CN108014827A - A kind of preparation method of high-ratio surface nanometer fluorine oxygen chrome catalysts - Google Patents
A kind of preparation method of high-ratio surface nanometer fluorine oxygen chrome catalysts Download PDFInfo
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- CN108014827A CN108014827A CN201711321346.1A CN201711321346A CN108014827A CN 108014827 A CN108014827 A CN 108014827A CN 201711321346 A CN201711321346 A CN 201711321346A CN 108014827 A CN108014827 A CN 108014827A
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- chromium
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- fluorine oxygen
- oxygen
- chrome catalysts
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- UOBPHQJGWSVXFS-UHFFFAOYSA-N [O].[F] Chemical compound [O].[F] UOBPHQJGWSVXFS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 35
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- CHFYPGXSQIHAPY-UHFFFAOYSA-N [Cr].[O].[F] Chemical compound [Cr].[O].[F] CHFYPGXSQIHAPY-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 4
- 229920005862 polyol Polymers 0.000 abstract description 3
- 150000003077 polyols Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XVOFZWCCFLVFRR-UHFFFAOYSA-N oxochromium Chemical compound [Cr]=O XVOFZWCCFLVFRR-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WHEOOESXUFDZMQ-UHFFFAOYSA-N [O-2].[Cr+3].[F].[O-2].[O-2].[Cr+3] Chemical compound [O-2].[Cr+3].[F].[O-2].[O-2].[Cr+3] WHEOOESXUFDZMQ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of high-ratio surface nanometer fluorine oxygen chrome catalysts.Be in order to solve in existing preparation method there are cost of material is high, synthesis technique is complicated, charomic fluoride is difficult to oxygen element uniformly to mix, crystallite dimension can not Effective Regulation the problems such as.The preparation method of the nanocrystalline fluorine oxygen chromium of the present invention comprises the following steps：(1) solution of the presoma of source containing chromium, polyol solvent and complexing agent component is prepared, is flowed back at 30~80 DEG C；(2) fluorination reagent is added to the solution that (1) obtain to be fluorinated, flow back stirring to obtain suspension at 140~200 DEG C；(3) by suspension at 100~160 DEG C aging, wash, solid be obtained by filtration, finally roasted at 200 DEG C~350 DEG C and high-ratio surface nanometer fluorine oxygen chrome catalysts be made.
Description
Technical field
The present invention relates to a kind of fluorine oxygen chrome catalysts, and in particular to a kind of temperature of high-ratio surface nanometer fluorine oxygen chrome catalysts
With, simple and environmental-friendly preparation method.
Background technology
In the reaction of the fluorine-containing halogenated hydrocarbons of gas phase catalytic synthesis, such as third generation refrigerant hydrofluorocarbon (HFCs), forth generation system
In the preparation process of cryogen HF hydrocarbon (HFOs), one of severe corrosive HF or reactant or it can generate in the reaction, therefore
Used catalyst must be the material that can be stabilized under high temperature HF atmosphere.So far, the oxidation after fluorination treatment
Chromium has been demonstrated to be stabilized for a long time in above-mentioned severe corrosive atmosphere.Importantly, result of study show to prepare it is fluorine-containing
The catalytic active center of halogenated hydrocarbons is the fluorine oxygen chromium generated after being fluorinated.However, fluorine oxygen chromium will be used as catalyst, it is necessary to have big
Specific surface area, could obtain considerable catalytic activity, but both at home and abroad correlation prepare the document of bigger serface fluorine oxygen chromium, patent compared with
It is few.Based on this, high-specific surface area, nanometer fluorine oxygen chromium are prepared to developing the fluorine-containing halogenated hydrocarbons catalyst meaning of high activity vapor- phase synthesis
It is very great.
In only report, Chinese patent CN105435775 discloses a kind of preparation of high-specific surface area fluorination catalyst
Method, is mutually to mix the mixed aqueous solution in chromium source, silicon source with ammonium hydroxide precipitation reaction occurs first, then through high-temperature roasting, High Temperature Gas
The processing of phase fluorination hydrogen obtains fluorination catalyst.Chinese patent CN105457661 discloses a kind of Gao Bibiao products chromium-based catalysts
Preparation method, is that sol gel occurs for chromic nitrate in the presence of the chelating agent of carboxylate-containing first, then through being lighted in air atmosphere
Catalyst precursor is obtained, is most handled afterwards through High Temperature Gas phase fluorination hydrogen and obtains chromium-based catalysts.Chinese patent CN103143344 is public
A kind of high preparation method than table chromium-based fluorination catalyst has been opened, has been that the alcohol of the chromic salts in the presence of ionic liquid, polyethylene glycol is molten
Liquid occurs precipitation reaction with precipitating reagent and obtains catalyst precursor, then is handled through high temperature gas phase fluorination hydrogen and obtain chromium-based catalysts.
From above-mentioned patent, the preparation method of existing chromium-based catalysts still suffers from complex process, severe reaction conditions, the difficulty of pollution weight
Topic.
The height of above-mentioned report still at least has problems with than table chromium-based catalysts preparation method：(1) complex process, all
It is first acquisition chromium-containing oxide presoma, then handled through high-temperature fluorination and obtain catalyst, syntheti c route is grown, product batches stability
Difference；(2) high-temperature fluorination hydrofluorination treatment conditions are harsh, pollution is heavy, and high-temperature fluorination reaction is strongly exothermic process, and technological operation is difficult
Degree is big；(3) hydrogen fluoride used in gas phase fluorination is significantly excessive, causes cost of material high, and outer waste discharge hydrogen fluoride causes serious pollution to the environment；
(4) chromium-based catalysts after gained fluorination, Oil repellent is low, and specific surface area is small, and particle size is big, and activity is low.
The content 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 preparation method is simple, operation
Gently, the preparation method of the high-ratio surface nanometer fluorine oxygen chrome catalysts environmental-friendly, production cost is low.This fluorine oxygen of the present invention
Chromium is big with specific surface area, and particle size can be controlled in nanoscale, so as to obtain excellent catalytic performance.
Polyol process is that Gao Bibiao, the high efficiency method of nanometer fluorine oxygen chrome catalysts are prepared under a kind of temperate condition.It is warm herein
In fluorination process, with chromium source ion ligand complex effect occurs for polyol solvent, it is suppressed that generates the increasing of fluoride crystal grain
Long, reunion, so that the charomic fluoride particle diameter of generation is within nanometer range.In addition, by the modulation to polyalcohol, chromium source can be made
The coordination ability of ion therewith changes, and makes the charomic fluoride of generation have different oxygen contents, so that obtain with different fluorine/
The fluorine chromium oxide of oxygen ratio.In addition, in the process using various concentrations fluorination reagent aqueous solution can further modulation gained
The crystal water content of charomic fluoride, acquisition have more wide in range oxygen doping charomic fluoride.
The high-ratio surface nanometer fluorine oxygen chrome catalysts of the present invention, it is characterised in that it is hydroxyl charomic fluoride composite material, its
Chemical expression is：Cr(OH)xFy, the mass percentage of fluorine in the material is 20%~50%；Specific surface area is 50 after roasting
~150m2/ g, centralized particle diameter are adopted the following technical scheme that and are achieved in 60~110nm：
A kind of preparation method of high-ratio surface nanometer fluorine oxygen chrome catalysts, it is characterised in that comprise the following steps：
(1) chromium source, complexing agent and polynary alcohol phase are mixed, flow back more than 6h at 30 DEG C~80 DEG C, obtains reaction solution A；
The chromium source is chromic nitrate, chromium chloride, chromium sulfate, one kind in chromium acetate or any several combination form；
Polyalcohol is ethylene glycol, a kind of in tirethylene glycol, 1,3- propane diols, 1,2- propane diols, glycerine or any several
The combination composition of kind；
Complexing agent is polyethylene glycol, polyvinylpyrrolidone, peregal, citric acid, cyclodextrin, polyvinyl alcohol, epoxy second
A kind of or arbitrarily several combination composition in alkane；The mass ratio of the chromium source and complexing agent is 1:0.5~10；
(2) under agitation, fluorination reagent is added to and fluorination treatment is carried out in reaction solution A, after addition, in 140 DEG C~
Continue to be refluxed more than 6h at 200 DEG C, obtain suspension；
The fluorination reagent is hydrogen fluoride, a kind of composition in ammonium fluoride aqueous solution；The concentration of the fluorination reagent is
20wt.%~90wt.%；The molar ratio in the fluorination reagent and chromium source is 3~6:1；
(3) after suspension being stood aging 24h at 100 DEG C~160 DEG C, then it is washed, solid is obtained by filtration；
(4) solid is finally being roasted into more than 4h at 200 DEG C~350 DEG C, the catalysis of high-ratio surface nanometer fluorine oxygen chromium is made
Agent；Roasting is carried out under one kind in air, nitrogen, oxygen, hydrogen atmosphere；
Further, in step (1), it is characterised in that the mass ratio of the chromium source and polyalcohol is 1:100~20.
