CN109718813A - Gas phase fluorination synthesizes 3,3,3- trifluoro propene chromium-free environment-friendly catalyst - Google Patents
Gas phase fluorination synthesizes 3,3,3- trifluoro propene chromium-free environment-friendly catalyst Download PDFInfo
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- CN109718813A CN109718813A CN201811540700.4A CN201811540700A CN109718813A CN 109718813 A CN109718813 A CN 109718813A CN 201811540700 A CN201811540700 A CN 201811540700A CN 109718813 A CN109718813 A CN 109718813A
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Abstract
The present invention discloses a kind of tetra- chloropropane of gas phase catalysis 1,1,1,3- and synthesizes 3,3,3- trifluoro propene chromium-free environment-friendly catalyst and preparation method thereof with hydrogen fluoride reaction.A series of the problems such as being that there are environmental problems in order to solve traditional chromium-based fluorination catalyst, largely causing serious pollutions, health using heavy metal chromium.Catalyst group disclosed by the invention becomes M/MgF2, wherein matrix MgF2To be greater than 120m with Rutile Type and nanometer spherical structure, specific surface area2/ g, the superior high stability MgF of anti-sintering property in 500 DEG C2, active component M is selected from Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+、Cu2+One or more of.Catalyst preparation is added dropwise fluorination reagent at 150~240 DEG C and obtains catalyst xerogel the following steps are included: the polyhydric alcohol solutions of (1) preparation source containing magnesium and doped metal ion；(2) xerogel is roasted at 300~500 DEG C, finally Chrome-free high performance catalyst is made in fluorination treatment at 150~400 DEG C.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to a kind of 1,1,1,3- tetra- chloropropane of gas phase catalysis and hydrogen fluoride reaction
Synthesize 3,3,3- trifluoro propene chromium-free environment-friendly catalyst.
Background technique
3,3,3- trifluoro propenes, abbreviation HFO-1243zf or TFP, ozone depletion value (ODP) are 0, the latent value of greenhouse effects
(GWP) it is only 0.29, can be used as the base stock of 2,3,3,3- tetrafluoropropene (HFO-1234yf) of synthesizing environment-friendly refrigerant, it can also
It is used to prepare mix refrigerant substitution R22, R134a and R410A, also acts as the high scores such as monomer synthesis fluorine silicone rubber, fluorosilicon oil
Sub- material.
So far, in known numerous HFO-1243zf synthetic methods, with 1,1,1,3- tetra- chloropropane and anhydrous hydrogen fluoride
For raw material through step gas phase fluorination synthesis with raw material is cheap and easy to get, route is short, easy to operate, space-time yield is high, is easy to amplify
The characteristics of, most by the concern of industry, wherein core technology is corresponding fluorination catalyst.United States Patent (USP) US4465786 is disclosed
It is a kind of to realize that gas phase fluorination synthesizes HFO-1243zf using the oxyfluoride of chromium as catalyst.Chinese patent CN102001912A is public
It has opened a kind of using chromium, aluminium, zinc, cobalt, magnesium, the fluoride of indium or oxyfluoride as the above-mentioned gas phase fluorination of catalyst realization.In
State patent CN102388006B realizes gas phase fluorination synthesis HFO-1243zf in the presence of disclosing a kind of zinc/chromium oxide catalyst.
Chinese patent CN100500626C, which is disclosed, realizes gas phase fluorination synthesis HFO-1243zf using a kind of chromium base high-performance catalyst.
The gas phase fluorination catalyst of above-mentioned report is using chromium as core component, however chromium is as a heavy metal species
Element, a large amount of discharges can cause ecological environment seriously to pollute；Especially Cr VI is a kind of extremely toxic substance to animal, human health
It constitutes and greatly threatens.Based on this, to cope with increasingly serious Environmental Protection Situation and stringent laws and regulations, there is an urgent need to design,
High-performance chromium-free catalyst is prepared for the synthesis HFO-1243zf reaction of tetra- chloropropane of gas phase fluorination 1,1,1,3-.
Summary of the invention
In view of the defects existing in the prior art with deficiency, the object of the present invention is to provide a kind of without chromium, environmental-friendly, living
The high gas phase fluorination catalyst of property.This catalyst of the invention, which has, is free of heavy metal, environmentally protective, specific surface area
Greatly, the good feature of the anti-caking power of nanometer spherical structure, high temperature, to obtain the gas phase catalytic fluorination of high activity, high stability
Reactivity worth.
Traditional chromium-based fluorination catalyst large specific surface area, generally in 80~150m2/ g, high-specific surface area create a large amount of anti-
Active sites are answered, it is thus achieved that the Efficient Conversion of gas phase fluorination.In consideration of it, by design, constructing in high temperature containing fluorine atmosphere
The high-specific surface area MgF that can be equally stabilized down2, and then by adulterate other metal ions realize its surface acid center and
The regulation of texturizing properties can be obtained equally and have active sites needed for catalytic vapor phase fluorination reacts.In addition, passing through control MgF2Ruler
Very little can be greatly improved mass-transfer efficiency in nanoscale and spherical structure, so that macrodynamics reaction row in heterogeneous catalysis process
To be improved and carbon deposition rate being effectively reduced.The foundation of above-mentioned multiple unique texture, structure is so that environmental type Chrome-free is high
The preparation of performance catalysts for gas phase fluorination is achieved.
