CN102274734A - 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
- Publication number
- CN102274734A CN102274734A CN2010102022416A CN201010202241A CN102274734A CN 102274734 A CN102274734 A CN 102274734A CN 2010102022416 A CN2010102022416 A CN 2010102022416A CN 201010202241 A CN201010202241 A CN 201010202241A CN 102274734 A CN102274734 A CN 102274734A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- catalytic hydrogenation
- hexafluoroacetone hydrate
- hexafluoroisopropanol
- phase catalytic
- 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.)
- Granted
Links
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 relate to and be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol.
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 the manufacturing and the cleaning of most advanced and sophisticated instrument and equipment as senior cleaning agent.HFIP can also well dissolve the big molecule of amino acids, 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, as synthetic current state-of-the-art suction-type anesthetic-Sevoflurane.
The technology that with the Hexafluoro acetone is catalytic material hydrogenation preparing hexafluoroisopropanol has atom economy, yield advantages of higher, becomes the key industry method of present production hexafluoroisopropanol.Can be divided into the gaseous state Hexafluoro acetone according to the different existence forms of raw material Hexafluoro acetone and to be the catalytic hydrogenation process of raw material and to be the catalytic hydrogenation process of raw material with the hexafluoroacetone hydrate.
Patent US3702872, BE634368, NL6610936, US3607952, GB2073181, US3356742, US7524995, JP2009051798 have reported that with the gaseous state Hexafluoro acetone be the feedstock production hexafluoroisopropanol.Though this technology of some of them patent report can reach higher product yield, also exist many defectives that are difficult to overcome simultaneously, 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, contain impurity such as HF, HCl in the raw material usually, these impurity are easy to cause the hydrogenation catalyst inactivation in hydrogenation process, shorten catalyst life etc.
And be that the catalytic hydrogenation process of raw material can overcome above-mentioned defective with the hexafluoroacetone hydrate.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, normal temperature is down for liquid, 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 technology mostly adopts liquid-phase hydrogenatin technology to prepare hexafluoroisopropanol, patent CN1962589 for example, JP2002275107, JP6184025, JP1301631, JP59204142 and US4564716 report, the employing hexafluoroacetone hydrate is a raw material, be hydrogenation catalyst with noble metal catalyst such as palladium, ruthenium, nickel, copper etc. respectively, in reactor, carry out liquid-phase hydrogenatin prepared in reaction hexafluoroisopropanol.Liquid-phase hydrogenatin technological reaction temperature is low, the hydrogen utilization ratio height, 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 be that raw material is after vaporization with the hexafluoroacetone hydrate, prepare hexafluoroisopropanol by the Fixed Bed Gas Phase catalytic hydrogenation process, the comprehensive two-fold advantage of preceding two kinds of technologies then, avoid the defective of its existence simultaneously, this technological reaction mild condition, the product yield height is beneficial to industrial continuous production, has bright development prospect.The key of this technology is to have the catalyst of excellent hydrogenation performance, but the research report about this technology is considerably less, the only central nitre patent US4467124 of subsidiary report, with the hexafluoroacetone hydrate is 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): 32-33) also reported with the hexafluoroacetone hydrate to be raw material, 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 impurity such as a spot of 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 industrialization demands, and document " study on the synthesis of hexafluoroisopropanol " (Wang Yi, Ren Jiangang, Li Huili, the Shaanxi chemical industry, 1997 (9): 32-33) Bao Dao product yield shows that less than 90% also there is big gap in nickel chromium triangle copper catalyst activity apart from industry's enlarging production.Therefore develop a kind of high activity, be applicable to this reaction system, have the hydrogenation catalyst of better stability simultaneously concurrently,, realize that the suitability for industrialized production of hexafluoroisopropanol has great importance for the advantage of giving full play to the hexafluoroacetone hydrate gas-phase catalytic hydrogenation preparation technology who is raw material.
Summary of the invention
The object of the present invention is to provide a kind of hexafluoroacetone hydrate gas-phase catalytic hydrogenation to prepare the catalyst of hexafluoroisopropanol, this Preparation of catalysts technology and application, this catalyst has advantages such as catalytic hydrogenation activity height, the hexafluoroisopropanol selectivity is good, catalyst stability is excellent, reaction condition is gentle, catalyst preparation process is simple.
For achieving the above object, the present invention adopts following technological means.
A kind ofly be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol, comprise first catalyst, second catalyst and carrier;
Described first catalyst is palladium and copper;
Described 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.
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 activity of such catalysts, improve the stability of catalyst, can also reduce the load capacity of precious metal palladium simultaneously, reduce the Catalyst Production cost.
Second catalyst of the present invention mainly plays modification, modifying function to first catalyst.Second catalyst and palladium atomic interaction, can change palladium atom Cloud Distribution on every side, thereby improve selection of catalysts, the interpolation of second catalyst can also improve the dispersity of main active component at carrier surface, regulate the interaction force between the active component, it is grained sintered to suppress active constituent, strengthens the anti-carbon deposit performance 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 a total catalyst weight in first catalyst, the consumption of copper is 0.5～15.0% of a total catalyst weight, and described second catalyst consumption is 0.05～5.0% of a total catalyst weight, and its surplus is a carrier; As preferably, the consumption of palladium is 0.5～3.0% of a total catalyst weight in first catalyst, and the consumption of copper is 1.0～10.0% of a total catalyst weight, and described second catalyst consumption is 0.05～3.0% of a total catalyst weight, and its surplus is a 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, for example hydrofluoric acid, hydrochloric acid, chloric acid, hydrobromic acid, bromic acid etc.; Sulfur acid, for example sulfuric acid, sulfurous acid, hydrosulphuric acid etc.; Nitrogen acid, for example nitric acid, industry nitric acid etc.; Phosphoric acid, for example phosphoric acid, industry phosphoric acid, hypophosphorous acid etc.; And inorganic acid such as carbonic acid.The organic acid example has acetate, 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 ℃ of treatment temperatures, processing time 1～5h;
(2) the washing absorbent charcoal carrier is constant until eluate pH value;
(3) vacuum drying absorbent charcoal carrier, 80～120 ℃ of baking temperatures, drying time 2～5h.
Preparation of catalysts of the present invention adopts infusion process, may further comprise the steps:
(1) the soluble-salt solution of configuration first catalyst and 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 also can be flooded altogether, can flood palladium-impregnated and copper behind second catalyst earlier, or palladium-impregnated behind dipping second catalyst and the copper earlier, also can second catalyst, copper and the disposable dipping of palladium finish.
Hexafluoroacetone hydrate gas-phase catalytic hydrogenation of the present invention prepares hexafluoroisopropanol and is reflected in the fixed bed reactors and carries out, 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, feed 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
-1Carry out operation then, 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 a normal pressure.The catalytic hydrogenation reaction temperature is preferably 110～150 ℃.Product is through condensation separation, and hydrogen emptying is adopted gas chromatographic analysis conversion ratio and selectivity 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, reduce to room temperature, deionized water washs to the eluate pH value constant, and 100 ℃ of vacuum drying 4.0h are standby.
Embodiment 2Pd-Cu-K/C Preparation of Catalyst and activity rating
Take by weighing 0.1gKCl, add the 10g deionized water dissolving, in solution, add processed active carbon carrier among the 10g embodiment 1, dipping 10.0h, 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 then
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, standby through 500 ℃ of roasting 3.0h again.
Take by weighing the catalyst sample 3.0ml that the prepares fixed bed reactors of packing into, feed 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 selectivity 99.9%.
Embodiment 3Pd-Cu-La/C Preparation of 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 processed active carbon carrier among the embodiment 1 in mixed solution, dipping 12.0h, 90 ℃ of vacuum drying 5.0h.Take by weighing 8.0g chlorine palladium aqueous acid (the quality percentage composition 2.55% of palladium) then, add 2.0g deionized water wiring solution-forming, in solution, add the front and flooded La, the active carbon of Cu, dipping 24.0h, 90 ℃ of vacuum drying 5.0h, standby 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 selectivity 99.7%.
