.
The GC-MS analytical method: product is got gaseous sample and is carried out the GC-MS analysis after washing, alkali cleaning and drying.170 ℃ of column temperatures, 200 ℃ of detector temperatures, 200 ℃ of temperature of vaporization chamber.
Embodiment 1
Chromic nitrate is dissolved in the water, adds precipitating reagent ammoniacal liquor, between the control pH value of solution 7.5-8.5 scope at 60 ℃, it is fully precipitated under stirring condition,, spend deionised water to neutral with the slurry by filtration that forms, 150 ℃ of dryings 12 hours, obtain Cr (OH) then
3
With gained Cr (OH)
3Is 70% and 30% evenly to mix with ammonium hexa-fluorotitanate by the quality percentage composition, compression molding, make catalyst precursor, catalyst precursor 400 ℃ of roastings 10 hours in Muffle furnace, the tubular reactor of packing into then is warming up to 300 ℃, feed hydrogen fluoride gas activation earlier 2 hours, heating rate with 1 ℃/min is warming up to 350 ℃ then, continues activation 10 hours, makes Dehydrofluorination catalyst.
The specific area of measuring catalyst with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature is 56.1m
2G
-1, pore volume is 0.20mlg
-1, and the aperture is 36% less than the boring ratio example of 2nm.
At internal diameter is in the 38mm nickel pipe fixed bed type reactor, the above-mentioned Dehydrofluorination catalyst that makes of the 30ml that packs into, 350 ℃ of reaction temperatures, HFC-236cb air speed 50h
-1, to react after 100 hours, product is formed with the GC-MS analyzing organic substance after washing, alkali cleaning and drying, and obtaining the HFC-236cb conversion ratio is 92%, and the Z-HFO-1225ye selectivity is 94%.
Embodiment 2
Preparation of catalysts technology is substantially the same manner as Example 1, and that different is Cr (OH)
3With the percentage composition of ammonium hexa-fluorotitanate quality be 80% and 20%.
The specific area of measuring catalyst with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature is 53.5m
2G
-1, pore volume is 0.18mlg
-1, and the aperture is 33% less than the boring ratio example of 2nm.
At internal diameter is in the 38mm nickel pipe fixed bed type reactor, the above-mentioned Dehydrofluorination catalyst that makes of the 30ml that packs into, 350 ℃ of reaction temperatures, HFC-236ea air speed 100h
-1, to react after 100 hours, sampling is after washing, alkali cleaning and drying, and GC-MS analyzes, and obtaining the HFC-236ea conversion ratio is 98%, and the Z-HFO-1225ye selectivity is 96%.
Embodiment 3
Preparation of catalysts technology is substantially the same manner as Example 1, and that different is Cr (OH)
3With the percentage composition of ammonium hexa-fluorotitanate quality be 60% and 40%.
The specific area of measuring catalyst with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature is 46.3m
2G
-1, pore volume is 0.19mlg
-1, and the aperture is 32% less than the boring ratio example of 2nm.
At internal diameter is in the 38mm nickel pipe fixed bed type reactor, the above-mentioned Dehydrofluorination catalyst that makes of the 30ml that packs into, 350 ℃ of reaction temperatures, HFC-245eb air speed 50h
-1, to react after 100 hours, sampling is after washing, alkali cleaning and drying, and GC-MS analyzes, and obtaining the HFC-245eb conversion ratio is 95%, and the Z-HFO-1234ze selectivity is 90%.
Embodiment 4
Preparation of catalysts technology is substantially the same manner as Example 1, and different is that ammonium hexa-fluorotitanate changes the hexafluoro-antimonic acid ammonium into, Cr (OH)
3With the percentage composition of hexafluoro-antimonic acid ammonium quality be 65% and 35%.
The specific area of measuring catalyst with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature is 51.4m
2G
-1, pore volume is 0.18mlg
-1, and the aperture is 34% less than the boring ratio example of 2nm.
At internal diameter is in the 38mm nickel pipe fixed bed type reactor, the above-mentioned Dehydrofluorination catalyst that makes of the 30ml that packs into, 350 ℃ of reaction temperatures, HFC-245fa air speed 50h
-1, react after 100 hours,, sampling is after washing, alkali cleaning and drying, and GC-MS analyzes, and obtaining the HFC-245fa conversion ratio is 100%, and the Z-HFO-1234ze selectivity is 95%.
Embodiment 5
Preparation of catalysts technology is substantially the same manner as Example 1, and different is that ammonium hexa-fluorotitanate changes hexafluoro stannic acid ammonium into, Cr (OH)
3With the percentage composition of hexafluoro stannic acid ammonium quality be 75% and 25%.
The specific area of measuring catalyst with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature is 52.7m
2G
-1, pore volume is 0.16mlg
-1, and the aperture is 32% less than the boring ratio example of 2nm.
At internal diameter is in the 38mm nickel pipe fixed bed type reactor, the above-mentioned Dehydrofluorination catalyst that makes of the 30ml that packs into, 350 ℃ of reaction temperatures, HFC-236ea air speed 100h
-1, react after 100 hours,, sampling is after washing, alkali cleaning and drying, and GC-MS analyzes, and obtaining the HFC-236ea conversion ratio is 100%, and the Z-HFO-1225ye selectivity is 97%.
Embodiment 6
Preparation of catalysts technology is substantially the same manner as Example 1, and difference is the Cr (OH) that will make
3Roasting obtained Cr in 6 hours in 350 ℃ of hydrogen atmospheres
2O
3, Cr
2O
3With the percentage composition of ammonium hexa-fluorotitanate quality be 65% and 35%.
