CN103143344B - A kind of high than table chromium-based fluorination catalyst and preparation method thereof - Google Patents

A kind of high than table chromium-based fluorination catalyst and preparation method thereof Download PDF

Info

Publication number
CN103143344B
CN103143344B CN201110400233.7A CN201110400233A CN103143344B CN 103143344 B CN103143344 B CN 103143344B CN 201110400233 A CN201110400233 A CN 201110400233A CN 103143344 B CN103143344 B CN 103143344B
Authority
CN
China
Prior art keywords
fluorination catalyst
application
active component
catalyst
chromium
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
Application number
CN201110400233.7A
Other languages
Chinese (zh)
Other versions
CN103143344A (en
Inventor
刘坤峰
杨会娥
张文庆
曾昌华
赵新堂
王�锋
李忠
陈蜀康
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinochem Corp
Sinochem Lantian Co Ltd
Sinochem Modern Environmental Protection Chemicals Xian Co Ltd
Original Assignee
Sinochem Lantian Co Ltd
Sinochem Modern Environmental Protection Chemicals Xian Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sinochem Lantian Co Ltd, Sinochem Modern Environmental Protection Chemicals Xian Co Ltd filed Critical Sinochem Lantian Co Ltd
Priority to CN201110400233.7A priority Critical patent/CN103143344B/en
Publication of CN103143344A publication Critical patent/CN103143344A/en
Application granted granted Critical
Publication of CN103143344B publication Critical patent/CN103143344B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention provides the chromium-based fluorination catalyst and preparation method thereof of a kind of Gao Bibiao, high activity, high stability.Chromium-based fluorination catalyst of the present invention comprises the first active component and the second active component, wherein: the first active component is Cr; Second active component is selected from one or more combinations in Mg, Zn, Al, Co, Y, Ga or Pr; The mol ratio of the second active component and the first active component is 0.001 ~ 0.5:1; The specific area of fluorination catalyst is 320 ~ 500m 2/ g.Chromium-based fluorination catalyst of the present invention is realized by the organic composite additive adding polyethylene glycol and the composite formation of ionic liquid in preparation process.Chromium-based fluorination catalyst prepared by the present invention is especially suitable for preparing HFC-125 and HFC-134a.

