CN102274734B - Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof - Google Patents
Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst used for gas phase catalytic hydrogenation of a hexafluoroacetone hydrate for preparing hexafluoroisopropanol. The catalyst comprises a first catalyst, a second catalyst and a carrier, wherein the first catalyst consists of palladium and copper; the second catalyst is selected from one or the combination of K, La and Bi; and the catalyst is loaded on an active carbon carrier. The invention further discloses a preparation method of the catalyst and application of the catalyst to gas phase catalytic hydrogenation of the hexafluoroacetone hydrate for preparing hexafluoroisopropanol. The catalyst prepared with the method has the advantages of high catalytic hydrogenation activity, high hexafluoroisopropanol selectivity, superior catalyst stability, mild reaction condition, simple preparation process, and the like.
Description
Technical field
The invention belongs to and relate to the catalyst for preparing hexafluoroisopropanol for used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate.
Background technology
Hexafluoroisopropanol (HFIP) is a kind of novel fluorochemical, is the fluorine-containing alcohol that has using value.It is easy to mix with water and many organic solvents, Heat stability is good, and good for the permeability of ultraviolet light.These characteristics make HFIP can become a kind of ideal solvent in many polymerization systems, also are used for manufacturing and the cleaning of most advanced and sophisticated instrument and equipment as senior cleaning agent.HFIP is the large molecule of Dissolved Amino Acids class well, and to the destruction of protide natural fiber much smaller than other solvent, thereby also can be used as the spin solvent of regenerated silk.Simultaneously, it also is widely used in anesthetic, agricultural chemicals, medical synthesizing, such as synthetic current state-of-the-art suction-type anesthetic-Sevoflurane.
The technique of standby hexafluoroisopropanol has atom economy, yield advantages of higher take Hexafluoro acetone as the catalytic material Hydrogenation, becomes the key industry method of present production hexafluoroisopropanol.Can be divided into catalytic hydrogenation process and the catalytic hydrogenation process take hexafluoroacetone hydrate as raw material take the gaseous state Hexafluoro acetone as raw material according to the different existence forms of raw material Hexafluoro acetone.
Patent US3702872, BE634368, NL6610936, US3607952, GB2073181, US3356742, US7524995, JP2009051798 have reported take the gaseous state Hexafluoro acetone as raw material and have prepared hexafluoroisopropanol.Although this technique of some of them patent report can reach higher product yield, also exist simultaneously many defectives that are difficult to overcome, for example: (1) gaseous state Hexafluoro acetone boiling point is low, and toxicity is very high, is difficult to transportation and storage; (2) industrially be more difficult to get highly purified gaseous state Hexafluoro acetone, usually contain the impurity such as HF, HCl in the raw material, these impurity are easy to cause the hydrogenation catalyst inactivation in hydrogenation process, shorten catalyst life etc.
And the catalytic hydrogenation process take hexafluoroacetone hydrate as raw material can overcome defects.Hexafluoroacetone hydrate is absorbed by gaseous state Hexafluoro acetone water and just can obtain easily, compare with the gaseous state Hexafluoro acetone, hexafluoroacetone hydrate toxicity is low, be liquid under the normal temperature, Hexafluoro acetone all stores and transportation with the form of hexafluoroacetone hydrate industrial, hexafluoroacetone hydrate is relatively easily purified in addition, can obtain the raw material of higher degree, is beneficial to the life-span that prolongs hydrogenation catalyst.This technique mostly adopts liquid-phase hydrogenatin technique to prepare hexafluoroisopropanol, patent CN1962589 for example, JP2002275107, JP6184025, JP1301631, JP59204142 and US4564716 report, the employing hexafluoroacetone hydrate is raw material, take noble metal catalyst such as palladium, ruthenium, nickel, copper etc. as hydrogenation catalyst, in reactor, carry out liquid-phase hydrogenatin reaction preparation hexafluoroisopropanol respectively.Liquid-phase hydrogenatin technological reaction temperature is low, and hydrogen utilization ratio is high, but that shortcoming is to react required time is longer, and reaction pressure is higher, and is intermittent reaction, is unfavorable for industrial serialization production.
And take hexafluoroacetone hydrate as raw material through the vaporization after, prepare hexafluoroisopropanol by the Fixed Bed Gas Phase catalytic hydrogenation process, the comprehensive two-fold advantage of front two kinds of techniques then, avoid simultaneously the defective of its existence, this technological reaction mild condition, product yield is high, is beneficial to industrial continuous production, has good development prospect.The key of this technique is to have the catalyst of excellent Hydrogenation, but the research report about this technique is considerably less, only the central nitre patent US4467124 of subsidiary reports, take hexafluoroacetone hydrate as raw material, catalyst is nickel, palladium or both combinations, can also can be unsupported catalyst for supported catalyst, carries out catalytic hydrogenation reaction by beds and hydrogen after raw material is at first vaporized, temperature 40-200 ℃, feed stock conversion and product selectivity are up to more than 99%.Other has document " study on the synthesis of hexafluoroisopropanol " (Wang Yi, Ren Jiangang, Li Huili, the Shaanxi chemical industry, 1997 (9): reported also take hexafluoroacetone hydrate as raw material that 32-33) nickel chromium triangle copper is hydrogenation catalyst, prepares hexafluoroisopropanol through the Fixed Bed Gas Phase catalytic hydrogenation reaction.
Yet above-mentioned reaction system is the fluorochemical catalytic hydrogenation reaction, unavoidably in course of reaction, can produce a small amount of impurity such as HF, the hexafluoroacetone hydrate system has stronger acidity simultaneously, these reaction characteristicses are easy to cause the hydrogenation catalyst inactivation, 20h has only been carried out in reaction among the patent US4467124, also has very large gap with industrialized requirement, and document " study on the synthesis of hexafluoroisopropanol " (Wang Yi, Ren Jiangang, Li Huili, the Shaanxi chemical industry, 1997 (9): 32-33) product yield of report shows that less than 90% also there is larger gap in nickel chromium triangle copper catalyst active distance industry's enlarging production.Therefore develop a kind of high activity, be applicable to this reaction system, have simultaneously the hydrogenation catalyst of better stability concurrently, for the advantage of giving full play to the gas-phase catalytic hydrogenation preparation technology take hexafluoroacetone hydrate as raw material, realize that the suitability for industrialized production of hexafluoroisopropanol has great importance.
Summary of the invention
The object of the present invention is to provide a kind of used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate to prepare the catalyst of hexafluoroisopropanol, preparation technology and the application of this catalyst, this catalyst has selectively good, the advantage such as catalyst stability is excellent, reaction condition is gentle, catalyst preparation process is simple of catalytic hydrogenation activity height, hexafluoroisopropanol.
For achieving the above object, the present invention adopts following technological means.
A kind ofly prepare the catalyst of hexafluoroisopropanol for used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, comprise the first catalyst, the second catalyst and carrier;
Described the first catalyst is palladium and copper;
Described the second catalyst is one or more the combination that is selected among K, La and the Bi;
Described catalyst cupport is on absorbent charcoal carrier.
The first catalyst of the present invention is the combination of palladium and copper, forms bimetallic catalyst with palladium behind the interpolation copper, can dilute the palladium component, regulate the activity of catalyst, improve the stability of catalyst, can also reduce the load capacity of precious metal palladium simultaneously, reduce the Catalyst Production cost.
The second catalyst of the present invention mainly plays modification, modifying function to the first catalyst.The second catalyst and palladium atomic interaction, can change palladium atom Cloud Distribution on every side, thereby improve the selective of catalyst, the interpolation of the second catalyst can also improve main active component in the dispersity of carrier surface, regulate the interaction force between the active component, it is grained sintered to suppress active constituent, strengthens the anti-Coking Behavior of catalyst, thereby makes catalyst have higher catalytic activity and reaction stability.
In the catalyst of the present invention, the consumption of palladium is 0.1～5.0% of total catalyst weight in the first catalyst, the consumption of copper is 0.5～15.0% of total catalyst weight, and the consumption of described the second catalyst is 0.05～5.0% of total catalyst weight, and its surplus is carrier; As preferably, the consumption of palladium is 0.5～3.0% of total catalyst weight in the first catalyst, and the consumption of copper is 1.0～10.0% of total catalyst weight, and the consumption of described the second catalyst is 0.05～3.0% of total catalyst weight, and its surplus is carrier.
The preferred cocoanut active charcoal of absorbent charcoal carrier of the present invention, specific area is preferably 1000～1300m
2Between/the g, pore volume is preferably 0.6～0.9cm
3Between/the g, apparent density is preferably 0.45～0.55g/cm
3Between.
Absorbent charcoal carrier of the present invention before using preferably through the overpickling preliminary treatment.There is no particular limitation to the pickling washing agent in the present invention, and this area inorganic acid or organic acid commonly used all can use.The non-limiting example of described acid has: contain hydracid, such as hydrofluoric acid, hydrochloric acid, chloric acid, hydrobromic acid, bromic acid etc.; Sulfur acid, such as sulfuric acid, sulfurous acid, hydrosulphuric acid etc.; Nitrogen acid, such as nitric acid, industry nitric acid etc.; Phosphoric acid, such as phosphoric acid, industry phosphoric acid, hypophosphorous acid etc.; And the inorganic acid such as carbonic acid.The organic acid example has acetic acid, Hexafluoro acetone or hexafluoroisopropanol.Preferably the service property (quality) percentage composition is 30% salpeter solution.
Absorbent charcoal carrier pickling preliminary treatment of the present invention may further comprise the steps:
(1) adopt acid solution absorbent charcoal carrier to be carried out pickling processes, 60～100 ℃ for the treatment of temperatures, processing time 1～5h;
(2) the washing absorbent charcoal carrier is until eluate pH value is constant;
(3) vacuum drying absorbent charcoal carrier, 80～120 ℃ of baking temperatures, drying time 2～5h.
Infusion process is adopted in the preparation of catalyst of the present invention, may further comprise the steps:
(1) the soluble-salt solution of configuration the first catalyst and the second catalyst, Immesion active carbon carrier, dip time 〉=5h;
(2) vacuum drying 2～5h, 80～120 ℃ of baking temperatures;
(3) high-temperature roasting 2～5h, 300～600 ℃ of sintering temperatures.
Above-mentioned soluble-salt solution is preferably deionized water solution.
Catalyst soakage method of the present invention, but step impregnation, but also total immersion stain can be flooded first palladium-impregnated and copper behind the second catalyst, or flood first palladium-impregnated behind the second catalyst and the copper, also can the second catalyst, copper and the disposable dipping of palladium finish.
Used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate of the present invention prepares the hexafluoroisopropanol reaction to carry out in fixed bed reactors, material 316L stainless steel, internal diameter 7.3mm, length 200mm, catalyst preferably at first reduced processing before reaction, with the catalyst reactor of packing into, pass into hydrogen nitrogen mixed gas and carry out heating reduction, the hydrogen ratio is 5～50% in the hydrogen nitrogen mixed gas, preferred 150～300 ℃ of reduction temperature, preferred 1.0～3.0h of recovery time, the reducing gases air speed is preferred 〉=300h
-1Then carry out operation, at first adopt micro pump to squeeze into the raw material hexafluoroacetone hydrate, the liquid air speed is preferably 0.05～0.8h
-1, and after mixing, hydrogen enters the vaporizer vaporization, vapourizing temperature is preferably 110～180 ℃, hydrogen: the ketone hydrate molar ratio is preferred 1～3 in the hexafluoro, and reaction pressure is normal pressure.The catalytic hydrogenation reaction temperature is preferably 110～150 ℃.Product is through condensation separation, and gas chromatographic analysis conversion ratio and selective is adopted in hydrogen emptying after liquid phase material is collected.
The specific embodiment
Below by specific embodiment the present invention is specifically described.Following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.
The preliminary treatment of embodiment 1 carrier active carbon
The configuration quality percentage composition is 30% salpeter solution 500ml in proportion, takes by weighing the 150g cocoanut active charcoal and adds salpeter solution, is warming up to 90 ℃, stirring, backflow 2.0h, be down to room temperature, deionized water is washed to the eluate pH value constant, and 100 ℃ of vacuum drying 4.0h are for subsequent use.
The preparation of embodiment 2Pd-Cu-K/C catalyst and activity rating
Take by weighing 0.1gKCl, add the 10g deionized water dissolving, in solution, add the absorbent charcoal carrier of processing among the 10g embodiment 1, dipping 10.0h, then 90 ℃ of vacuum drying 5.0h take by weighing 6.0g chlorine palladium aqueous acid (the quality percentage composition 2.55% of palladium), 1.35gCuCl
22H
2O adds the 4.0g deionized water and is made into mixed solution, adds the active carbon that the front had been flooded K in solution, dipping 10.0h, and 90 ℃ of vacuum drying 5.0h, for subsequent use through 500 ℃ of roasting 3.0h again.
Take by weighing the catalyst sample 3.0ml that the prepares fixed bed reactors of packing into, pass into hydrogen nitrogen mixed gas and carry out heating reduction, the hydrogen ratio is 30%, 250 ℃ of reduction temperatures, recovery time 2h, reducing gases air speed 500h
-1Reduction finishes laggard promoting the circulation of qi phase catalytic hydrogenation reaction, 130 ℃ of vapourizing temperatures, 120 ℃ of reaction temperatures, hexafluoroacetone hydrate liquid air speed 0.3h
-1, hydrogen: hexafluoroacetone hydrate ratio 2, pressure are normal pressure.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 100% behind the stable reaction 5h, hexafluoroisopropanol selective 99.9%.
The preparation of embodiment 3Pd-Cu-La/C catalyst and activity rating
Take by weighing 0.31gLa (NO
3)
36H
2O, 0.38gCu (NO
3)
33H
2O adds the 10g deionized water dissolving, adds the absorbent charcoal carrier of processing among the embodiment 1 in mixed solution, dipping 12.0h, 90 ℃ of vacuum drying 5.0h.Then take by weighing 8.0g chlorine palladium aqueous acid (the quality percentage composition 2.55% of palladium), add 2.0g deionized water wiring solution-forming, adding the front in the solution had flooded La, the active carbon of Cu, dipping 24.0h, 90 ℃ of vacuum drying 5.0h, for subsequent use through 300 ℃ of roasting 5.0h again.
Catalyst reduction and activity rating method are with embodiment 2, and wherein the hydrogen ratio is 10% in the reducing gases, 180 ℃ of reduction temperatures, recovery time 3h, reducing gases air speed 800h
-1Reduction finishes laggard promoting the circulation of qi phase catalytic hydrogenation reaction, 110 ℃ of vapourizing temperatures, 110 ℃ of reaction temperatures, hexafluoroacetone hydrate liquid air speed 0.6h
-1, hydrogen: hexafluoroacetone hydrate ratio 1, pressure are normal pressure.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 100%, hexafluoroisopropanol selective 99.7%.
The preparation of embodiment 4Pd-Cu-Bi/C catalyst and activity rating
Take by weighing 0.38gBiCl
3, add the 10g deionized water dissolving, in solution, add the absorbent charcoal carrier of processing among the embodiment 1, dipping 5h, 90 ℃ of vacuum drying 5.0h take by weighing 2.70gCuCl successively again
22H
2O, add the 10g deionized water dissolving, in solution, add the active carbon that had flooded Bi, dipping 24h, 90 ℃ of vacuum drying 5.0h, then take by weighing 2.0g chlorine palladium aqueous acid (the quality percentage composition 2.55% of palladium), add in the solution and flooded Bi, the active carbon of Cu, dipping 10h, 90 ℃ of vacuum drying 5.0h, for subsequent use through 550 ℃ of roasting 3.0h again.