The specific area of measuring catalyst with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature is 50.8m
2G
-1, pore volume is 0.18mlg
-1, and the aperture is 31% less than the boring ratio example of 2nm.
At internal diameter is in the 38mm nickel pipe fixed bed type reactor, the above-mentioned Dehydrofluorination catalyst that makes of the 30ml that packs into, 350 ℃ of reaction temperatures, HFC-236ea air speed 100h
-1, react after 100 hours,, sampling is after washing, alkali cleaning and drying, and GC-MS analyzes, and obtaining the HFC-236ea conversion ratio is 98%, and the Z-HFO-1225ye selectivity is 95%.
Claims (2)
1. Dehydrofluorination catalyst, the presoma that it is characterized in that this catalyst is made up of the fluoride of trivalent chromium compound and metal acid ammonium, its quality percentage composition: trivalent chromium compound is 40%～80%, the fluoride of metal acid ammonium is 20%～60%, wherein trivalent chromium compound is chromium oxide or chromium hydroxide, the fluoride of metal acid ammonium is ammonium hexa-fluorotitanate, hexafluoro-antimonic acid ammonium or hexafluoro stannic acid ammonium, and this catalyst obtains by being prepared as follows method:
(1) fluoride with trivalent chromium compound and metal acid ammonium mixes by mass percentage, and compression moulding obtains catalyst precursor;
(2) catalyst precursor that step (1) is obtained carries out roasting after 6～15 hours at 300 ℃～450 ℃, and 250 ℃～350 ℃ with hydrogen fluoride activation 6～15 hours, makes Dehydrofluorination catalyst.
2. Dehydrofluorination catalyst according to claim 1, it is characterized in that the presoma of this catalyst is made up of chromium hydroxide and ammonium hexa-fluorotitanate, its quality percentage composition: chromium hydroxide is 65%, ammonium hexa-fluorotitanate is 35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101626187A CN101637732B (en) | 2009-08-14 | 2009-08-14 | Dehydrofluorination catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101626187A CN101637732B (en) | 2009-08-14 | 2009-08-14 | Dehydrofluorination catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101637732A CN101637732A (en) | 2010-02-03 |
| CN101637732B true CN101637732B (en) | 2011-05-25 |
Family
ID=41613022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101626187A Active CN101637732B (en) | 2009-08-14 | 2009-08-14 | Dehydrofluorination catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101637732B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105327695A (en) * | 2014-08-06 | 2016-02-17 | 浙江蓝天环保高科技股份有限公司 | Chromium based catalyst for dehydrofluorination, and preparation method and application thereof |
| CN105330513B (en) * | 2015-10-22 | 2017-08-08 | 北京宇极科技发展有限公司 | A kind of method that catalyzes and synthesizes ring-type HF hydrocarbon of high selectivity |
-
2009
- 2009-08-14 CN CN2009101626187A patent/CN101637732B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101637732A (en) | 2010-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104907065B (en) | Fluorination catalyst, Preparation method and use | |
| Silahua-Pavon et al. | Production of 5-HMF from glucose using TiO2-ZrO2 catalysts: Effect of the sol-gel synthesis additive | |
| CN102513136B (en) | Fluorinated chrome base fluorination catalyst and application thereof | |
| CN104475080B (en) | A kind of mesoporous chromium oxide-based catalyst for de-hydrogen halide | |
| Liu et al. | Promoting effect of unreducible metal doping on OMS-2 catalysts for gas-phase selective oxidation of ethanol | |
| US11406965B2 (en) | Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons | |
| US11452990B2 (en) | Catalyst and process using the catalyst for manufacturing fluorinated hydrocarbons | |
| CN104907063A (en) | Chromium base catalyst, and preparation method and use thereof | |
| CN102836722B (en) | Catalyst used in preparation of fluorine-containing olefin through dehydrohalogenation of halohydrofluoroalkane and preparation method of catalyst | |
| JP5928894B2 (en) | Polyhydric alcohol hydrocracking catalyst, and method for producing 1,3-propanediol using the catalyst | |
| CN101214448A (en) | Chromium base fluorating catalyst and preparation thereof | |
| CN110975876A (en) | Activated carbon supported chromium-based catalyst and preparation method and application thereof | |
| CN107540011A (en) | A kind of catalyst of high-specific surface area, its preparation method and application | |
| CN103041819B (en) | Catalyst for fluoridation and preparation method for same | |
| CN107126954B (en) | Impregnation method for preparing molybdenum-based and tungsten-based fluorine-chlorine exchange catalyst | |
| CN100522356C (en) | Fluorating catalyst and preparation thereof | |
| CN101637732B (en) | Dehydrofluorination catalyst | |
| CN100584457C (en) | Aluminum fluoride base fluorating catalyst, preparation method and application | |
| RU2402378C1 (en) | Catalyst, preparation method thereof and method of fluorinating halogenated hydrocarbons | |
| CN101637733B (en) | Dehydrofluorination catalyst | |
| Sato et al. | Vapor-phase dehydration of 1, 5-pentanediol into 4-penten-1-ol | |
| CN101214446B (en) | Fluorating catalyst and preparation method | |
| CN112774701B (en) | Acid radical intercalation hydrotalcite derived composite oxide and preparation method and application thereof | |
| CN109499589B (en) | Chromium-free environment-friendly catalyst for gas-phase fluorination synthesis of 1,1,1,3,3, 3-hexafluoro-2-butene | |
| CN101214447B (en) | Naluminum fluoride base fluorating catalyst and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |