CN102746114B - Preparation method of isopropanol - Google Patents
Preparation method of isopropanol Download PDFInfo
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- CN102746114B CN102746114B CN201110101116.0A CN201110101116A CN102746114B CN 102746114 B CN102746114 B CN 102746114B CN 201110101116 A CN201110101116 A CN 201110101116A CN 102746114 B CN102746114 B CN 102746114B
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- acetone
- virahol
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Abstract
The invention relates to a preparation method of isopropanol through gas phase hydrogenation of acetone, and aims to mainly solve the problems that noble metal catalysts are expensive and Cu-based catalysts have poor stability in the prior art. The method of the invention adopts a technical scheme composed of: taking acetone and hydrogen as raw materials, using isopropanol as a solvent, and under the conditions of a molar ratio of hydrogen to acetone of 1-15:1, a reaction temperature of 100-180DEG C, a reaction pressure of 0.1-5.0MPa, and a total liquid space velocity of 0.5-8.0h<-1>, contacting the raw materials with a catalyst for reaction to generate isopropanol. Specifically, the catalyst comprises the following components by weight: a) 5.0-15.0% of NiO; b) 5.0-25.0% of MoOx; c) 5.0-15.0% of P or its oxide; d) 45.0-75.0% ofA2O3; and e) 5.0-15.0% of at least one of MgO, BaO or CaO. The technical scheme of the invention well solves the problems, and can be used in the industrial production of isopropanol through hydrogenation of acetone.
Description
Technical field
The present invention relates to a kind of method by acetone hydrogenation preparing isopropanol.
Background technology
In recent years, in order to meet the growing demand of phenol, all enlarging or newly-built production equipments one after another of domestic and international many phenol production producer, propylene shortage of resources has restricted the raising of China's phenol yield, and phenol needs the situation of a large amount of dependence on import also will continue.Within 2008～2011 years, whole world phenol device capability newly-built and enlarging reaches 287.6 ten thousand tons/year, and wherein Asia accounts for 94%, and China's Mainland accounts for 43%.Mitsui Chemicals is drafted in 2013～2014 years and is built 400,000 tons/year of phenol devices in China or Singapore, and these new devices all adopt cumene method.By 2012, global phenol production capacity will reach 1,250 ten thousand tons/year, and within 2017, global phenol production capacity will reach 1,390 ten thousand tons/year, and acetone is 8,700,000 tons/year.Chemical industry on-line prediction, within 2011, global acetone production capacity will reach 727.0 ten thousand tons/year, and demand is 631.5 ten thousand tons, and the imbalance of phenol and acetone demand causes acetone day by day superfluous.
How to utilize unnecessary acetone to become the difficult problem that many phenol production producer faces, it is exactly one of outlet that acetone hydrogenation changes into Virahol.Virahol is a kind of organic solvent of excellent property, is widely used as the aspect such as important intermediate and oil-fired antifreeze additive of solvent, organic compound, and exploitation prospect is wide.According to chemical industry Online statistics, within 2009, global Virahol production capacity is about more than 260 ten thousand tons, and there are the transnational large petrochemical plants such as DOW Chemical, Exxon Mobil, shell in main production firm.What China had on a large scale a device has these two of Jinzhou and Shandong Hai Ke chemical industry limited liability companys, and within 2009, import Virahol reaches 10.2 ten thousand tons, and the degree of self-sufficiency of Virahol is only 50%.For satisfying the demands, Jinzhou plans newly-built a set of 100,000 tons/year of Virahol device projects and implements.
On January 22nd, 2010, Novapex goes into operation at 40,000 tons/year of newly-built Virahol devices of French Roussilin, with acetone, H
2for raw material.LG company is also becoming Virahol acetone conversion, and this will alleviate potential surplus.Mitsui Chemicals improves isopropyl benzene manufacturing phynol/acetone technique, and according to the variation in acetone market, the acetone hydrogenation that isopropyl benzene is prepared through dicumyl peroxide obtains Virahol.
Acetone hydrogenation can adopt the catalyzer such as precious metals pd, Pt, Ru, Ru, carry out, but these catalyzer prices is very expensive on fixed-bed reactor.
In Chinese patent CN1255482A, adopting the CuO-ZnO mixture of compression molding is catalyzer, carries out acetone hydrogenation reaction, 150～250 ℃ of temperature of reaction at fixed-bed reactor, reaction pressure is under 1.0～5.0MPa condition, and acetone conversion and generation Virahol selectivity all can reach 99%.
In sum, catalyzer prepared by prior art, is applied in preparing isopropyl alcohol by acetone hydrogenation process, adopts noble metal catalyst to exist expensive, the poor problem of existence and stability while adopting Cu catalyst based.
Summary of the invention
Technical problem to be solved by this invention is that catalyzer prepared by prior art is applied in preparing isopropyl alcohol by acetone hydrogenation process and exists and adopt the problem that noble metal catalyst is expensive, adopt the catalyst based poor stability of Cu, provides a kind of new acetone gas phase hydrogenation to prepare the method for Virahol.Catalyzer that the method adopts has advantages of that price is low, good stability.
Solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of acetone gas phase hydrogenation is prepared the method for Virahol, take acetone and hydrogen as raw material, take Virahol as solvent, the mol ratio of hydrogen/acetone is 1～15: 1, temperature of reaction is at 100～180 ℃, and reaction pressure is at 0.1～5.0MPa, and the total air speed of liquid phase volume is 0.5～8.0h
-1under condition, raw material contacts with catalyzer, and reaction generates Virahol product, and wherein used catalyst comprises following component by weight percentage: a) 5.0～15.0%NiO; B) 5.0～25.0%MoO
x; C) 5.0～15.0%P or its oxide compound; D) 45.0～75.0%Al
2o
3; E) 5.0～15.0% be selected from least one in MgO, BaO or CaO.
In technique scheme, the total air speed preferable range of liquid phase volume is 1.0～5.0h
-1, the ratio of hydrogen/acetone is take molar ratio computing preferable range as 4～10: 1.In described acetone liquid phase feed, acetone content is 20～50% by weight percentage, and isopropanol content is 50～80%.Described hydrogenation reaction temperature preferable range is 140～170 ℃; Reaction pressure preferable range is 1.0～4.0MPa.Being selected from by weight percentage at least one consumption preferable range in MgO, BaO or CaO is 5.0～10.0%.
The catalyzer preparation of using in the present invention comprises the following steps: 1) with HNO
3, H
3pO
4for binding agent, take pseudo-boehmite and sesbania powder as Al source, introduce water and the Mg of aequum
2+, Ba
2+or Ca
2+in at least one, be extruded into the right cylinder that diameter is 2mm, wet bar at ambient temperature after airing at 120 ℃ dry 12h, then at 600 ℃, roasting 4h obtains support of the catalyst; 2) take a certain amount of Ni (NO
3)
26H
2o and (NH
4)
6mo
7o
244H
2o is dissolved in distilled water, then adds a certain amount of (NH
4)
2hPO
4, drip wherein dense HNO
3by resolution of precipitate, and adjust pH value between 4～5, form solution I; 3) calculate by weight percentage, in solution I, add citric acid, keep its concentration 2～5%, form solution II; 4) solution II is heated to 70 ℃, is added drop-wise to while hot Al
2o
3on carrier, calculate by weight Al
2o
3carrier water-intake rate is between 0.85～0.9; 5) sample after dipping, roasting 12 hours at 400～700 ℃ after drying at 120 ℃; 6) catalyzer uses front at H
2under in 450～700 ℃ reduction 12 hours.
Compared with the method for preparing isopropyl benzene with employing precious metal catalyst hydrogenation acetone, the catalyzer price that the method provides is low.Generate in the process of Virahol at acetone hydrogenation, the one, part acetone can generate hexone by direct-coupling, and also easily there is etherificate and form by product in the Virahol of generation.Therefore, the acidic site of catalyzer needs to mate with hydrogenation activity.The acid site quantity of catalyzer and strength of acid can regulate by the content of oxide compound and handling procedure; The hydrogenation activity of catalyzer need to be controlled by the content of reasonably controlling Ni, Mo, P, thereby makes the Ni based metal catalysts of preparation keep good activity, stability and selectivity.
Adopt method provided by the invention, at catalyzer after 650 ℃ of hydrogen reducings, be 2.0h in 140～170 ℃ of temperature of reaction, reaction pressure 1.0～4.0MPa, raw material (25% acetone-75% Virahol by weight percentage) the total air speed of liquid phase volume
-1, under the reaction conditions that the mol ratio of hydrogen and acetone is 4.0, be applied to acetone hydrogenation petrohol process, react after 24 hours, acetone conversion can reach 100%, generates isopropyl benzene selectivity and can be greater than 99%; Reaction is carried out after 72h continuously, and catalytic activity and selectivity do not change; This catalyzer price is low compared with noble metal catalyst, and this catalyzer has good stabilized hydrogenation simultaneously, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Carrier preparation: take commercially available pseudo-boehmite as Al source, by weight percentage with 3%HNO
3the aqueous solution is binding agent, introduces appropriate Mg
2+after extruded moulding through 120 ℃ of oven dry, 600 ℃ of roastings, it consists of 5%MgO-95%Al
2o
3.
Take 6.7g Ni (NO
3)
26H
2o and 2.4g (NH
4)
6mo
7o
246H
2o4H
2o is dissolved in 10.0g distilled water, adds a certain amount of 1.7g NH
4h
2pO
4or 2.4g (NH
4)
2h
2pO
4, drip wherein dense HNO
3by resolution of precipitate, and adjust pH value between 4～5, form solution I; In solution I, add 3.5g citric acid, form solution II; Solution II is heated to 70 ℃, is added drop-wise to while hot on 10.0g carrier, roasting 8 hours at 550 ℃ after drying at 120 ℃.Catalyzer uses front at H
2under in 650 ℃ reduction 12 hours.Catalyzer consists of: 12%NiO-10MoOx-5%POx-3.6%MgO-69.4%Al
2o
3.This catalyzer is at 150 ℃, and reaction pressure 3.0MPa, total liquid volume air speed are 2.0h
-1, under the reaction conditions that the mol ratio of hydrogen and acetone is 4.0, by weight percentage, 25% acetone-75% Virahol is that liquid phase feed is carried out hydrogenation reaction, reaction result is in table 1.
[embodiment 2]
Carrier preparation: take commercially available pseudo-boehmite as Al source, by weight percentage with 1.5%HNO
3and 1.5%H
3pO
4solution is binding agent, introduces appropriate Mg
2+after extruded moulding through 120 ℃ of oven dry, 600 ℃ of roastings, it consists of 5%MgO-95%Al
2o
3.Method for preparing catalyst and appreciation condition are with embodiment 1, and reaction result is in table 1.
[embodiment 3]
Carrier preparation: the roasting at 600 ℃ of commercially available pseudo-boehmite powder is obtained to δ-Al for 4 hours
2o
3, get equivalent δ-Al
2o
3with pseudo-boehmite be Al source, in weight ratio with 1.5%HNO
3and 1.5%H
3pO
4solution is binding agent, introduces appropriate Mg
2+, Ca
2+after extruded moulding through 120 ℃ of oven dry, 600 ℃ of roastings, it consists of 5%MgO-5%CaO-90%Al
2o
3.Method for preparing catalyst is with embodiment 1.Method for preparing catalyst and evaluation method are with embodiment 1, and reaction result is in table 1.
[embodiment 4]
Carrier preparation: the roasting at 900 ℃ of commercially available pseudo-boehmite powder is obtained to γ-Al for 4 hours
2o
3, get equivalent γ-Al
2o
3with pseudo-boehmite be Al source, in weight ratio with 1.5%HNO
3and 1.5%H
3pO
4solution is binding agent, introduces appropriate Mg
2+, Ca
2+after extruded moulding through 120 ℃ of oven dry, 600 ℃ of roastings, it consists of 5%MgO-5%CaO-90%Al
2o
3.Method for preparing catalyst and appreciation condition are with embodiment 1, and reaction result is in table 1.
[embodiment 5]
Carrier preparation: the roasting at 600 ℃ of commercially available pseudo-boehmite powder is obtained to δ-Al for 4 hours
2o
3, get equivalent γ-Al
2o
3with pseudo-boehmite be Al source, in weight ratio with 1.5%HNO
3and 2.5%H
3pO
4solution is binding agent, introduces appropriate Ba
2-after extruded moulding through 120 ℃ of oven dry, 600 ℃ of roastings, it consists of 5%CaO-95%Al
2o
3.Method for preparing catalyst and appreciation condition are with embodiment 1.Reaction result is in table 1.
[embodiment 6]
Carrier preparation: the roasting at 1100 ℃ of commercially available pseudo-boehmite Al powder is obtained to α-Al for 4 hours
2o
3, with this α-Al
2o
3for Al powder, in weight ratio with 1.5%HNO
3and 2.5%H
3pO
4for binding agent, introduce appropriate Ba
2+after extruded moulding through 120 ℃ of oven dry, 600 ℃ of roastings, it consists of 5%BaO-95%Al
2o
3.Method for preparing catalyst and evaluation method are with embodiment 1.Reaction result is in table 1.
The acetone hydrogenation reactivity worth of table 1 catalyzer 1～6
As can be seen from Table 1, under identical reaction conditions, catalyzer 4,5,6 have good stability and selectivity.
[embodiment 7～13]
According to the preparation method of embodiment 5, the composition that just changes catalyzer is prepared catalyzer 7～13, and its composition is in table 2.
[comparative example 1]
According to Chinese patent CN1255482A, adopting the 30%CuO-70%ZnO mixture of compression molding is catalyzer.
The composition of table 2 catalyzer and preparation condition
The acetone hydrogenation performance of catalyzer 7～13 and comparative example catalyzer is in table 3, and comparative example catalyzer adopts and counts 5%H with volume percent
2-95%N
2gas mixture at 230 ℃, reduce after 12 hours for hydrogenation reaction.
The acetone hydrogenation reactivity worth of table 3 different catalysts
Select catalyzer 8 in embodiment 8, just change different examination conditions, reaction 72h, its reaction result is listed in table 4.
Acetone hydrogenation evaluating catalyst result under table 4 differential responses condition
From table 2,3,4 can find out, this technology is applied to be prepared Virahol and obtained good reaction result, is 1.0～4.0h in 140～170 ℃ of temperature of reaction, reaction pressure 1.0～4.0Mpa, the total air speed of stock liquid phase volume
-1, the activity of catalyzer and selectivity are substantially good, and compared with noble metal catalyst, this catalyzer price is low, and this catalyzer has good acetone hydrogenation stability simultaneously.
Claims (5)
1. acetone gas phase hydrogenation is prepared a method for Virahol, take acetone and hydrogen as raw material, take Virahol as solvent, the mol ratio of hydrogen/acetone is 1～15: 1, temperature of reaction is at 100～180 ℃, and reaction pressure is at 0.1～5.0MPa, and the total air speed of liquid phase volume is 0.5～8.0h
-1under condition, raw material contacts with catalyzer, and reaction generates Virahol product, and wherein used catalyst is following component by weight percentage: a) 5.0～15.0%NiO; B) 5.0～25.0%MoO
x; C) 5.0～15.0%P or its oxide compound; D) 45.0～75.0%Al
2o
3; E) 5.0～15.0% be selected from least one in MgO, BaO or CaO.
2. the method for preparing Virahol according to claim 1, is characterized in that the total air speed of liquid phase volume is 1.0～5.0h
-1, the ratio of hydrogen/acetone is take molar ratio computing as 4～10: 1.
3. the method for preparing Virahol according to claim 1, is characterized in that in described acetone liquid phase feed that acetone content is 20～50% by weight percentage, and isopropanol content is 50～80%.
4. the method for preparing Virahol according to claim 1, is characterized in that described hydrogenation reaction temperature is 140～170 ℃; Reaction pressure is preferred 1.0～4.0MPa.
5. the method for preparing Virahol according to claim 1, it is characterized in that being selected from by weight percentage at least one consumption in MgO, BaO or CaO is 5.0～10.0%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110101116.0A CN102746114B (en) | 2011-04-20 | 2011-04-20 | Preparation method of isopropanol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110101116.0A CN102746114B (en) | 2011-04-20 | 2011-04-20 | Preparation method of isopropanol |
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| CN102746114B true CN102746114B (en) | 2014-05-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347758A (en) * | 2001-09-11 | 2002-05-08 | 中国石油天然气股份有限公司 | Sec-octanone hydrogenating process of preparing sec-octanol and its copper-containing catalyst |
| CN101191078A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Nickel catalyst with composite pore structure used for selective hydrogenation |
| CN101927168A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof |
-
2011
- 2011-04-20 CN CN201110101116.0A patent/CN102746114B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347758A (en) * | 2001-09-11 | 2002-05-08 | 中国石油天然气股份有限公司 | Sec-octanone hydrogenating process of preparing sec-octanol and its copper-containing catalyst |
| CN101191078A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Nickel catalyst with composite pore structure used for selective hydrogenation |
| CN101927168A (en) * | 2009-06-26 | 2010-12-29 | 中国石油化工股份有限公司 | Nickel-based catalyst for preparing isopropyl alcohol by acetone hydrogenation and application thereof |
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