Description

A kind of high than table chromium-based fluorination catalyst and preparation method thereof
Technical field
The present invention relates to a kind of for fluorination reaction, the height ratio especially for halogenated hydrocarbons gas phase fluorination shows chromium-based fluorination catalyst and preparation method thereof.
Background technology
In gas phase fluorination, the catalyst that the catalyst used is generally is main active component with chromium element.Up to now, the method improving catalyst performance is normally undertaken by increasing specific surface area of catalyst or adding assistant metal.
The chromium-based catalysts precursor Cr of freon substitute hydrogen fluorohydrocarbon is produced at present for vapor phase method 2o 3nH 2the preparation method that O (0 < n < 3) is conventional is the precipitation method.With NaOH, (NH 4) 2cO 3, the precipitating reagent such as ammoniacal liquor precipitation chromic nitrate hydrate, chromium trichloride, the solubility chromic salts such as chrome alum generate chromium hydroxide state catalyst, filters, washing, becomes Cr after 100 ~ 200 DEG C of dryings 2o 3nH 2o (0 < n < 3), can be used as the catalyst synthesizing hydrogen fluorohydrocarbon, but the specific area of catalyst is usually at 100 ~ 200m further across shaping, roasting, activation 2/ g, although this preparation method step compared with infusion process is various, activity is higher.
Such as, EP295885A1 reports the method preparing R134a, and its catalyst is with commodity γ-Al 2o 3for carrier (specific area > 100m 2/ g), after impregnated activated metallic compound, fluoridize, the γ-Al after fluoridizing with HF in reaction tube 2o 3all change AlF into 3.
EP408004 describes and is being loaded in specific area at least 25m 2the AlF of/g 3on chromium salt catalyst existence under, in 220 DEG C ~ 280 DEG C, make tetrachloro-ethylene carry out hydrofluorination reaction in gas phase and HF, obtained chloro-1,1, the 2-HFC-143a (HCFC-123) of 1,2-bis-.The conversion ratio of the method tetrachloro-ethylene is very low.
From reporting above, at γ-Al 2o 3in fluorination process, fluoridize and can produce a large amount of water, make the loss of active component flooded, in addition, fluoridize the too high meeting of temperature and cause AlF 3crystalline substance become.And use AlF 3the specific surface area of catalyst that direct impregnation obtains is very little, makes the conversion ratio of raw material very low.
Chinese patent CN95115476.1 discloses a kind of containing SiO 2γ-Al 2o 3obtained active A lF 3, its specific area>=40m 2/ g, pore volume>=0.18m 2/ g, average pore size≤9nm, AlF 3content>=90%, then flood Cr 3+, Co 2+, Mg 2+soluble-salt, drying, roasting, fluoridize obtained fluorination catalyst with nitrogen and hydrofluoric mist.In order to obtain the AlF of high-specific surface area 3, generally at Al 2o 3middle interpolation SiO 2, utilize hydrogen fluoride and SiO 2reaction generates volatility fluorosilicone compound and improves AlF 3the specific area of carrier, but easily cool condensation due to volatility fluorosilicone compound, causes pipeline blockage, makes that the preparation process of catalyst is more difficult carries out continuously; Meanwhile, need strict control to fluoridize temperature, the reappearance of catalyst cannot be ensured.
Patent document US5849658 there was reported the catalytic activity of catalyst and its specific area has sizable relation, improves Cr 2o 3nH 2the specific area of O (0 < n < 3) contributes to improving its catalytic activity
Chinese patent CN1068521A discloses the method that a kind of ammonia precipitation process chromic salts (chromic nitrate hydrate, chromium trichloride, chrome alum etc.) solution prepares high specific surface chrome catalysts, the method adopts the chromium nitrate aqueous solution of ammonia precipitation process, by the concentration, reaction temperature, ammoniacal liquor rate of addition etc. that control chromic salts and ammoniacal liquor in preparation process because of usually increasing specific surface area.
Chinese patent CN1408476 describes high active long-acting fluorating catalyst and manufacture method thereof, it adopts the precipitation method that active component soluble-salt (but nitrate, sulfate, chloride) is configured to certain density solution, react with precipitating reagent (ammoniacal liquor, NaOH, KOH etc.) at 20 ~ 100 DEG C, control final pH value 6.5 ~ 9.5 to, obtain catalyst precursor through filtration, washing, drying, roasting after after precipitation, the catalyst precursor specific area obtained is greater than 200m 2/ g.But specific surface area of catalyst prepared by these preparation methods can not be entirely satisfactory, therefore need to seek a kind of raising Cr 2o 3nH 2the method of the specific area of O (0 < n < 3).
In order to overcome the undesirable shortcoming of specific surface area of catalyst of the prior art, the present inventor devises the preparation method of the precursor of high-ratio surface chromium-based catalysts.
Summary of the invention
The object of the present invention is to provide the chromium-based fluorination catalyst of a kind of high activity, high stable, bigger serface and the preparation method of precursor thereof, this precursor can be used for the catalyst of gas phase fluorination halogenated hydrocarbons after super-dry, roasting, activation.
For reaching goal of the invention the technical solution used in the present invention be:
One is used for by C 1-C 4halogenated hydrocarbons prepare the chromium-based fluorination catalyst of corresponding hydrogen fluorohydrocarbon, comprise the first active component and the second active component, wherein:
First active component is Cr;
Second active component is selected from one or more combinations in Mg, Zn, Al, Co, Y, Ga or Pr;
The mol ratio of the second active component and the first active component is 0.001 ~ 0.5: 1;
The specific area of described fluorination catalyst is 320 ~ 500m 2/ g, is preferably 380 ~ 500m 2/ g.
The mol ratio of above-mentioned second active component and the first active component is preferably 0.01 ~ 0.1: 1.
Present invention also offers a kind of preparation method of above-mentioned chromium-based fluorination catalyst, comprise the steps:
(1) be that the polyethylene glycol of 400 ~ 6000 and the organic composite additive of the composite formation of ionic liquid join in the alcohols solvent of chromic salts by molecular weight, in the alcohol solution of chromic salts, add the salt of the second active component, the mass ratio of described organic composite additive and chromic salts is 0.1: 1 ~ 0.8: 1 simultaneously;
(2) add precipitating reagent under agitation to precipitate, control the PH of solution 6.5 ~ 10.0, after filtration, wash, be drying to obtain catalyst precursor;
(3) use fluorization agent fluorating catalyst former body, obtain chromium-based fluorination catalyst.
Form colloidal sol after having added each component in above-mentioned steps (1) in the alcohol solution of chromic salts, in described step (2), catalyst precursor is preferably dimensioned to be 20 ~ 250nm.
In above-mentioned steps (1), chromic salts can provide with the form of the salt of any applicable trivalent chromic ion, and the salt of trivalent chromic ion is preferably: chromic nitrate (Cr (NO 3) 3) or its crystalline hydrate compound, chromium chloride (CrCl 3) or its crystalline hydrate compound.
Intermediate ion liquid of the present invention add the surface acidity that can change catalyst, the difference of its addition can change it and adapt to different fluorine halogen substitution reactions, and the adsorption desorption ability that can increase material in fluorination reaction process, thus improve catalytic activity greatly.Above-mentioned ionic liquid is preferably glyoxaline ion liquid, i.e. 1-alkyl-3-methyl tetrafluoroborate, and wherein the carbon chain lengths of alkyl is 2 ~ 10, has following (I) structural formula:
[C nmin]BF 4(I)
Wherein: n is integer and 2≤n≤10,
In glyoxaline ion liquid, the carbon chain lengths of alkyl is preferably 4≤n≤8.
The present invention controls specific area and the surface acidity of chromium-based fluorination catalyst presoma by adding organic composite additive in the preparation process of chromium-based fluorination catalyst presoma.The quality proportioning of above-mentioned polyethylene glycol and ionic liquid is preferably 0.5 ~ 3: 1, and more preferably 1 ~ 1.5: 1.
The molecular weight of above-mentioned polyethylene glycol is preferably 400 ~ 2000, and more preferably 600 ~ 1000.
Above-mentioned alcohols solvent is preferably positive alcohol or different alcohols, more preferably methyl alcohol and/or the ethanol of≤3 carbon.
It is 2 ~ 15% ammoniacal liquor that above-mentioned precipitating reagent is preferably concentration.
In the preparation method of above-mentioned chromium-based fluorination catalyst, the second active component and the first active component mol ratio are preferably 0.001 ~ 0.5: 1, and more preferably 0.01 ~ 0.1: 1.
In the present invention, chromium-based fluorination catalyst obtains by catalyst precursor materials being carried out fluoridizing, the common fluorization agent for activating catalyst all can be used for fluorating catalyst former body of the present invention, from the angle be easy to get, preferably use the mist of hydrogen fluoride or hydrogen fluoride and inert gas.Preferred activity methods is by the roasting in the nitrogen of 350 DEG C ~ 550 DEG C of the presoma of chromium-based fluorination catalyst, then passes into nitrogen and hydrofluoric mist is fluoridized at 200 ~ 400 DEG C, makes chromium-based fluorination catalyst.
In above-mentioned steps (2), drying is preferably carried out in two steps, and first carry out vacuum freeze drying, vacuum is not less than 0.09Mpa; And then drying is carried out at the temperature of 80 ~ 110 DEG C; Drying time is 0.5 ~ 5 hour.
In the present invention, gas phase fluorination refers to the exchange chloride for fluoride that carries out under chromium-based fluorination catalyst exists, and the essential condition of impact reaction has temperature, pressure, the proportioning of two kinds of raw materials (halogenated hydrocarbons and fluoride) and material by the air speed (wherein air speed is mass flow/catalyst volume) etc. of beds.
The invention provides the application of described chromium-based fluorination catalyst in preparation HFC-125, take HCFC-123 as raw material, under chromium-based fluorination catalyst exists, HFC-125 is prepared with HF gas-phase reaction, the mol ratio of described HF and HCFC-123 is preferably 3 ~ 10: 1, be preferably 2 ~ 10 seconds time of contact, reaction temperature is preferably 280 ~ 350 DEG C.
The present invention also provides the application of described chromium-based fluorination catalyst in preparation HFC-134a, take HCFC-133a as raw material, under chromium-based fluorination catalyst exists, HFC-134a is prepared with HF gas-phase reaction, the mol ratio of described HF and HCFC-133a is preferably 2 ~ 10: 1, be preferably 2 ~ 10 seconds time of contact, reaction temperature is preferably 300 ~ 360 DEG C.
Instant invention overcomes the deficiencies in the prior art, on the one hand by adding organic composite additive, the specific area of great raising catalyst precursor, improve the activity of catalyst significantly, ionic liquid in organic composite additive then can change the surface acidity of catalyst according to demand, catalyst particle is controlled on the other hand by forming colloidal sol in chromic salts alcoholic solution, Particle size control is at 20 ~ 250nm, thus make catalyst have great specific area, thus solve the undesirable problem of catalyst activity, chromium-based fluorination catalyst of the present invention is made to have high conversion, high selectivity and good stability.
Figure of description
Catalyst test collection of illustrative plates described in Fig. 1 Catalyst Preparation Example 1
Catalyst test collection of illustrative plates described in Fig. 2 catalyst comparative example 1
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these detailed description of the invention.One skilled in the art would recognize that all alternatives, improvement project and the equivalents that present invention encompasses and may comprise in Claims scope.
Catalyst Preparation Example 1
Take 120g CrCl 36H 2o is dissolved in 480ml ethanolic solution, in above-mentioned solution, then add 24gPEG-600 and [C 4min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 450m 2/ g.And adopt Micromeritics AutoChemII 2920 type auto-programming intensification chemical adsorption instrument to carry out temperature programmed desorption (TPD) and test spectrogram to fluoridizing rear catalyst and see Figure of description 1.
Catalyst Preparation Example 2
Take 120g CrCl 36H 2o and 0.05g magnesium nitrate is dissolved in 480ml ethanol, in above-mentioned solution, then add 36g PEG-1000 and [C 4min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 480m 2/ g.
Catalyst Preparation Example 3
Take 120g CrCl 36H 2o and 0.06g zinc nitrate is dissolved in 480ml ethanol, in above-mentioned solution, then add 12g PEG-1000 and [C 2min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 410m 2/ g.
Catalyst Preparation Example 4
Take 120g CrCl 36H 2o and 0.06g zinc nitrate is dissolved in 600ml ethanol, in above-mentioned solution, then add 12g PEG-1000 and [C 2min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 370m 2/ g.
Catalyst Preparation Example 5
Take 120g CrCl 36H 2o and 0.06g zinc nitrate is dissolved in 600ml ethanol, in above-mentioned solution, then add 36g PEG-1000 and [C 2min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 500m 2/ g.
Catalyst Preparation Example 6
Take 120g CrCl 36H 2o and 0.06g zinc nitrate is dissolved in 300ml ethanol, in above-mentioned solution, then add 24g PEG-600 and [C 6min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 370m 2/ g.
Catalyst Preparation Example 7
