CN103030525B

CN103030525B - Method for preparing isopropanol by liquid-phase hydrogenation of acetone

Info

Publication number: CN103030525B
Application number: CN201110293314.1A
Authority: CN
Inventors: 王辉; 刘仲能; 王德举; 李则俊; 王燕波
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2011-09-29
Filing date: 2011-09-29
Publication date: 2015-01-07
Anticipated expiration: 2031-09-29
Also published as: CN103030525A

Abstract

The present invention relates to a method for preparing isopropanol by liquid-phase hydrogenation of acetone, and mainly solves the problems that precious metal Ru catalyst is expensive and Cu-based catalyst is low in activity in the prior art. According to the present invention, acetone and hydrogen are used as raw materials, isopropanol is used as a solvent, the reaction temperature is 100-200 DEG C, the reaction pressure is 0.1-5.0 MPa, the raw materials are contacted with the catalyst to react to produce isopropanol, wherein the catalyst comprises the following components by weight: a) 10.0-40.0% of Ni; b) 2.0-8.0% of B; c) 55.0-70.0% of Al2O3; and d) 3.0-15.0% of at least one selected from the group consisting of MgO, BaO or CaO. The technical solution solves the problem well, and the method can be used for preparing isopropanol by acetone hydrogenation.

Description

The method of Virahol is prepared in acetone liquid-phase hydrogenatin

Technical field

The present invention relates to a kind of method preparing Virahol, particularly a kind of method of acetone liquid-phase hydrogenatin preparing isopropanol

Background technology

In recent years, domestic and international many phenol production producers extend or newly-built production equipment one after another, and propylene shortage of resources constrains 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 that is 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 and was built 400,000 tons/year of phenol devices in 2013 ~ 2014 years 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.

The difficult problem how effectively utilizing unnecessary acetone to become many phenol production producers to face, acetone hydrogenation being changed into Virahol is exactly one of outlet.Acetone hydrogenation can adopt the catalyzer such as precious metals pd, Pt, Ru, and fixed-bed reactor carry out, but these catalyzer prices are very expensive.Amorphous alloy has short range order, longrange disorder, homogeneous, the structure that do not have crystal boundary and general mechanics, electricity, magnetics and chemical property not available for material, good radiation resistance and resistance to corrosion, is therefore a kind of type material with broad prospect of application.Amorphous alloy component is homogeneous, and composition is adjustable, have excellent hydrogenation specific activity and selectivity.

Flat 2-278643 adopts Ru/Al ₂o ₃catalyzer carries out acetone hydrogenation, take Virahol as solvent, and under 9.0MPa hydrogen pressure, peak rate of conversion and selectivity all reach 99.9%.This catalyzer is higher owing to using precious metal Ru to there is price, reacts at 9.0Mpa H ₂carry out there is the high problem of reaction pressure under pressure.

In Chinese patent CN1255482A, the CuO-ZnO mixture adopting compression molding is catalyzer, carries out acetone hydrogenation reaction, temperature of reaction 150 ~ 250 DEG C 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, there is active low problem when adopting Cu catalyst based.

Summary of the invention

Technical problem to be solved by this invention is that prior art prepares the feature that in Virahol process, the expensive pressure of existence employing noble metal Ru catalyst is high, the problem that the catalyst based activity of employing Cu is low, provides a kind of new acetone liquid-phase hydrogenatin to prepare the method for Virahol.The method adopt catalyzer to have price is low, pressure is low, active high advantage.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: take Virahol as solvent, in raw material and solvent mixture by weight percentage, acetone content is 10 ~ 80%, and isopropanol content is 20 ~ 90%, is 100 ~ 200 DEG C in temperature of reaction, reaction pressure is 1.0 ~ 5.0MPa, raw material and catalyst exposure, reaction generates Virahol, and wherein catalyst comprises following component: a) 10.0 ~ 40.0%Ni; B) 2.0 ~ 8.0%B; C) 55.0 ~ 70.0%Al ₂o ₃; E) 3.0 ~ 15.0% at least one in MgO, BaO or CaO is selected from.

In above technical scheme, in catalyzer, Ni content is 15.0 ~ 30.0% by weight percentage, in the mixture of described raw material and solvent, acetone content is 25.0 ~ 75.0% by weight percentage, and isopropanol content is 25.0 ~ 75.0%, and hydrogenation reaction temperature is 150 ~ 180 DEG C; Reaction pressure is 2.0 ~ 4.0MPa, and the consumption being selected from least one in MgO, BaO or CaO is by weight percentage 5.0 ~ 10.0%.

This catalyst preparing comprises the following steps: the water and the Mg that 1) introduce aequum ²⁺, Ba ²⁺or Ca ²⁺middle at least one, adopts the method for incipient impregnation to be impregnated into Al ₂o ₃on carrier, then roasting 4h at 600 DEG C, mechanical disintegration obtains support of the catalyst; 2) a certain amount of Ni (NO is taken ₃) ₂6H ₂o is dissolved in distilled water, then adds appropriate carrier and forms mixture I; 3) calculate by weight percentage, in mixture I, add 10.0 ~ 30.0% sodium borohydrides or solution of potassium borohydride, keep B/Ni molar ratio to be 1: 1 ~ 1: 3; 4) washing is about 7.0 to pH, and catalyzer is kept in water for subsequent use.

Compared with preparing the method for Virahol 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, one is that part acetone can generate hexone by direct-coupling, and the Virahol of generation etherificate also easily occurs and forms by product.Therefore, the acidic site of catalyzer needs to mate with hydrogenation activity.The acid site quantity of catalyzer and strength of acid are by introducing basic oxide in the carrier to regulate; The hydrogenation activity of catalyzer needs to be controlled by the content of reasonably control Ni, B, thus makes activity, stability and the selectivity that the Ni based metal catalysts of preparation keeps good.Compared with noble metal Ru catalyst, this catalyzer price is low, and react and carry out under 1.0 ~ 5.0MPa, pressure is low.Compared with catalyst based with Cu, this catalyst activity is high.