Catalyst reduction and activity rating method are with embodiment 2, and wherein the hydrogen ratio is 40% in the reducing gases, 200 ℃ of reduction temperatures, recovery time 3h, reducing gases air speed 300h
-1Reduction finishes laggard promoting the circulation of qi phase catalytic hydrogenation reaction, 150 ℃ of vapourizing temperatures, 150 ℃ of reaction temperatures, hexafluoroacetone hydrate liquid air speed 0.1h
-1, hydrogen: hexafluoroacetone hydrate ratio 3, pressure are normal pressure.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 99.0%, hexafluoroisopropanol selective 100%.
The preparation of embodiment 5Pd-Cu-K-La/C catalyst and activity rating
Take by weighing 0.2gKCl, 0.62gLa (NO
3)
36H
2O adds the 10g deionized water dissolving, adds the absorbent charcoal carrier of processing among the 10g embodiment 1 in solution, dipping 15.0h, and then 90 ℃ of vacuum drying 5.0h take by weighing 4.0g chlorine palladium aqueous acid (the quality percentage composition 2.55% of palladium), 3.04gCuCl successively
22H
2O, dipping 24h, 90 ℃ of vacuum drying 5.0h, for subsequent use through 450 ℃ of roasting 4.0h again.
Catalyst reduction and activity rating method are with embodiment 2, and wherein the hydrogen ratio is 50% in the reducing gases, 300 ℃ of reduction temperatures, recovery time 1h, reducing gases air speed 600h
-1Reduction finishes laggard promoting the circulation of qi phase catalytic hydrogenation reaction, 170 ℃ of vapourizing temperatures, 140 ℃ of reaction temperatures, hexafluoroacetone hydrate liquid air speed 0.15h
-1, hydrogen: hexafluoroacetone hydrate ratio 1.5, pressure are normal pressure.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 99.9%, hexafluoroisopropanol selective 100%.
Comparative example 1 commercial Pd/C catalyst activity is estimated
Employing Pd load capacity is 1.5% commercial Pd/C catalyst, and method, the condition of catalyst reduction and activity rating are identical with embodiment 2.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 99.2%, hexafluoroisopropanol selective 99.7%.
The preparation of comparative example 2Ni-Cr-Cu catalyst and activity rating
According to document " study on the synthesis of hexafluoroisopropanol " (Wang Yi, Ren Jiangang, Li Huili, the Shaanxi chemical industry, 1997 (9): the method 32-33) prepares the Ni-Cr-Cu catalyst, reactivity Appraising Methods, condition are identical with embodiment 2.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 85.0%, hexafluoroisopropanol selective 93.0%.
The reaction stability experiment of embodiment 6 catalyst P d-Cu-K/C and Pd/C
According to reduction and the activity rating method of catalyst among the embodiment 2, respectively catalyst P d-Cu-K/C and Pd/C are carried out the estimation of stability test, two kinds of loaded catalysts are identical.The experimental result that obtains is listed in the table 1, initial activity and the catalyst difference of the present invention that can find out commercial Pd/C catalyst are little, hexafluoroacetone hydrate conversion ratio and hexafluoroisopropanol are selectively all more than 99%, but can find out from stability data, at front 100 hours that react after beginning, the high active of hydrogenation catalysis of commercial Pd/C catalyst is comparatively stable, its catalytic activity begins to descend gradually behind the reaction 100h, and begin the active obviously decline that occurs from 150h, show inactivation aggravation of catalyst, when reacting to 250h, the hexafluoroacetone hydrate conversion ratio is down to 72.58%, and its catalytic efficiency of 150h only is 105g HFIP/gcat. before reaction.
And for Pd-Cu-K/C catalyst of the present invention, the stability test experiment is operation 1000h continuously, the hexafluoroacetone hydrate conversion ratio slightly has decline after reaction reaches 700h, but still remain on more than 99.5%, hexafluoroisopropanol does not selectively have significant change, in whole stability test process, catalyst efficiency is up to 705gHFIP/gcat..Show the present invention with palladium copper as major catalyst, by add among K, La, the Bi one or more co-catalysts to major catalyst modify, modification, the combined reaction performance of prepared active carbon-supported palladium copper bimetallic catalyst, particularly its reaction stability has obtained remarkable lifting, is characterized in obvious.