Take 120g CrCl 36H 2o and 0.06g zinc nitrate is dissolved in 300ml ethanol, in above-mentioned solution, then add 12g PEG-1000 and [C 2min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 320m 2/ g.
Catalyst Preparation Example 8
Take 120g CrCl 36H 2o and 0.06g magnesium nitrate is dissolved in 480ml ethanol, in above-mentioned solution, then add 36g PEG-2000 and [C 10min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 460m 2/ g.
Catalyst Preparation Example 9
Take 120g CrCl 36H 2o and 0.06g cobalt nitrate is dissolved in 600ml ethanol, in above-mentioned solution, then add 36g PEG-400 and [C 8min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 430m 2/ g.
Catalyst Preparation Example 10
Take 120g CrCl 36H 2o and 0.05g aluminum nitrate is dissolved in 300ml ethanol, in above-mentioned solution, then add 36g PEG-5000 and [C 6min] BF 4the homogeneous solvent of 1: 1 compound in mass ratio, the ammonia spirit of 10% concentration of 150g is added again in above-mentioned solution, control solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, material is put into when-40 DEG C of vacuums reach 0.09Mpa, the first step is warming up to 0 DEG C, and keep 4 hours, second step is warming up to 90 DEG C, after dry 2h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
The specific area adopting BET to analyze its presoma is 380m 2/ g.
Catalyst comparative example 1
Take 120g CrCl 36H 2o is dissolved in 480ml deionized water, in above-mentioned solution, then add the 10% concentration ammonia spirit of 150g, controls solution final ph between 6.5-10.0, filter described solution, sediment is spent deionized water to neutral, after 110 DEG C of dry 16h, obtained catalyst precursor.
Then by described catalyst precursor compression molding, then load in reactor, 400 DEG C of roastings in nitrogen atmosphere, then pass into nitrogen and hydrofluoric mist is fluoridized at 200-400 DEG C, make chromium-based fluorination catalyst.
Adopting specific area and pore structure tester (hereinafter referred to as BET) to analyze its presoma specific area is 220m 2/ g.And adopt Micromeritics AutoChem II 2920 type auto-programming intensification chemical adsorption instrument to carry out temperature programmed desorption (TPD) and test spectrogram to fluoridizing rear catalyst and see Figure of description 2.
Test example 1 different catalysts is to synthesis HFC-125 (CF 3cHF 2) impact
The chromium-based fluorination catalyst of comparative example 1 and embodiment 1 is respectively charged into the middle part of nickel alloy pipe (φ 46 × 3mm) fixed bed reactors, concrete filling process is: respectively to the chromium-based fluorination catalyst (noting not shaking graduated cylinder in adition process) of the comparative example 1 and embodiment 1-9 that slowly vertically add 100mL in graduated cylinder; And then join in reactor by vertical with the chromium-based fluorination catalyst of embodiment 1-9 for the comparative example 1 in graduated cylinder respectively, install reactor.
Before starting reaction, first at 400 DEG C, purge 4 hours with nitrogen, then pass into HF and HCFC-123 (CF 3cHCl 2) react, the mol ratio of control HF and HCFC-123 is 5: 1, and time of contact is 5 seconds, and reaction temperature is 350 DEG C, and the reaction time is 24 hours; After reaction terminates, product is removed HCl and HF through washing, alkali cleaning, then with gas chromatographic analysis product composition.The results are shown in Table 1.
Table 1 different catalysts is to HFC-125 (CF 3cHF 2) synthesis result impact
Test example 2 different catalysts is to synthesis HFC-134a (CF 3cH 2f) impact
The chromium-based fluorination catalyst of comparative example 1 and embodiment 1 is respectively charged into the middle part of nickel alloy pipe (φ 46 × 3mm) fixed bed reactors, concrete filling process is: respectively to the chromium-based fluorination catalyst (noting not shaking graduated cylinder in adition process) of the comparative example 1 and embodiment 1-9 that slowly vertically add 100mL in graduated cylinder; And then join in reactor by vertical with the chromium-based fluorination catalyst of embodiment 1-9 for the comparative example 1 in graduated cylinder respectively, install reactor.
Before starting reaction, first at 400 DEG C, purge 4 hours with nitrogen, then pass into HF and HCFC-133a (CF 3cH 2cl) react, the mol ratio of control HF and HCFC-133a is 5: 1, and time of contact is 5 seconds, and reaction temperature is 310 DEG C, and the reaction time is 24 hours; After reaction terminates, product is removed HCl and HF through washing, alkali cleaning, then with gas chromatographic analysis product composition.The results are shown in Table 2.
Table 2 different catalysts is to HFC-134a (CF 3cH 2f) impact of result is synthesized

Claims (16)

1. an application for fluorination catalyst, for by C 1-C 4halogenated hydrocarbons prepare corresponding hydrogen fluorohydrocarbon, it is characterized in that described fluorination catalyst is chromium-based fluorination catalyst, comprise the first active component and the second active component, wherein:
First active component is Cr;
Second active component is selected from one or more combinations in Mg, Zn, Al, Co, Y, Ga or Pr;
The mol ratio of the second active component and the first active component is 0.001 ~ 0.5:1;
The specific area of described fluorination catalyst is 320 ~ 500m 2/ g.
2., according to the application of fluorination catalyst according to claim 1, it is characterized in that the specific area of described fluorination catalyst is 380 ~ 500m 2/ g.
3., according to the application of fluorination catalyst according to claim 1, it is characterized in that the mol ratio of described second active component and the first active component is 0.01 ~ 0.1:1.
4., according to the application of fluorination catalyst according to claim 1, it is characterized in that the preparation method of described fluorination catalyst comprises the steps:
(1) be that the polyethylene glycol of 400 ~ 6000 and the organic composite additive of the composite formation of ionic liquid join in the alcohols solvent of chromic salts by molecular weight, in the alcohol solution of chromic salts, add the salt of the second active component, the mass ratio of described organic composite additive and chromic salts is 0.1:1 ~ 0.8:1 simultaneously;
(2) add precipitating reagent under agitation to precipitate, control the pH of solution 6.5 ~ 10.0, after filtration, wash, be drying to obtain catalyst precursor;
Use fluorization agent fluorating catalyst former body, obtain chromium-based fluorination catalyst.
5., according to the application of fluorination catalyst according to claim 4, it is characterized in that in described step (1), each component forms colloidal sol, in described step (2), catalyst precursor is of a size of 20 ~ 250nm.
6. according to the application of fluorination catalyst according to claim 4, it is characterized in that described chromic salts is chromic salt, be selected from chromic nitrate or its crystalline hydrate compound, chromium chloride or its crystalline hydrate compound.
7. according to the application of fluorination catalyst according to claim 4, it is characterized in that described ionic liquid is glyoxaline ion liquid 1-alkyl-3-methyl tetrafluoroborate, there is following (I) structural formula:
Wherein: n is integer and 2≤n≤10.
8., according to the application of fluorination catalyst according to claim 7, it is characterized in that the carbon chain lengths n of alkyl in described glyoxaline ion liquid is 4≤n≤8.
9. according to the application of fluorination catalyst according to claim 4, it is characterized in that the molecular weight of described polyethylene glycol is 400 ~ 2000, the quality proportioning of polyethylene glycol and ionic liquid is 0.5 ~ 3:1.
10. according to the application of fluorination catalyst according to claim 9, it is characterized in that the molecular weight of described polyethylene glycol is 600 ~ 1000, the quality proportioning of polyethylene glycol and ionic liquid is 1 ~ 1.5:1.
11. according to the application of fluorination catalyst according to claim 4, and it is characterized in that described alcohols solvent is the positive alcohol of≤3 carbon or different alcohols, described precipitating reagent is concentration is 2 ~ 15% ammoniacal liquor.
12., according to the application of fluorination catalyst according to claim 11, is characterized in that described alcohols solvent is methyl alcohol and/or ethanol.
13. according to the application of fluorination catalyst according to claim 4, and it is characterized in that described second active component and the first active component mol ratio are 0.01 ~ 0.1:1, described fluorization agent is the mist of hydrogen fluoride or hydrogen fluoride and inert gas.
14. according to the application of fluorination catalyst according to claim 4, it is characterized in that in step (2), drying is carried out in two steps, first carry out vacuum freeze drying, vacuum is not less than 0.09Mpa, and then drying is carried out at the temperature of 80 ~ 110 DEG C, drying time is 0.5 ~ 5 hour.
15. according to the fluorination catalyst application one of claim 1 to 14 Suo Shu, it is characterized in that described fluorination catalyst is for the preparation of HFC-125, take HCFC-123 as raw material, under chromium-based fluorination catalyst exists, HFC-125 is prepared with HF gas-phase reaction, the mol ratio of described HF and HCFC-123 is 3 ~ 10:1, and time of contact is 2 ~ 10 seconds, and reaction temperature is 280 ~ 350 DEG C.
16. according to the fluorination catalyst application one of claim 1 to 14 Suo Shu, it is characterized in that described fluorination catalyst is for the preparation of HFC-134a, take HCFC-133a as raw material, under chromium-based fluorination catalyst exists, HFC-134a is prepared with HF gas-phase reaction, the mol ratio of described HF and HCFC-133a is 2 ~ 10:1, and time of contact is 2 ~ 10 seconds, and reaction temperature is 300 ~ 360 DEG C.
CN201110400233.7A 2011-12-06 2011-12-06 A kind of high than table chromium-based fluorination catalyst and preparation method thereof Active CN103143344B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110400233.7A CN103143344B (en) 2011-12-06 2011-12-06 A kind of high than table chromium-based fluorination catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110400233.7A CN103143344B (en) 2011-12-06 2011-12-06 A kind of high than table chromium-based fluorination catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN103143344A CN103143344A (en) 2013-06-12
CN103143344B true CN103143344B (en) 2015-10-14