Adopt method of the present invention, catalyzer is obtained by the method for chemical reduction, take Virahol as solvent, acetone hydrogenation petrohol process is applied under the reaction conditions of temperature of reaction 100 ~ 200 DEG C, reaction pressure 1.0 ~ 5.0MPa, react after 4 hours, acetone conversion can reach more than 96%, generates isopropyl benzene selectivity and is greater than 95%.This catalyzer price is low compared with noble metal catalyst, and reaction pressure is low, and compared with catalyst based with Cu, this catalyst activity is high, achieves good technique effect.

Below by embodiment, the present invention is further elaborated.

Embodiment

[embodiment 1]

Prepared by carrier: with commercially available pseudo-boehmite for A1 source, after 600 DEG C of roastings, obtain Al ₂o ₃, take 33.74gMg (NO ₃) ₂6H ₂o is made into the 180ml aqueous solution, adopts the method for dipping to be impregnated into 100g Al ₂o ₃on, through 120 DEG C of oven dry, 600 DEG C of roastings, obtain consisting of 5.0%MgO-95%Al ₂o ₃carrier.

Take 29.08g Ni (NO ₃) ₂6H ₂o, 22.39g 5%MgO-95%Al ₂o ₃be positioned in 100.0g distilled water, under magnetic agitation, form mixture I.Take 7.56gNaBH ₄be dissolved in 20.g distilled water, form solution I; Solution I is slowly added drop-wise in mixture I, after dropwising, after continuing magnetic agitation 1.0h, makes to be washed with distilled water to pH to about 7.0, Yu Shuizhong and preserve.Catalyzer 1 consists of: 20.0%Ni-3.7%B-3.8%MgO-72.5%Al ₂o ₃.With 300ml batch reactor for reactor, add this catalyzer 3.0g, at 180 DEG C, hydrogen pressure 3.0MPa, add 150ml by weight percentage 25% acetone-75% isopropanol mixture carry out hydrogenation reaction, reaction result is in table 2.

[embodiment 2 ~ 10]

Catalyst agent preparation method is with embodiment 1, and catalyst preparation conditions and composition are in table 1.With 300ml batch reactor for reactor, add this catalyzer 3.0g, at 180 DEG C, hydrogen pressure 3.0MPa, add 150ml by weight percentage 25% acetone-75% isopropanol mixture carry out hydrogenation reaction, reaction result is in table 2

[comparative example 1]

According to Chinese patent CN1255482A, the 30%CuO-70%ZnO mixture adopting compression molding is catalyzer.With 300ml batch reactor for reactor, add this catalyzer 3.0g, at 200 DEG C, hydrogen pressure 3.0MPa, add 150ml by weight percentage 25% acetone-75% isopropanol mixture material carry out hydrogenation reaction, reaction result is in table 2.

The composition of table 1 catalyzer and preparation condition

Catalyzer	Catalyzer composition (weight percent %)	Ni/B mol ratio
			1	20.0％Ni-3.7％B-3.8％MgO-72.5％Al ₂O ₃	1/2
2	20.0％Ni-3.7％B-3.8％CaO-72.5％Al ₂O ₃	1/2
			3	20.0％Ni-3.7％B-3.8％BaO-72.5％Al ₂O ₃	1/2
4	10.0％Ni-1.85％B-5.0％BaO-5.0％MgO-78.15％Al ₂O ₃	1/3
			5	20.0％Ni-3.7％B-5.0％CaO-5.0％MgO-66.3％Al ₂O ₃	1/1
6	20.0％Ni-3.7％B-5.0％SiO ₂-5.0％MgO-66.3％Al ₂O ₃	1/2
			7	30.0％Ni-3.7％B-5.0％SiO ₂-5.0％MgO-56.3％Al ₂O ₃	1/2
8	30.0％Ni-3.7％B-10.0％MgO-56.3％Al ₂O ₃	1/2
			9	15.0％Ni-1.85％B-5.0％MgO-78.15％Al ₂O ₃	1/1.5
10	40.0％Ni-3.7％B-3.8％CaO-52.5％Al ₂O ₃	1/2

The acetone hydrogenation reactivity worth of table 2 catalyzer 1 ~ 10

As can be seen from Table 2, under identical reaction conditions, catalyzer 3,8 have good stability and selectivity.Adopt catalyzer 8 to carry out test technology condition evaluating, evaluation result is in table 3.

Acetone hydrogenation evaluating catalyst result under table 3 differential responses condition

From table 2,3 can find out, this technology is applied to be prepared Virahol and achieves good reaction result, at temperature of reaction 160 ~ 180 DEG C, reaction pressure 2.0 ~ 4.0Mpa, the activity of catalyzer and selectivity are substantially good, and compared with noble metal catalyst, this catalyzer price is low, compared with catalyst based with Cu, reactive behavior is high, achieves good technique effect.

Claims

1. a method for Virahol is prepared in acetone liquid-phase hydrogenatin, and step is as follows:

Catalyst support preparation: with commercially available pseudo-boehmite for Al source, obtain Al after 600 DEG C of roastings ₂o ₃, take 33.74gMg (NO ₃) ₂6H ₂o is made into the 180ml aqueous solution, adopts the method for dipping to be impregnated into 100g Al ₂o ₃on, through 120 DEG C of oven dry, 600 DEG C of roastings, obtain consisting of 5.0%MgO-95%Al ₂o ₃carrier;

Catalyst preparing: take 29.08g Ni (NO ₃) ