CN103752327A - Catalyst for producing isopropyl alcohol through acetone hydrogenation and method for catalytically producing isopropyl alcohol - Google Patents

Catalyst for producing isopropyl alcohol through acetone hydrogenation and method for catalytically producing isopropyl alcohol Download PDF

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CN103752327A
CN103752327A CN201310713969.9A CN201310713969A CN103752327A CN 103752327 A CN103752327 A CN 103752327A CN 201310713969 A CN201310713969 A CN 201310713969A CN 103752327 A CN103752327 A CN 103752327A
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catalyst
isopropyl alcohol
acetone
platinum
producing isopropyl
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CN103752327B (en
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李亚栋
纪永军
赵国锋
王定胜
彭卿
刘磊
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Tsinghua University
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Abstract

The invention discloses a catalyst for producing isopropyl alcohol through acetone hydrogenation and a method for catalytically producing the isopropyl alcohol, and belongs to the technical field of preparation of chemical materials. The catalyst comprises an inorganic oxide carrier and an active ingredient, wherein the active ingredient is platinum or an alloy of platinum and transitional metal M; the transitional metal M is Fe, Sn or Co preferably. The catalyst is easy to industrially prepare; by replacing an original catalyst with the catalyst disclosed by the invention, the problems of production of a toxic catalyst such as a Cr-containing catalyst and the subsequent environment pollution can be avoided. The catalyst is used for an acetone hydrogenation reaction, and is high in yield of isopropyl alcohol products and good in selectivity.

Description

Acetone hydrogenation is produced the catalyst of isopropyl alcohol and the method for catalytic production isopropyl alcohol thereof
Technical field
The present invention relates to a kind of acetone hydrogenation and produce the catalyst of isopropyl alcohol, specifically relate to a kind of platinum based catalyst, belong to chemical industry financial resources preparing technical field.
Background technology
Industrial isopropyl alcohol is produced the general method that adopts propylene hydration and is obtained, esterification process as indirect in sulfuric acid, solid acid catalyst or cation exchange resin catalyst direct hydration method.
Industrial acetone is mainly obtained by isopropylbenzene peroxidating method, and in phenol coproduction.Due to the increase of phenol demand, produce a large amount of acetone, there is the imbalance of demand, cause the situation of acetone surplus, and H 2low price easily obtains, and so just making becomes an economically feasible route by preparing isopropyl alcohol by acetone hydrogenation, also meets Atom economy.
The available Ni-based or copper-based catalysts of acetone hydrogenation reaction or adopt the catalysis such as precious metals pt, Pd, Ru, Rh.Reaction unit mainly adopts fixed bed reactors, and acetone and hydrogen enter the reactor that catalyst is housed continuously with gas phase form with certain proportioning, and under proper temperature and hydrogen pressure, Hydrogenation obtains isopropyl alcohol.
Nickel-base catalyst is take Raney Ni as best, and the flat 3-141235 of Japanese Patent Laid discloses acetone, and on raney nickel catalyst, Hydrogenation is for the reaction of isopropyl alcohol, and acetone conversion and isopropyl alcohol are selectively up to 99.9%.But raney nickel catalyst price is relatively high, and more complicated when Catalyst packing, operation.
The advantage of copper-based catalysts is that preparation is simple, low price and easy operating are used.Copper-based catalysts is generally carried on carrier, or compound as catalyst with other metal oxide.Improved copper-based catalysts can reach good catalytic effect same with nickel-base catalyst, but can cause some other side reactions, causes isopropyl alcohol selectively not high.In addition, adopt some poisonous oxides as Cr 2o 3as auxiliary agent is compound, can produce problem of environmental pollution (Russian Patent SU1051055A, SU1118632A, the flat 3-41038 of Japan Patent).
, although activity and selectivity is higher, price is more expensive for noble metal catalyst (as Pt, Pd, Ru, Rh).In addition, hydrogenation technique condition harshness, reaction pressure is too high.The flat 2-279643 of Japan Patent discloses Ru/Al 2o 3catalysis acetone hydrogenation technique, under the pressure of 9MPa, reaches as high as 99.9% conversion ratio, and isopropyl alcohol is selectively also up to 99.9%.
Summary of the invention
The object of the invention is to provide for global acetone surplus and the deficiencies in the prior art a kind of and produce the catalyst of isopropyl alcohol and the method that acetone catalytic hydrogenation is produced isopropyl alcohol thereof for acetone catalytic hydrogenation.
Technical scheme of the present invention is as follows:
Acetone catalytic hydrogenation is produced a catalyst for isopropyl alcohol, it is characterized in that: this catalyst comprises inorganic oxide carrier and active component, and active component is the alloy of platinum or platinum and transition metal M.
Technical characterictic of the present invention is also: the load capacity of described platinum on carrier is 1wt%～5wt% by weight; Described Pt and the mol ratio of transition metal M are 1:3～3:1.
In technique scheme, described inorganic oxide carrier is Fe 2o 3, Fe 3o 4, Al 2o 3, CeO 2, ZrO 2and TiO 2in at least one; Described transition metal M is Fe, Sn or Co.
A kind of method that adopts described catalyst acetone hydrogenation to produce isopropyl alcohol provided by the invention, is characterized in that: adopt fixed bed by carrying out to dirty method or autoclave; Adopt fixed bed to press to dirty method, reaction condition is that temperature is 60～150 ℃, and pressure is normal pressure; Adopt autoclave, reaction condition is that temperature is 100～150 ℃, and pressure is 2MPa.
The present invention has the following advantages and the technique effect of high-lighting: catalyst of the present invention is easy to preparation of industrialization, with the original catalyst of this catalyst replaced, can avoid containing poisonous Catalyst Production and follow-up problem of environmental pollutions such as Cr simultaneously, adopt catalyst of the present invention, under above-mentioned mild reaction conditions, can obtain high acetone conversion and isopropyl alcohol selective.
The specific embodiment
The catalyst that acetone catalytic hydrogenation provided by the invention is produced isopropyl alcohol comprises inorganic oxide carrier and active component, and active component is the alloy of platinum or platinum and transition metal M.The load capacity of described platinum on inorganic oxide carrier is 1wt%～5wt% by weight; Described Pt and the mol ratio of transition metal M are 1:3～3:1; Described inorganic oxide carrier is Fe 2o 3, Fe 3o 4, Al 2o 3, CeO 2, ZrO 2and TiO 2in at least one.Described transition metal M is preferably Fe, Sn or Co.
The acetone catalytic hydrogenation of the described catalyst of employing provided by the invention is produced the method for isopropyl alcohol, and the method is to adopt fixed bed by carrying out to dirty method or autoclave; Adopt fixed bed to press to dirty method, reaction condition is that temperature is 60～150 ℃, and pressure is normal pressure; Adopt autoclave, reaction condition is that temperature is 100～150 ℃, and pressure is 2MPa.
Catalyst of the present invention can adopt following methods to prepare:
First by octadecylamine in 80 ℃～100 ℃ dissolvings, add carrier that it is mixed; Then be warming up to 240 ℃～280 ℃, under vigorous stirring, by being dissolved in the acetylacetone,2,4-pentanedione platinum of oleyl amine or the salt of acetylacetone,2,4-pentanedione platinum and transition metal M, inject, continue to stir 15min～30min; The load capacity of described platinum on carrier is 1wt%～5wt% by weight, and carrier is Fe 2o 3, Fe 3o 4, Al 2o 3, CeO 2, ZrO 2and TiO 2in at least one, the salt of transition metal M adopts acetylacetonate, chloride or nitrate, transition metal M is the one in Fe, Sn and Co, the mol ratio of Pt and M is 1:3～3:1; Reaction finishes to be cooled to 70 ℃～80 ℃, adds absolute ethyl alcohol sedimentation, topples over supernatant liquor, then with absolute ethanol washing for several times after, dryly obtain described acetone hydrogenation to produce the load type platinum of isopropyl alcohol catalyst based.
Below by several embodiment, the invention will be further described, and its object is only better to understand research contents of the present invention but not limits the scope of the invention.
Embodiment 1
5g octadecylamine, in 80 ℃ of dissolvings, is then warming up to 240 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum is dissolved in to ultrasonic 5min in 2.5mL oleyl amine, inject above-mentioned system under vigorous stirring, continue to stir 15min, reaction finishes to be cooled to 70 ℃, adds 0.2g Fe 2o 3it is mixed, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 2
5g octadecylamine, in 100 ℃ of dissolvings, is then warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum is dissolved in to ultrasonic 5min in 2.5mL oleyl amine, inject above-mentioned system under vigorous stirring, continue to stir 20min, reaction finishes to be cooled to 80 ℃, adds 0.2g Fe 3o 4it is mixed, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 3
5g octadecylamine, in 80 ℃ of dissolvings, is added to 0.2g Al 2o 3it is mixed, then be warming up to 280 ℃, 0.004g acetylacetone,2,4-pentanedione platinum is dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 30min, reaction finishes to be cooled to 70 ℃, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 4
5g octadecylamine, in 80 ℃ of dissolvings, is added to 0.2g TiO 2it is mixed, then be warming up to 240 ℃, 0.020g acetylacetone,2,4-pentanedione platinum is dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 5
5g octadecylamine, in 80 ℃ of dissolvings, is then warming up to 240 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum is dissolved in to ultrasonic 5min in 2.5mL oleyl amine, inject above-mentioned system under vigorous stirring, continue to stir 15min, reaction finishes to be cooled to 70 ℃, adds 0.1g Fe 2o 3with 0.1g Fe 3o 4mixture it is mixed, add ethanol sedimentation, topple over supernatant liquor, then with absolute ethanol washing for several times after, 70 ℃ are dry.
Embodiment 6
5g octadecylamine, in 80 ℃ of dissolvings, is then warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0035g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, adds 0.2g Fe 3o 4it is mixed, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 7
5g octadecylamine, in 80 ℃ of dissolvings, is then warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0318g ferric acetyl acetonade are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, adds 0.2g Fe 3o 4it is mixed, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 8
5g octadecylamine, in 80 ℃ of dissolvings, is added to 0.2g Al 2o 3it is mixed, then be warming up to 260 ℃, 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0087g cabaltous nitrate hexahydrate are dissolved in to ultrasonic 5min in 2.5mL oleyl amine, under vigorous stirring, inject above-mentioned system, continue to stir 15min, reaction finishes to be cooled to 70 ℃, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ dry.
Embodiment 9
5g octadecylamine, in 80 ℃ of dissolvings, is then warming up to 260 ℃, by 0.0118g acetylacetone,2,4-pentanedione platinum and 0.0057gSnCl 22H 2o is dissolved in ultrasonic 5min in 2.5mL oleyl amine, injects above-mentioned system under vigorous stirring, continues to stir 15min, and reaction finishes to be cooled to 70 ℃, adds 0.05g Fe 2o 3, 0.05g Fe 3o 4, 0.025g Al 2o 3, 0.025g CeO 2, 0.025g ZrO 2with 0.025g TiO 2, add ethanol sedimentation, topple over supernatant liquor, then with after absolute ethanol washing several, 70 ℃ are dry.
Embodiment 10
The explanation of this example generates in isopropanol reaction at acetone hydrogenation, and catalyst provided by the invention is for the catalytic reaction result of fixed bed.
Reaction unit is normal pressure continuous-flow fixed bed, and reactor inside diameter is 7mm, and the loadings of catalyst is 0.1g, and catalyst grain size is 20～40 orders.
Acetone sample rate is 1.8mL/h, and nitrogen flow is 30mL/min, and hydrogen flowing quantity is 30mL/min, and reaction pressure is normal pressure, and the reaction time is 1h.
Before catalyst reaction, need at 300 ℃ at N 2(30mL/min) and H 2(30mL/min) in mixed atmosphere, activate 2h.
Reactant acetone and hydrogen enter beds continuously with gas phase, and product is passed through capillary gas chromatography, flame ionization ditector online.
Embodiment 11
The explanation of this example generates in isopropanol reaction at acetone hydrogenation, and catalyst provided by the invention is for the catalytic reaction result of autoclave.
Reaction unit is autoclave, and the consumption of catalyst is 0.1g, the feeding intake as 5mmol of acetone, and cyclohexane is 15mL, and reaction pressure is 2MPa, and the reaction time is 4h.
Product is by capillary gas chromatography, flame ionization ditector.
Figure BDA0000442985330000051
Experimental result shows, adopts catalyst provided by the invention to preparing isopropyl alcohol by acetone hydrogenation, and product yield is high, selectively good.

Claims (5)

1. acetone catalytic hydrogenation is produced a catalyst for isopropyl alcohol, it is characterized in that: this catalyst comprises inorganic oxide carrier and active component, and active component is the alloy of platinum or platinum and transition metal M.
2. the catalyst of producing isopropyl alcohol according to a kind of acetone catalytic hydrogenation claimed in claim 1, is characterized in that: the load capacity of described platinum on inorganic oxide carrier is 1wt%～5wt% by weight; Described Pt and the mol ratio of transition metal M are 1:3～3:1.
3. the catalyst of producing isopropyl alcohol according to a kind of acetone catalytic hydrogenation described in claim 1 or 2, is characterized in that: described inorganic oxide carrier is Fe 2o 3, Fe 3o 4, Al 2o 3, CeO 2, ZrO 2and TiO 2in at least one.
4. the catalyst of producing isopropyl alcohol according to a kind of acetone catalytic hydrogenation described in claim 1 or 2, is characterized in that: described transition metal M is Fe, Sn or Co.
5. adopt the method that the acetone catalytic hydrogenation of catalyst is produced isopropyl alcohol as claimed in claim 1 or 2, it is characterized in that: the method adopts fixed bed by carrying out to dirty method or autoclave; Adopt fixed bed to press to dirty method, reaction condition is that temperature is 60～150 ℃, and pressure is normal pressure; Adopt autoclave, reaction condition is that temperature is 100～150 ℃, and pressure is 2MPa.
CN201310713969.9A 2013-12-20 2013-12-20 Acetone hydrogenation produces the catalyst of isopropyl alcohol and the method for catalytic production isopropyl alcohol thereof Active CN103752327B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107930638A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 The copper-based catalysts of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone
CN112044434A (en) * 2020-10-20 2020-12-08 北京单原子催化科技有限公司 Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5476972A (en) * 1994-01-28 1995-12-19 Texaco Chemical Inc. Isopropyl alcohol and ether production from crude by-product acetone
CN101801896A (en) * 2007-09-19 2010-08-11 三井化学株式会社 Method for producing alcohol and acid-treated raney catalyst
CN103153930A (en) * 2010-09-23 2013-06-12 国际人造丝公司 Production of alcohols

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5476972A (en) * 1994-01-28 1995-12-19 Texaco Chemical Inc. Isopropyl alcohol and ether production from crude by-product acetone
CN101801896A (en) * 2007-09-19 2010-08-11 三井化学株式会社 Method for producing alcohol and acid-treated raney catalyst
CN103153930A (en) * 2010-09-23 2013-06-12 国际人造丝公司 Production of alcohols

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107930638A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 The copper-based catalysts of Status of OneStep Synthesis of Methyl isoButyl Ketone from Acetone
CN112044434A (en) * 2020-10-20 2020-12-08 北京单原子催化科技有限公司 Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof
CN112044434B (en) * 2020-10-20 2023-03-28 北京单原子催化科技有限公司 Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof

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