Family

ID=48541820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110400233.7A Active CN103143344B (en) 2011-12-06 2011-12-06 A kind of high than table chromium-based fluorination catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103143344B (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103611525A (en) * 2013-11-13 2014-03-05 浙江衢化氟化学有限公司 Catalyst for producing pentafluoroethane through vapor phase method and preparation method thereof
CN107074696B (en) 2014-08-14 2019-11-22 科慕埃弗西有限公司 The method of E-1,3,3,3- tetrafluoropropene (HFC-1234ze) is prepared by dehydrofluorination
CN105435775B (en) * 2014-08-15 2019-02-19 中化近代环保化工(西安)有限公司 A kind of fluorination catalyst of high-specific surface area, preparation method and application
CN104888781A (en) * 2015-06-02 2015-09-09 江苏三美化工有限公司 Preparation method of fluorination catalyst
CN105344365A (en) * 2015-11-23 2016-02-24 山东东岳化工有限公司 Method for preparing fluorinated catalyst by homogeneous precipitation method
CN106902806B (en) * 2017-03-31 2020-08-21 北京宇极科技发展有限公司 High-activity molybdenum-based catalyst, preparation method and application
CN106902808B (en) * 2017-03-31 2020-02-11 北京宇极科技发展有限公司 High-activity tungsten-based catalyst, preparation method and application
CN107597135B (en) * 2017-08-07 2018-10-16 乳源东阳光氟有限公司 A kind of preparation method of fluorination catalyst
CN107552064B (en) * 2017-08-11 2018-12-04 乳源东阳光氟有限公司 A kind of fluorination catalyst and preparation method thereof
CN111036225B (en) * 2019-12-17 2023-03-07 山东东岳化工有限公司 Method for preparing high-activity pentafluoroethane chromium-based catalyst through sectional roasting and sectional fluorination
CN110922832B (en) * 2019-12-19 2021-11-26 和县卜集振兴标准件厂 Anti-slip thread rust-proof treatment process for bolt surface
CN111013612B (en) * 2019-12-20 2022-12-06 山东东岳化工有限公司 Preparation method of solid fluorination catalyst
CN114644544A (en) * 2020-12-17 2022-06-21 陕西中化蓝天化工新材料有限公司 Preparation method of fluoroalkane
CN116139890A (en) * 2023-04-24 2023-05-23 北京宇极科技发展有限公司 Boron element-made high specific surface area chromium-based catalyst and preparation method of high-proportion Z-fluoroolefin/E-fluoroolefin

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408476A (en) * 2001-09-26 2003-04-09 西安金珠近代化工有限责任公司 High active long-acting fluorating catalyst and its producing method
CN1911512A (en) * 2005-07-07 2007-02-14 独立行政法人产业技术综合研究所 Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts
CN101417816A (en) * 2007-10-26 2009-04-29 江苏梅兰化工有限公司 Method for preparing high specific surface area chromium series fluorating catalyst former body chromic oxide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2807751B1 (en) * 2000-04-12 2005-05-20 Solvay PROCESS FOR THE PREPARATION OF A HYDRO (CHLORO) FLUOROALCANE AND CATALYST

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408476A (en) * 2001-09-26 2003-04-09 西安金珠近代化工有限责任公司 High active long-acting fluorating catalyst and its producing method
CN1911512A (en) * 2005-07-07 2007-02-14 独立行政法人产业技术综合研究所 Fluorination catalysts, method for their preparation, and method for producing fluorinated compounds using the catalysts
CN101417816A (en) * 2007-10-26 2009-04-29 江苏梅兰化工有限公司 Method for preparing high specific surface area chromium series fluorating catalyst former body chromic oxide

Also Published As

Publication number Publication date
CN103143344A (en) 2013-06-12

Similar Documents

Publication Publication Date Title
CN103143344B (en) A kind of high than table chromium-based fluorination catalyst and preparation method thereof
Xuan et al. Metal-organic frameworks MOF-808-X as highly efficient catalysts for direct synthesis of dimethyl carbonate from CO2 and methanol
Sun et al. H 3 PW 12 O 40/SiO 2 for sorbitol dehydration to isosorbide: High efficient and reusable solid acid catalyst
CN105727929B (en) A kind of fluorination catalyst of high-specific surface area, preparation method and application
CN101081877B (en) Polymerization catalyst systems, methods of making and uses therefor
Ardila-Suárez et al. Synthesis of ordered microporous/macroporous MOF-808 through modulator-induced defect-formation, and surfactant self-assembly strategies
CN100372607C (en) Florination catalyst, its manufacturing method and use
CN104475080A (en) Mesoporous chromium-oxide-based catalyst for dehydrohalogenation reaction
EP2329881A1 (en) Methanol dehydrogenation catalyst for producing methyl formate and method for producing methyl formate
CN106000428A (en) Catalyst for generating trifluoroethylene from 1, 1, 1, 2-tetrafluoroethane by means of catalytic pyrolysis and in-situ regeneration method
Ahmad et al. Synthesis of oxymethylene dimethyl ethers (OMEn) via methanol mediated COx hydrogenation over Ru/BEA catalysts
CN101269323A (en) Catalyst for producing tetrafluoromethane with gas-phase fluoridation and production method
CN105251516A (en) Catalyst for compounding fluorine-containing halohydrocarbon and preparation method of catalyst
CN100584457C (en) Aluminum fluoride base fluorating catalyst, preparation method and application
CN105268442A (en) Copper-based methanol synthesis catalyst and preparation method therefor
CN105457661B (en) A kind of method for preparing high-specific surface area chromium-based fluorination catalyst
CN107497461B (en) Mesoporous chromium-based fluorination catalyst and preparation method thereof
CN112062086B (en) Simultaneous nano-confinement and catalysis of LiBH by Ni-MOF4Preparation method and application of hydrogen storage material
CN102580767B (en) Chromium-based fluorination catalyst and preparation method thereof
CN113171764A (en) IL/MOF/COF composite material, and preparation method and application thereof
CN101214446B (en) Fluorating catalyst and preparation method
Jia et al. Synergistic roles of surface acidity and Ni species in NiF2/AlF3 catalysts for pyrolysis of 1, 1, 1, 2-tetrafluoroethane
CN101507922A (en) Gas-phase fluorination catalyst and preparation method thereof
CN101214447B (en) Naluminum fluoride base fluorating catalyst and preparation thereof
CN109718813B (en) Chromium-free environment-friendly catalyst for gas-phase fluorination synthesis of 3,3, 3-trifluoropropene

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
TR01 Transfer of patent right

Effective date of registration: 20200316

Address after: 310051 Binjiang District Jiangnan Road, Zhejiang, No. 96, No.

Co-patentee after: SINOCHEM MODERN ENVIRONMENTAL CHEMICAL INDUSTRIAL ( XI 'AN)CO., Ltd.

Patentee after: SINOCHEM LANTIAN Co.,Ltd.

Co-patentee after: SINOCHEM Corp.

Address before: 310051, 96 Jiangnan Avenue, Ningbo, Zhejiang, Binjiang District

Co-patentee before: SINOCHEM MODERN ENVIRONMENTAL CHEMICAL INDUSTRIAL ( XI 'AN)CO., Ltd.

Patentee before: SINOCHEM LANTIAN Co.,Ltd.

TR01 Transfer of patent right