Table 1 catalyst P d-Cu-K/C and Pd/C reaction stability experimental result
Claims (10)
1. a catalyst prepares application in the hexafluoroisopropanol reaction at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that
Described catalyst comprises the first catalyst, the second catalyst and carrier;
Described the first catalyst is palladium and copper;
Described the second catalyst is one or more the combination that is selected among K, La and the Bi;
Described catalyst cupport is on absorbent charcoal carrier;
The consumption of palladium is 0.1～5.0% of total catalyst weight in described the first catalyst, and the consumption of copper is 0.5～15.0% of total catalyst weight, and the consumption of described the second catalyst is 0.05～5.0% of total catalyst weight, and its surplus is carrier;
Reaction temperature is 110～150 ℃, and the hexafluoroacetone hydrate vapourizing temperature is 110～180 ℃, and hexafluoroacetone hydrate liquid air speed is 0.05～0.8h
-1, the mol ratio of hydrogen and hexafluoroacetone hydrate is 1～3.
2. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 1 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, the consumption that it is characterized in that palladium in described the first catalyst is 0.5～3.0% of total catalyst weight, the consumption of copper is 1.0～10.0% of total catalyst weight, the consumption of described the second catalyst is 0.05～3.0% of total catalyst weight, and its surplus is carrier.
3. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 1 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that described active carbon is the coconut husk charcoal, specific area is at 1000～1300m
2Between/the g, pore volume is at 0.6～0.9cm
3Between/the g, apparent density is at 0.45～0.55g/cm
3Between.
4. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 1 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that described absorbent charcoal carrier needs through the pickling preliminary treatment.
5. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 4 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that described pickling preliminary treatment may further comprise the steps:
(1) adopt acid solution absorbent charcoal carrier to be carried out pickling processes, 60～100 ℃ for the treatment of temperatures, processing time 1～5h;
(2) the washing absorbent charcoal carrier is until eluate pH value is constant;
(3) vacuum drying absorbent charcoal carrier, 80～120 ℃ of baking temperatures, drying time 2～5h.
6. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 5 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that described acid solution is that the quality percentage composition is 30% salpeter solution.
7. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 1 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that infusion process is adopted in the preparation of described catalyst, may further comprise the steps:
(1) the soluble-salt solution of configuration the first catalyst and the second catalyst, Immesion active carbon carrier, dip time 〉=5h;
(2) vacuum drying 2～5h, 80～120 ℃ of baking temperatures;
(3) high-temperature roasting 2～5h, 300～600 ℃ of sintering temperatures.
8. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 7 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that described soluble-salt solution is deionized water solution.
9. prepare application in the hexafluoroisopropanol reaction according to catalyst claimed in claim 1 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that catalyst at first needed to reduce processing before reaction.
10. prepare application in the hexafluoroisopropanol reaction according to the described catalyst of claim 9 at used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate, it is characterized in that reducing gas is hydrogen nitrogen mixed gas, wherein the hydrogen ratio is 5～50%, reduction temperature is 150～300 ℃, recovery time is 1.0～3.0h, reducing gases air speed 〉=300h
-1
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| CN111111672B (en) * | 2019-12-30 | 2022-07-08 | 天津市长芦化工新材料有限公司 | Catalyst with hydrogen storage performance and preparation method and application thereof |
| CN110961040B (en) * | 2019-12-30 | 2023-11-24 | 天津市长芦化工新材料有限公司 | Device for preparing hexafluoroisopropanol by catalytic hydrogenation and application method thereof |
| CN111205166B (en) * | 2019-12-30 | 2022-04-22 | 天津市长芦化工新材料有限公司 | Method for preparing hexafluoroisopropanol by gas-phase hydrogenation |
| CN111097426B (en) * | 2019-12-30 | 2022-08-30 | 天津市长芦化工新材料有限公司 | Copper-based gas phase catalyst and preparation method and application thereof |
| CN111790401A (en) * | 2020-06-22 | 2020-10-20 | 山东东岳高分子材料有限公司 | Catalyst for synthesizing hexafluoroisopropanol, preparation method and application |
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