In order to realize above-mentioned technical assignment, the present invention is realised by adopting the following technical scheme:
A kind of 3,3,3- trifluoro propene chromium-free environment-friendly catalyst of gas phase fluorination synthesis, it is characterised in that the catalyst group
As M/MgF2, wherein matrix MgF2To be greater than 120m with Rutile Type and nanometer spherical structure, specific surface area2/g、500℃
The interior superior high stability MgF of anti-sintering property2, active component M is selected from Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4 +、Cu2+One or more of, M mass accounts for the 5%~20% of catalyst gross mass；
The method for preparing catalyst is as follows:
(1) to containing Mg at 150~240 DEG C2+And fluorination reagent is added dropwise in the polyhydric alcohol solutions of M, continue after being added dropwise
6~12h is stirred, M/MgF is obtained2Xerogel；
Mg used2+Selected from one of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium methoxide, magnesium ethylate, magnesium acetate；
M used is selected from one or more of nitrate, chloride, sulfate；
Polyalcohol used is selected from one or more of ethylene glycol, propylene glycol, glycerine, tirethylene glycol；
Fluorination reagent used is selected from one of aqueous solution, alcoholic solution, ethereal solution of hydrogen fluoride；
Mg2+Molar ratio with hydrogen fluoride is 1:3~12；
(2) made xerogel in (1) is heat-treated at 300~500 DEG C, then to heat at 150~400 DEG C
Xerogel carries out fluorination treatment and M/MgF is made after processing2Catalyst；
Heat-treating atmosphere is carried out selected from one of air, nitrogen, hydrogen atmosphere；
Fluorine reagent used in fluorination treatment is in hydrogen fluoride, dicholorodifluoromethane, F-22, monochlorotrifluoromethane
One kind；
Gas phase fluorination described further synthesizes 3,3,3- trifluoro propene chromium-free environment-friendly catalyst, it is characterised in that M Fe3 +、La3+Combination, Fe3+With La3+Molar ratio be 1:0.2~1.
Gas phase fluorination described further synthesizes preparation method of 3,3, the 3- trifluoro propenes with chromium-free environment-friendly catalyst, feature
The concentration for being the fluorination reagent is 20wt.%~70wt.%.
Chromium-free environment-friendly catalyst described further, it is characterised in that catalyst is used for 1,1,1,3- tetra- chloropropane and hydrogen fluoride
The gas phase catalytic fluorination synthesis 3,3,3- trifluoro propene reaction of progress.
Beneficial effects of the present invention: compared with prior art, the present invention having following beneficial technical effect:
1. the present invention provides one kind without chromium and other heavy metals, environment friend compared with traditional chromium-based fluorination catalyst
The good MgF of large specific surface area well, nanometer spherical structure, the anti-caking power of high temperature2Base fluorating catalyst and preparation method thereof；②
Preparation method provided by the invention can be easily achieved the modulation to made catalyst texture, structure and surface acidity, can be made
Specific surface area is greater than 120m2/ g, the superior fluorination magnesium-base catalyst of anti-sintering property in 500 DEG C；3. the present invention is to magnesium source used
It has no special requirements, applicability is wide, at low cost；4. nanometer spherical prepared by the present invention is fluorinated magnesium-base catalyst, facilitate material
In catalyst surface adsorption desorption, improve mass transfer, and then improves reaction efficiency, inhibits carbon distribution.
Detailed description of the invention
Fig. 1 is M/MgF2The representative TEM of catalyst schemes
Specific embodiment
Specific embodiments of the present invention are given below, but do not limit the scope of the invention.
Catalyst performance evaluation is as follows: measuring 30mL catalyst and is transferred in fixed-bed tube reactor, is warming up to 260 DEG C simultaneously
It is passed through hydrogen fluoride gas after dry 2h, then passes to 1,1,1,3- tetra- chloropropane, hydrogen fluoride and 1,1,1,3- tetra- chloropropane rubs
You are than being 10:1, and time of contact is 8 seconds, and product absorbs hydrogen fluoride, the laggard gas-chromatography of hydrogen chloride through water, alkali cleaning after operation 12h
Instrument is analyzed, and calculates the conversion ratio of 1,1,1,3- tetra- chloropropane using area normalization method and target product HFO-1243zf is selected
Selecting property.
Embodiment 1: preparation M/MgF2Catalyst
1.0M magnesium source and 0.01~0.1M modified metal ion are dissolved in 50mL polyol solvent, stirred at 150~240 DEG C
Mix it is lower fluorination reagent is added drop-wise in above-mentioned solution, time for adding 15min is stirred for 6~12h after being added dropwise, obtains M/
MgF2Xerogel；Then 5h or more is roasted at air atmosphere or 300~500 DEG C of nitrogen atmosphere, finally in 150~400 DEG C of program liters
Temperature carries out fluorination treatment to material after roasting and obtains catalyst, and fluorine reagent selects gaseous hydrogen fluoride, dicholorodifluoromethane, a chlorine two
Any one in fluoromethane, monochlorotrifluoromethane.Under different magnesium sources, polyol solvent, coagulant, fluorination reagent, maturing temperature
Magnesium fluoride texture property obtained is shown in Table 1.