Embodiment 4Pd-Cu-Bi/C Preparation of Catalyst and activity rating
Take by weighing 0.38gBiCl
3, add the 10g deionized water dissolving, in solution, add processed active carbon carrier 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, take by weighing 2.0g chlorine palladium aqueous acid (the quality percentage composition 2.55% of palladium) then, in solution, add and flooded Bi, the active carbon of Cu, dipping 10h, 90 ℃ of vacuum drying 5.0h, standby 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 selectivity 100%.
Embodiment 5Pd-Cu-K-La/C Preparation of Catalyst and activity rating
Take by weighing 0.2gKCl, 0.62gLa (NO
3)
36H
2O adds the 10g deionized water dissolving, adds processed active carbon carrier among the 10g embodiment 1 in solution, dipping 15.0h, and 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 then successively
22H
2O, dipping 24h, 90 ℃ of vacuum drying 5.0h, standby 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 selectivity 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 selectivity 99.7%.
Comparative example 2Ni-Cr-Cu Preparation of 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, method, condition that reactivity is estimated are identical with embodiment 2.Gas chromatographic analysis hexafluoroacetone hydrate conversion ratio is 85.0%, hexafluoroisopropanol selectivity 93.0%.
The reaction stability experiment of embodiment 6 catalyst P d-Cu-K/C and Pd/C
According to the 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, the initial activity of commercial as can be seen Pd/C catalyst and catalyst difference of the present invention are little, hexafluoroacetone hydrate conversion ratio and hexafluoroisopropanol selectivity are all more than 99%, but as can be seen from stability data, at preceding 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 catalyst inactivation aggravation, when reacting to 250h, the hexafluoroacetone hydrate conversion ratio reduces 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 has decline slightly after reaction reaches 700h, but still remain on more than 99.5%, the hexafluoroisopropanol selectivity does not 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 tangible.
Table 1 catalyst P d-Cu-K/C and Pd/C reaction stability experimental result
Claims (13)
1. one kind is used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol, it is characterized in that described catalyst comprises first catalyst, second catalyst and carrier;
Described first catalyst is palladium and copper;
Described 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.
2. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 1 is described, the consumption that it is characterized in that palladium in described first catalyst is 0.1～5.0% of a total catalyst weight, the consumption of copper is 0.5～15.0% of a total catalyst weight, described second catalyst consumption is 0.05～5.0% of a total catalyst weight, and its surplus is a carrier.
3. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 2 is described, the consumption that it is characterized in that palladium in described first catalyst is 0.5～3.0% of a total catalyst weight, the consumption of copper is 1.0～10.0% of a total catalyst weight, described second catalyst consumption is 0.05～3.0% of a total catalyst weight, and its surplus is a carrier.
4. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 1 is described, 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.
5. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 1 is described, it is characterized in that described absorbent charcoal carrier needs through the pickling preliminary treatment.
6. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 5 is described, 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 ℃ of treatment temperatures, processing time 1～5h;
(2) the washing absorbent charcoal carrier is constant until eluate pH value;
(3) vacuum drying absorbent charcoal carrier, 80～120 ℃ of baking temperatures, drying time 2～5h.
7. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 6 is described, it is characterized in that described acid solution is 30% salpeter solution for the quality percentage composition.
8. one kind is used for the Preparation of catalysts method that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 1 is described, it is characterized in that adopting infusion process, may further comprise the steps:
(1) the soluble-salt solution of configuration first catalyst and 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.
9. be used for the Preparation of catalysts method that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 8 is described, it is characterized in that described soluble-salt solution is deionized water solution.
10. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 1 is described, it is characterized in that catalyst at first needed to reduce processing before reaction.
11. be used for the catalyst that the hexafluoroacetone hydrate gas-phase catalytic hydrogenation prepares hexafluoroisopropanol according to claim 10 is described, it is characterized in that reducing gas is a 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
12. prepare application in the hexafluoroisopropanol reaction at the hexafluoroacetone hydrate gas-phase catalytic hydrogenation according to each described catalyst of claim 1 to 11, it is characterized in that described reaction temperature is 110～150 ℃, the hexafluoroacetone hydrate vapourizing temperature is 110～180 ℃.