Beneficial effects of the present invention：Compared with prior art, the present invention with following beneficial technique effect：
1. compared with conventional method, it is easy to get the present invention provides a kind of raw material, is easy to operate, preparation condition is gentle, energy consumption
The preparation method of low, environmental-friendly high-ratio surface nanometer fluorine oxygen chrome catalysts；2. preparation method provided by the invention need not
Use expensive, the commercial ionic liquid being not easy, carboxylate；3. preparation method provided by the invention need not be through liquid phase
Precipitation method generation oxide precursor, the process again through gas phase fluorination generation fluoride, a step liquid-phase fluorination, precipitation generation fluorine oxygen
Compound, applicability is wide, is easy to industrial amplification production；4. preparation method provided by the invention can be easily achieved to made fluorine
Change the oxygen doping that chromium carries out atomic scale, gained catalyst each element is evenly distributed, and other methods are inherently to pass through table
Face gas phase fluorination obtains catalyst, it is difficult to accomplish the uniform mixing of body phase, table phase each element；5. preparation method provided by the invention
The modulation to made fluorine chrome oxide particle size can be easily achieved, and other methods can only often obtain the chromium of specific structure
Base catalyst, ability of regulation and control is poor, and specific surface area of catalyst is mainly carrier contribution, and the true specific surface area of fluorine oxygen chromium is small.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of high-ratio surface nanometer fluorine oxygen chromium
Fig. 2 is the N of high-ratio surface nanometer fluorine oxygen chromium2Adsorption desorption isothermal chart
Embodiment
Embodiment 1：Prepare high-ratio surface nanometer fluorine oxygen chrome catalysts
1.0M chromium source is dissolved in 50mL polyol solvents, the reflow treatment 6h under 30~80 DEG C of stirrings, then fluorination is tried
Agent is added drop-wise in above-mentioned solution under agitation, time for adding 30min, is flowed back and is stirred at 140 DEG C~200 DEG C after being added dropwise
6h is mixed, obtains suspension；Then static more than the aging 24h at 100~160 DEG C, then it is washed, solid is obtained by filtration；Finally
More than 4h is roasted at 200~350 DEG C of air atmosphere, high nano surface crystalline substance fluorine oxygen chrome catalysts material is made.It is DIFFERENT Cr source, polynary
Obtained fluorine oxygen chromium texture property is shown in Table 1 under alcoholic solvent, complexing agent, fluorination reagent, calcination temperature.
The high-ratio surface nanometer fluorine oxygen chrome catalysts physico-chemical property result of 1 embodiment 1 of table
Embodiment 2：Prepare high-ratio surface nanometer fluorine oxygen chrome catalysts
1.0M chromic nitrates and polyethylene glycol are dissolved in 50mL ethylene glycol, the reflow treatment 6h under 60 DEG C of stirrings, then by HF
Aqueous solution (40wt.%) is added drop-wise in above-mentioned solution under agitation, time for adding 30min, after being added dropwise at 160 DEG C
6h is refluxed, obtains suspension；Then static more than the aging 24h at 160 DEG C, then it is washed, solid is obtained by filtration；Finally
More than 4h is roasted at 300 DEG C, the nanocrystalline fluorine oxygen chromium of high-ratio surface is made.Fluorine oxygen chromium texture made from different polyethylene glycol dosages
It is shown in Table 2.
The high-ratio surface nanometer fluorine oxygen chrome catalysts physico-chemical property result of 2 embodiment 2 of table
| Numbering | Cr/ complexing agent mass ratioes | Fluorine oxygen chromium specific surface area/m2/g | Fluorine oxygen chromium particle diameter/nm |
| 1 | 1:0.5 | 32 | 76 |
| 2 | 1:3 | 78 | 68 |
| 3 | 1:6 | 150 | 37 |
| 4 | 1:10 | 137 | 40 |
Embodiment 3：Prepare high-ratio surface nanometer fluorine oxygen chrome catalysts
By 1.0M chromic nitrates and polyethylene glycol, (Cr/ complexing agents mass ratio is 1:3) it is dissolved in 50mL ethylene glycol, is stirred at 60 DEG C
Lower reflow treatment 6h is mixed, then HF aqueous solutions are added drop-wise in above-mentioned solution under agitation, time for adding 30min, is added dropwise
6h is refluxed at 160 DEG C afterwards, obtains suspension；Then static more than the aging 24h at 160 DEG C, then washed, filtering
Obtain solid；More than 4h is finally roasted at 300 DEG C, the nanocrystalline fluorine oxygen chromium of high-ratio surface is made.Fluorine made from different HF concentration
Oxygen chromium texture is shown in Table 3.
The high-ratio surface nanometer fluorine oxygen chrome catalysts physico-chemical property result of 3 embodiment 3 of table
Embodiment 4：Prepare high-ratio surface nanometer fluorine oxygen chrome catalysts
By 1.0M chromic nitrates and polyethylene glycol, (Cr/ glue complexing agents mass ratio is 1:3) it is dissolved in 50mL ethylene glycol, at 60 DEG C
The lower reflow treatment 6h of stirring, then HF aqueous solutions (40wt.%) are added drop-wise in above-mentioned solution under agitation, time for adding is
30min, is refluxed 6h at 160 DEG C after being added dropwise, obtains suspension；Then at 160 DEG C static aging 24h with
On, then it is washed, solid is obtained by filtration；More than 4h is finally roasted at 300 DEG C, the nanocrystalline fluorine oxygen chromium of high-ratio surface is made.No
It is shown in Table 4 with fluorine oxygen chromium texture made from Cr/HF molar ratios.
The high-ratio surface nanometer fluorine oxygen chrome catalysts physico-chemical property result of 4 embodiment 4 of table
Embodiment 5：Prepare high-ratio surface nanometer fluorine oxygen chrome catalysts
By 1.0M chromic nitrates and polyethylene glycol, (Cr/ complexing agents mass ratio is 1:3) it is dissolved in 50mL ethylene glycol, is stirred at 60 DEG C
Lower reflow treatment 6h is mixed, then HF aqueous solutions (40wt.%) are added drop-wise in above-mentioned solution under agitation, time for adding 30min,
6h is refluxed at 160 DEG C after being added dropwise, obtains suspension；Then static more than the aging 24h at 160 DEG C, then pass through
Wash, solid is obtained by filtration；More than 4h is finally roasted at 300 DEG C, the nanocrystalline fluorine oxygen chromium of high-ratio surface is made.Under different atmosphere
Obtained fluorine oxygen chromium texture is shown in Table 5.
Claims (2)
- A kind of 1. preparation method of high-ratio surface nanometer fluorine oxygen chrome catalysts, it is characterised in that the high-ratio surface nanometer fluorine Oxygen chrome catalysts are hydroxyl charomic fluoride composite materials, its chemical expression is：Cr(OH)xFy, the quality percentage of fluorine in the material contains Measure as 20%~50%；Specific surface area is 50~150m after roasting2/ g, centralized particle diameter is in 60~110nm；The preparation side Method comprises the following steps：(1) chromium source, complexing agent and polynary alcohol phase are mixed, flow back more than 6h at 30 DEG C~80 DEG C, obtains reaction solution A；The chromium source is chromic nitrate, chromium chloride, chromium sulfate, one kind in chromium acetate or any several combination form；Polyalcohol is ethylene glycol, a kind of in tirethylene glycol, 1,3- propane diols, 1,2- propane diols, glycerine or any several Combination composition；Complexing agent is polyethylene glycol, in polyvinylpyrrolidone, peregal, citric acid, cyclodextrin, polyvinyl alcohol, ethylene oxide A kind of or any several combination composition；The mass ratio of the chromium source and complexing agent is 1:0.5~10；(2) under agitation, fluorination reagent is added to and fluorination treatment is carried out in reaction solution A, after addition, in 140 DEG C~200 DEG C Under continue to be refluxed more than 6h, obtain suspension；The fluorination reagent is hydrogen fluoride, a kind of composition in ammonium fluoride aqueous solution；The concentration of the fluorination reagent is 20wt.% ~90wt.%；The molar ratio in the fluorination reagent and chromium source is 3~6:1；(3) after suspension being stood aging 24h at 100 DEG C~160 DEG C, then it is washed, solid is obtained by filtration；(4) solid is finally roasted into more than 4h at 200 DEG C~350 DEG C, high-ratio surface nanometer fluorine oxygen chrome catalysts is made；Roasting It is to be carried out under one kind in air, nitrogen, oxygen, hydrogen atmosphere.
- 2. the preparation method of high-ratio surface nanometer fluorine oxygen chrome catalysts as claimed in claim 1, it is characterised in that the chromium source Mass ratio with polyalcohol is 1:100~200.
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