The physico-chemical property result of the fluorination magnesium-base catalyst of 1 embodiment 1 of table
Embodiment 2
M/MgF is prepared using same procedure in embodiment 12Catalyst applies it to 1,1,1,3- tetrachloro of gas phase fluorination
Propane synthesizes in HFO-1243f reaction, and after running 12h, reaction result is as follows:
The reaction evaluating result of the fluorination magnesium-base catalyst of 2 embodiment 2 of table
Embodiment 3
M/MgF is prepared using same procedure in embodiment 12Catalyst applies it to 1,1,1,3- tetrachloro of gas phase fluorination
Propane synthesizes in HFO-1243f reaction, and after running 12h, reaction result is as follows:
The reaction evaluating result of the fluorination magnesium-base catalyst of 3 embodiment 3 of table
Claims (4)
1. a kind of gas phase fluorination synthesizes 3,3,3- trifluoro propene chromium-free environment-friendly catalyst, it is characterised in that the catalyst composition
For M/MgF2, wherein matrix MgF2To be greater than 120m with Rutile Type and nanometer spherical structure, specific surface area2/ g, in 500 DEG C
The superior high stability MgF of anti-sintering property2, active component M is selected from Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+、
Cu2+One or more of, M mass accounts for the 5%~20% of catalyst gross mass；
The method for preparing catalyst is as follows:
(1) to containing Mg at 150~240 DEG C2+And fluorination reagent is added dropwise in the polyhydric alcohol solutions of M, continue stirring 6 after being added dropwise
~12h obtains M/MgF2Xerogel；
Mg used2+Selected from one of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium methoxide, magnesium ethylate, magnesium acetate；
M used is selected from one or more of nitrate, chloride, sulfate；
Polyalcohol used is selected from one or more of ethylene glycol, propylene glycol, glycerine, tirethylene glycol；
Fluorination reagent used is selected from one of aqueous solution, alcoholic solution, ethereal solution of hydrogen fluoride；
Mg2+Molar ratio with hydrogen fluoride is 1:3~12；
(2) made xerogel in (1) is heat-treated at 300~500 DEG C, then to heat treatment at 150~400 DEG C
Xerogel carries out fluorination treatment and M/MgF is made afterwards2Catalyst；
Heat-treating atmosphere is carried out selected from one of air, nitrogen, hydrogen atmosphere；
Fluorine reagent used in fluorination treatment in hydrogen fluoride, dicholorodifluoromethane, F-22, monochlorotrifluoromethane one
Kind.
2. gas phase fluorination synthesizes 3,3,3- trifluoro propene chromium-free environment-friendly catalyst according to claim 1, it is characterised in that M
For Fe3+、La3+Combination, Fe3+With La3+Molar ratio be 1:0.2~1.
3. gas phase fluorination synthesizes the preparation method of 3,3,3- trifluoro propene chromium-free environment-friendly catalyst according to claim 1,
It is characterized in that the concentration of the fluorination reagent is 20wt.%~70wt.%.
4. chromium-free environment-friendly catalyst described in claim 1, the gas phase catalysis carried out for 1,1,1,3- tetra- chloropropane and hydrogen fluoride
Fluorination synthesis 3,3,3- trifluoro propene reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558386A (en) * | 2020-04-10 | 2020-08-21 | 西安近代化学研究所 | Iron fluoride-based catalyst for synthesizing hydrofluoroolefin by gas phase fluorination and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707631A (en) * | 2013-12-12 | 2015-06-17 | 西安近代化学研究所 | Chromium-free gas phase fluorination catalyst and use thereof |
| CN106745111A (en) * | 2016-12-19 | 2017-05-31 | 西安近代化学研究所 | A kind of preparation method of high-specific area nano crystalline substance magnesium fluoride |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707631A (en) * | 2013-12-12 | 2015-06-17 | 西安近代化学研究所 | Chromium-free gas phase fluorination catalyst and use thereof |
| CN106745111A (en) * | 2016-12-19 | 2017-05-31 | 西安近代化学研究所 | A kind of preparation method of high-specific area nano crystalline substance magnesium fluoride |
Non-Patent Citations (1)
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| 李雨臻等: ""氟化镁固体酸催化剂的制备及研究现状"", 《有机氟工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111558386A (en) * | 2020-04-10 | 2020-08-21 | 西安近代化学研究所 | Iron fluoride-based catalyst for synthesizing hydrofluoroolefin by gas phase fluorination and preparation method and application thereof |
| CN111558386B (en) * | 2020-04-10 | 2023-05-12 | 西安近代化学研究所 | Ferric fluoride-based catalyst for synthesizing hydro-fluoroolefin by gas phase fluorination, preparation method and application thereof |
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