13. prepare application in the hexafluoroisopropanol reaction according to the described catalyst of claim 12 at the hexafluoroacetone hydrate gas-phase catalytic hydrogenation, it is characterized in that hexafluoroacetone hydrate liquid air speed is 0.05～0.8h
-1, the mol ratio of hydrogen and hexafluoroacetone hydrate is 1～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010202241 CN102274734B (en) | 2010-06-13 | 2010-06-13 | Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010202241 CN102274734B (en) | 2010-06-13 | 2010-06-13 | Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102274734A true CN102274734A (en) | 2011-12-14 |
| CN102274734B CN102274734B (en) | 2013-10-16 |
Family
ID=45100649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010202241 Active CN102274734B (en) | 2010-06-13 | 2010-06-13 | Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102274734B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258803A (en) * | 2013-09-04 | 2015-01-07 | 赵世怀 | Method for preparing carbon monoxide filtering material |
| CN104368359A (en) * | 2014-11-12 | 2015-02-25 | 厦门大学 | Catalyst for preparing 3-pentanol through 3-pentanone hydrogenation and preparation method of catalyst for preparing 3-pentanol through 3-pentanone hydrogenation |
| CN109320398A (en) * | 2018-08-28 | 2019-02-12 | 浙江工业大学 | A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation |
| CN110961040A (en) * | 2019-12-30 | 2020-04-07 | 天津市长芦化工新材料有限公司 | Device for preparing hexafluoroisopropanol through catalytic hydrogenation and using method thereof |
| CN111097426A (en) * | 2019-12-30 | 2020-05-05 | 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 |
| CN111111672A (en) * | 2019-12-30 | 2020-05-08 | 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 |
| CN111205166A (en) * | 2019-12-30 | 2020-05-29 | 天津市长芦化工新材料有限公司 | Method for preparing hexafluoroisopropanol by gas-phase hydrogenation |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4467124A (en) * | 1980-11-11 | 1984-08-21 | Central Glass Company Limited | Preparation of 1,1,1,3,3,3-hexafluoropropane-2-ol by vapor phase catalytic reaction of hexafluoroacetone hydrate with hydrogen |
| CN1460549A (en) * | 2003-07-07 | 2003-12-10 | 大连振邦氟涂料股份有限公司 | Catalyst for preparing trifluorochloroethylene and trifluoroethylene by using CFC-113 catalytic hydro-dechlorination and its preparation method |
| CN102211028A (en) * | 2010-04-08 | 2011-10-12 | 中化蓝天集团有限公司 | Hydrogenation dechlorinating catalyst for synthesizing trifluoroethylene and novel preprocessing process of carrier of catalyst |
-
2010
- 2010-06-13 CN CN 201010202241 patent/CN102274734B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4467124A (en) * | 1980-11-11 | 1984-08-21 | Central Glass Company Limited | Preparation of 1,1,1,3,3,3-hexafluoropropane-2-ol by vapor phase catalytic reaction of hexafluoroacetone hydrate with hydrogen |
| CN1460549A (en) * | 2003-07-07 | 2003-12-10 | 大连振邦氟涂料股份有限公司 | Catalyst for preparing trifluorochloroethylene and trifluoroethylene by using CFC-113 catalytic hydro-dechlorination and its preparation method |
| CN102211028A (en) * | 2010-04-08 | 2011-10-12 | 中化蓝天集团有限公司 | Hydrogenation dechlorinating catalyst for synthesizing trifluoroethylene and novel preprocessing process of carrier of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 冯东东等: "六氟异丙醇的合成研究", 《有机氟工业》, no. 3, 31 December 2007 (2007-12-31), pages 23 - 26 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258803A (en) * | 2013-09-04 | 2015-01-07 | 赵世怀 | Method for preparing carbon monoxide filtering material |
| CN104368359A (en) * | 2014-11-12 | 2015-02-25 | 厦门大学 | Catalyst for preparing 3-pentanol through 3-pentanone hydrogenation and preparation method of catalyst for preparing 3-pentanol through 3-pentanone hydrogenation |
| CN104368359B (en) * | 2014-11-12 | 2016-08-17 | 厦门大学 | A kind of catalyst of propione Hydrogenation 3-amylalcohol and preparation method thereof |
| CN109320398A (en) * | 2018-08-28 | 2019-02-12 | 浙江工业大学 | A method of benzhydrol is synthesized by benzophenone catalytic hydrogenation |
