CN102728361A - Catalyst for isopropyl alcohol preparation through acetone hydrogenation and application thereof - Google Patents
Catalyst for isopropyl alcohol preparation through acetone hydrogenation and application thereof Download PDFInfo
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- CN102728361A CN102728361A CN2011100830795A CN201110083079A CN102728361A CN 102728361 A CN102728361 A CN 102728361A CN 2011100830795 A CN2011100830795 A CN 2011100830795A CN 201110083079 A CN201110083079 A CN 201110083079A CN 102728361 A CN102728361 A CN 102728361A
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- isopropyl alcohol
- acetone
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Abstract
The invention discloses a catalyst for isopropyl alcohol preparation through acetone hydrogenation and application thereof. In order to solve a problem of unsatisfactory catalyst usage in existing process of isopropyl alcohol preparation through acetone hydrogenation, the catalyst of the invention uses alumina with BET specific surface area of 150-350 m<2> / g and pore volume of 0.30-0.80 m<3> / g as a carrier, and comprises 8% -25% of nickel with surface area of 10-30 m<2> / g. The yield of isopropyl alcohol through acetone hydrogenation is significantly improved compared with existing technique, and the isopropyl alcohol yield reaches 99.4% under certain temperature and pressure. Compared with the existing nickel based catalyst, the catalyst of the invention has high activity and selectivity.
Description
Technical field
The present invention relates to a kind of be used for isopropyl alcohol Catalysts and its preparation method and application, more particularly, the present invention relates to the Catalysts and its preparation method and the application of nickel as the preparation isopropyl alcohol of catalyst master active component.
Background technology
The production of isopropyl alcohol can adopt the method for propylene hydration to make, like indirect esterification process and the acidic catalyst that adopts solid or the methods such as direct hydration method of cation exchange resin catalyst that adopts sulfuric acid.
Because industrial most of acetone is all obtained by isopropylbenzene peroxidating method, and with the phenol coproduction.Because the increase of the demand of phenol produces a large amount of acetone, unbalanced supply-demand occurred, often causes the situation of acetone overproduction.So just making becomes an economically viable route in some period by preparing isopropyl alcohol by acetone hydrogenation.
Preparing isopropyl alcohol by acetone hydrogenation can use Ni-based or copper-based catalysts, also can use like noble metal catalysts such as palladium, platinum, rhodium, rutheniums.Nickel-base catalyst is good with skeleton nickel (Raney Nickel), also can adopt load and carrier or composite oxides form.Copper catalyst then is many and other metal oxide is compound perhaps supports on carrier as catalyst.
Acetone is hydrogenation on the catalyst of above type, adopts fixed bed reactors more, and acetone and hydrogen get into beds continuously with certain proportioning under liquid phase or gas phase situation, and hydrogenation generates isopropyl alcohol under proper temperature and pressure.
Day disclosure special permission has been put down the 3-141235 patent report and has been adopted raney nickel catalyst to carry out the method for preparing isopropyl alcohol by acetone hydrogenation, and this patent introduces the acetone hydrogenation conversion ratio and the isopropyl alcohol selectivity all can reach 99.9%.Japan flat 2-279643 provide employing Ru/ γ-Al
2O
3Catalyst acetone hydrogenation technology through the isopropanol back end hydrogenation, under 9.0MPa pressure, reaches as high as 99.9% conversion ratio according to report acetone, and the selectivity of isopropyl alcohol also can reach 99.9% simultaneously.Though these two kinds of catalyst have good active and selectivity, the raney nickel catalyst price is higher relatively, and in when operation filling more complicated; Noble metal catalyst prices such as platinum, palladium, rhodium are expensive more, and reaction pressure is too high, and process conditions are harsh, and equipment requirements is higher.
All introduced the acetone hydrogenation method that adopts the Cu-Cr catalyst like the flat 3-41038 of Japan Patent, Russian Patent SU 1051055A and SU1118632A, Russ P RU 2047590 used contain NiO (25～65m%), (10～35m%) carry out acetone hydrogenation with the catalyst of (15～40%) produces isopropyl alcohol to CuO.Use the catalyst described in the above-mentioned patent all to have acetone conversion and the not high shortcoming of isopropyl alcohol selectivity, thereby cause the isopropyl alcohol yield to remain on a reduced levels.In addition, the Cr in the catalyst
2O
3Be prone to produce environmental pollution, do not meet the requirement of current " green " chemical industry.
Chinese patent CN 1255482A has reported that a kind of CuO-ZnO mixed oxide catalyst that adopts wafers carries out the method for preparing isopropyl alcohol by acetone hydrogenation, and under uniform temperature and pressure, acetone conversion and isopropyl alcohol selectivity all can reach 99.9%.But, cause its progressively inactivation and lower acetone conversion operation down because the high copper-based catalysts of reaction temperature melts knot easily.
Chinese patent CN 1962588A has reported that a kind of is raw material with acetone; With Ni-Co/AC is catalyst, and wherein consisting of of Ni-Co/AC catalyst: Ni is 10～70%, and Co is 1.1～30%; All the other are the active carbon component, and successive reaction prepares the method for isopropyl alcohol in gas phase.Concrete operating condition is: pressure: normal pressure～2.0MPa, and temperature: 70～200 ℃, acetone liquid phase air speed: 1.0～10.0h
-1, hydrogen ketone mol ratio: 3.0～15.0, catalyst amount: 0.2～2.0m
3Ketone (hr.m
3Catalyst).Though adopt this kind method can obtain highly purified medicine and cosmetics industry is used isopropyl alcohol through following process.But in this kind method nickel catalyst carried in preferred Ni content 50～65%, Co content is 2.0～20%, the Preparation of Catalyst cost is higher, has reduced the economy that acetone hydrogenation is produced isopropyl alcohol.
In order to improve activity of such catalysts, generally be as much as possible with the active component high degree of dispersion, make it have higher surface area, for example CN00803678.0 provides a kind of nickel surface area and is 80m at least
2The nickel of the total nickel amount of/g/transition alumina catalyst, it is used for the hydrogenation of oils or lipid.This invention utilizes the aqueous solution of nickel ammine to make transition alumina powder form slurries, and the heating slurries decompose nickel ammine, and deposit insoluble nickel compound, solids filtered residue from aqueous medium, drying, reduction.Require alumina powder to have the diameter of 1-20 micron.The first, the acetone hydrogenation catalyst makes catalyst can not use powder type, and should be the bulky grain shape because of factors such as the version of hydrogenation reactor and hydrogenation reaction heat.The second, the method for preparing catalyst of this invention adopts intermediate processing, if compressing tablet becomes graininess, can lose the pore structure and the nickel surface area of catalyst, thereby inapplicable acetone hydrogenation of the present invention.
Make a general survey of the prior art document, existing acetone hydrogenation is produced isopropyl alcohol technology and is existed severe reaction conditions and/or catalyst situation of non-ideal use.
Summary of the invention
The inventor produces catalyst problem of non-ideal use in the isopropyl alcohol technology in order to solve existing acetone hydrogenation; On the basis of existing catalyst, carried out more careful research; Find that catalyst of the present invention has desirable acetone hydrogenation performance; Carried out the test and the catalyst contrast test of simulation commercial production condition, result of the test shows uses catalyst of the present invention, and the yield of isopropyl alcohol can reach 99.4%.Compare with existing nickel-base catalyst, the isopropyl alcohol selectivity is higher, and the gas light component of the diisopropyl ether of by-product and 4-methyl-2-amylalcohol and by-product such as methane etc. are very low, thereby has improved the economic benefit of device.
Particularly, the catalyst that is used for preparing isopropyl alcohol by acetone hydrogenation of the present invention comprises the transition alumina carrier and loads on the nickel on the alumina support, in the gross weight of catalyst, contains 8%～25% nickel, and the surface area of nickel is 10～30m
2The total nickel amount of/g, said alumina support has 150～350m
2BET specific area and the 0.30～0.80m of/g
3The pore volume of/g.
Preferably, the specific area of said catalyst is 140～300m
2/ g, pore volume are 0.25～0.60m
3/ g.
Preferably, in the gross weight of catalyst, said catalyst contains 7%～18% nickel.
Alumina support used in the present invention satisfies desired index promptly can be used.In order to bring into play the better catalytic performance of catalyst, more preferably, said alumina support is produced by the Beijing Chemical Research Institute.
Catalyst of the present invention can prepare with conventional method, and for example infusion process, the precipitation method, spraying process etc. do not have special requirement to the preparation method; For example, take by weighing a certain amount of carrier, make active constituent loading to carrier through infusion process; Dry then; Roasting, reduction obtains said catalyst prod at last.For example, when adopting infusion process, generally be that the body formed back of carrying alumina is used.For instance, be shaped to needed shape with the boehmite powder after, drying, roasting at a certain temperature is the carrier that index is satisfied the demand.Utilize infusion process to carry out load active component then.When for example adopting the precipitation method again, earlier with the active component precipitation, in the precipitation slurry, add then alumina powder jointed, after filtration, dry supervisor, reshaping.
Specifically; The soluble-salt of the Ni of requirement is dissolved in the water, and wiring solution-forming is immersed in a period of time in the solution with alumina support; At 100～200 ℃ of down dry 2～8h; 250～500 ℃ of following roasting 2～8h with hydrogen reduction 10～80h under 200～500 ℃, obtain catalyst of the present invention more then.
The soluble-salt of Ni can be any soluble-salt, for example nickel nitrate, nickel acetate, citric acid nickel, nickel formate etc.
Another object of the present invention provides the Application of Catalyst that is used for the acetone hydrogenation petrohol of the present invention, under the situation that hydrogen exists, is raw material with acetone, and reaction generates isopropyl alcohol in the fixed bed reactors of catalyst of the present invention are housed.
More particularly, at normal pressure or add and depress, acetone and hydrogen react in fixed bed reactors and generate isopropyl alcohol, and reaction temperature is 80～180 ℃, and the liquid hourly space velocity (LHSV) of acetone is 0.05～1h
-1, the mol ratio of acetone and hydrogen is 1: 2～6.
Consider from industrial angle, preferably, in the charging of said fixed bed reactors, sneak into the circulation fluid of isopropyl alcohol process units, said circulation fluid is that the feed separation from fixed bed reactors goes out the remaining liquid of purification isopropyl alcohol behind the hydrogen.
Adopting catalyst of the present invention is the feedstock production isopropyl alcohol with acetone, and the conversion ratio of acetone is high, and the yield of isopropyl alcohol is high and selectivity is high, and the metal active constituent content of catalyst is low simultaneously, but has long service life, promptly has stability preferably.
The specific embodiment
Below in conjunction with embodiment content of the present invention is done further to explain and describe, but the present invention is not limited in following examples.
Embodiment 1
Adopt equi-volume impregnating, (produced by the Beijing Chemical Research Institute, BET specific area and pore volume are respectively 154m according to alumina support
2/ g and 0.32m
3/ g) water absorption rate is dissolved in the nickel nitrate of requirement and processes the volume solution identical with the water absorption of alumina support in the deionized water, alumina support is immersed in the solution drying, roasting, reduction.Process and contain 10%Ni catalyst A-1, measure the specific area and the pore volume of catalyst, be respectively 144m
2/ g, pore volume are 0.28m
3/ g, the surface area of nickel are 15m
2/ g nickel total amount.
Catalyst A-1 is packed in the fixed bed reactors, feed acetone and hydrogen, the mol ratio of acetone and hydrogen is 1: 2, at 85 ℃, normal pressure, acetone solution hourly space velocity 0.1h
-1The Catalytic Hydrogenation Properties of following evaluate catalysts.Result of the test is seen table 1.
Embodiment 2
Adopt equi-volume impregnating, (produced by the Beijing Chemical Research Institute, BET specific area and pore volume are respectively 344m according to alumina support
2/ g and 0.72m
3/ g) water absorption rate is dissolved in the nickel nitrate of requirement and processes the volume solution identical with the water absorption of alumina support in the deionized water, alumina support is immersed in the solution drying, roasting, reduction.Process and contain 22%Ni catalyst A-2, measure the specific area and the pore volume of catalyst, be respectively 284m
2/ g, pore volume are 0.58m
3/ g, the surface area of nickel are 25m
2/ g nickel total amount.
Catalyst A-2 is packed in the fixed bed reactors, feed acetone and hydrogen, the mol ratio of acetone and hydrogen is 1: 5, at 155 ℃, 2.0MPa, acetone solution hourly space velocity 0.9h
-1The Catalytic Hydrogenation Properties of following evaluate catalysts.Result of the test is seen table 1.
Embodiment 3
Adopt equi-volume impregnating, (produced by the Beijing Chemical Research Institute, BET specific area and pore volume are respectively 210m according to alumina support
2/ g and 0.47m
3/ g) water absorption rate is dissolved in the nickel nitrate of requirement and processes the volume solution identical with the water absorption of alumina support in the deionized water, alumina support is immersed in the solution drying, roasting, reduction.Process and contain 19%Ni catalyst A-3, measure the specific area and the pore volume of catalyst, be respectively 184m
2/ g, pore volume are 0.38m
3/ g, the surface area of nickel are 18m
2/ g nickel total amount.
Catalyst A-3 is packed in the fixed bed reactors, feed acetone and hydrogen, the mol ratio of acetone and hydrogen is 1: 4, at 125 ℃, 2.0MPa, acetone solution hourly space velocity 0.5h
-1The Catalytic Hydrogenation Properties of following evaluate catalysts.Result of the test is seen table 1.
Comparative Examples 1
Prepared according to the method for preparing catalyst that provides among the Chinese patent CN 1962588A that to contain Ni be 30%, Co is 10.5%, and all the other are the Ni-Co/AC catalyst of activated carbon composition, are numbered B-1.
Catalyst B-1 is packed in the fixed bed reactors, feed acetone and hydrogen, at 140 ℃, 2.0MPa, acetone solution hourly space velocity 0.5h
-1The Catalytic Hydrogenation Properties of following evaluate catalysts.Result of the test is seen table 1.
Table 1
Can know that through the experimental result in the table 1 catalyst of the present invention not only has higher acetone conversion, and have higher isopropyl alcohol yield.
Claims (7)
1. the catalyst of a preparing isopropyl alcohol by acetone hydrogenation is characterized in that, said catalyst comprises the transition alumina carrier and loads on the nickel on the alumina support, in the gross weight of catalyst, contains 8%～25% nickel, and the surface area of nickel is 10～30m
2The total nickel amount of/g, said alumina support has 150～350m
2BET specific area and the 0.30～0.80m of/g
3The pore volume of/g.
2. the catalyst that is used for preparing isopropyl alcohol by acetone hydrogenation as claimed in claim 1 is characterized in that, the specific area of said catalyst is 140～300m
2/ g, pore volume are 0.25～0.60m
3/ g.
3. the catalyst that is used for preparing isopropyl alcohol by acetone hydrogenation as claimed in claim 1 is characterized in that, in the gross weight of catalyst, said catalyst contains 7%～18% nickel.
4. like the described catalyst that is used for preparing isopropyl alcohol by acetone hydrogenation of one of claim 1～3, it is characterized in that said alumina support is produced by the Beijing Chemical Research Institute.
5. like the described Application of Catalyst that is used for preparing isopropyl alcohol by acetone hydrogenation of one of claim 1～4; It is characterized in that; Under the situation that hydrogen exists; With acetone is raw material, in being equipped with like the fixed bed reactors of the catalyst of the described preparing isopropyl alcohol by acetone hydrogenation of one of claim 1～4, hydrogenation reaction takes place and generates isopropyl alcohol.
6. application as claimed in claim 5 is characterized in that, at normal pressure or add and depress, acetone and hydrogen react in fixed bed reactors and generates isopropyl alcohol, and reaction temperature is 80～180 ℃, and the liquid hourly space velocity (LHSV) of acetone is 0.05～1h
-1, the mol ratio of acetone and hydrogen is 1: 2～6.
7. like claim 5 or 6 described application; It is characterized in that; In the charging of said fixed bed reactors, sneak into the circulation fluid of isopropyl alcohol process units, said circulation fluid is that the feed separation from fixed bed reactors goes out the remaining liquid of purification isopropyl alcohol behind the hydrogen.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391067A (en) * | 2011-07-21 | 2012-03-28 | 吉林市道特化工科技有限责任公司 | Method for synthesizing isopropyl alcohol by hydrogenating acetone |
| CN110981694A (en) * | 2019-12-25 | 2020-04-10 | 淄博诺奥化工股份有限公司 | Environment-friendly method for preparing isopropanol by catalytic distillation |
| CN111097499A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing isopropanol by acetone hydrogenation |
| CN112275276A (en) * | 2020-10-29 | 2021-01-29 | 吉林市道特化工科技有限责任公司 | Catalyst carrier, catalyst, preparation method and application |
| CN113024351A (en) * | 2021-03-24 | 2021-06-25 | 西南化工研究设计院有限公司 | Production method of isopropanol |
| CN113413890A (en) * | 2021-07-06 | 2021-09-21 | 湖北力拓能源化工装备有限公司 | Porous adsorption catalytic material and preparation method thereof |
| WO2022089570A1 (en) | 2020-10-31 | 2022-05-05 | 中国石油化工股份有限公司 | Preparation method and production device for propylene |
| RU2813540C1 (en) * | 2023-09-29 | 2024-02-13 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Method for producing isopropyl alcohol |
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Patent Citations (3)
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| CN101844081A (en) * | 2009-03-26 | 2010-09-29 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391067A (en) * | 2011-07-21 | 2012-03-28 | 吉林市道特化工科技有限责任公司 | Method for synthesizing isopropyl alcohol by hydrogenating acetone |
| CN111097499A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing isopropanol by acetone hydrogenation |
| CN110981694A (en) * | 2019-12-25 | 2020-04-10 | 淄博诺奥化工股份有限公司 | Environment-friendly method for preparing isopropanol by catalytic distillation |
| CN112275276A (en) * | 2020-10-29 | 2021-01-29 | 吉林市道特化工科技有限责任公司 | Catalyst carrier, catalyst, preparation method and application |
| CN112275276B (en) * | 2020-10-29 | 2022-10-28 | 吉林市道特化工科技有限责任公司 | Catalyst carrier, catalyst, preparation method and application |
| WO2022089570A1 (en) | 2020-10-31 | 2022-05-05 | 中国石油化工股份有限公司 | Preparation method and production device for propylene |
| CN113024351A (en) * | 2021-03-24 | 2021-06-25 | 西南化工研究设计院有限公司 | Production method of isopropanol |
| CN113413890A (en) * | 2021-07-06 | 2021-09-21 | 湖北力拓能源化工装备有限公司 | Porous adsorption catalytic material and preparation method thereof |
| RU2813540C1 (en) * | 2023-09-29 | 2024-02-13 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Method for producing isopropyl alcohol |
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Application publication date: 20121017 |