| CN109320398B (en) * | 2018-08-28 | 2022-03-18 | 浙江工业大学 | Method for synthesizing benzhydryl alcohol by catalytic hydrogenation of benzophenone |
| CN110961040A (en) * | 2019-12-30 | 2020-04-07 | 天津市长芦化工新材料有限公司 | Device for preparing hexafluoroisopropanol through catalytic hydrogenation and using method thereof |
| CN111097426A (en) * | 2019-12-30 | 2020-05-05 | 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 |
| CN111111672A (en) * | 2019-12-30 | 2020-05-08 | 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 |
| CN111205166A (en) * | 2019-12-30 | 2020-05-29 | 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102274734B (en) | 2013-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102274734B (en) | Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof | |
| CN107649124B (en) | Monoatomic dispersed noble metal catalyst and application thereof | |
| CN101347737B (en) | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid | |
| CN110898853B (en) | Catalyst for preparing cyclohexanone by phenol hydrogenation and preparation method thereof | |
| CN106512994B (en) | Anti-carbon deposition catalyst for preparing propylene by platinum-based propane dehydrogenation and preparation method thereof | |
| CN106748813B (en) | A kind of synthesis N, the method for N '-dibenzyl-ethylenediamin | |
| CN103877991B (en) | Anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof | |
| CN101767016B (en) | Aromatic aldehyde selective hydrogenation catalyst for refining terephthalic acid | |
| CN101347730A (en) | Hydrogenation catalyst for refinement of crude terephthalic acid | |
| CN110743544A (en) | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof | |
| CN101767004B (en) | Preparation method of crude terephthalic acid hydrogenation catalyst | |
| CN103880590A (en) | Process for preparing 1,3,3,3-tetrafluoropropene | |
| CN102698761A (en) | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application | |
| CN102416325A (en) | Preparation method of isobutyl ketone synthesis catalyst | |
| CN101462051B (en) | Catalyst for generating crotonyl alcohol by selective hydrogenation of gas-phase crotonaldehyde and preparation method thereof | |
| JP6301387B2 (en) | Catalyst and method for chlorine production by gas phase oxidation | |
| CN104971740A (en) | Catalyst for continuously preparing N-isopropyl-4-fluoroanilines, and preparation method and application of catalyst | |
| CN103044190B (en) | Preparation method of trifluoroethylene | |
| CN109952270B (en) | Method for producing chlorine by hydrogen chloride oxidation | |
| CN102553614B (en) | Preparation method of catalyst for producing difluoroethanol by hydrogenation of difluoro carboxylate | |
| CN114849694B (en) | Catalyst for hydrogenation of nitroaromatic hydrocarbon based on metal-loaded tungsten oxide, preparation method and application thereof | |
| KR102223388B1 (en) | Preparation method of ruthenium-platinum-tin catalyst for hydrogenation of cyclohexane dicarboxylic acid (CHDA) and method for producing cyclohexane dimethanol (CHDM) using said catalyst | |
| CN112452340B (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, preparation method and application thereof | |
| CN114054023B (en) | Preparation method and application of alloy monoatomic catalyst | |
| CN107540534A (en) | A kind of method that no water soluble alkali catalysis glucose dehydrogenation oxidation prepares gluconic acid |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210929 Address after: 312369 No. 5, Weiqi Road, Shangyu economic and Technological Development Zone, Hangzhou Bay, Shaoxing City, Zhejiang Province Patentee after: SINOCHEM LANTIAN FLUORINE MATERIAL Co.,Ltd. Patentee after: SINOCHEM LANTIAN Co.,Ltd. Patentee after: ZHEJIANG LANTIAN ENVIRONMENTAL PROTECTION HI-TECH Co.,Ltd. Address before: 310007 No. 487 Stadium Road, Hangzhou City, Zhejiang Province Patentee before: SINOCHEM LANTIAN Co.,Ltd. Patentee before: ZHEJIANG LANTIAN ENVIRONMENTAL PROTECTION HI-TECH Co.,Ltd. |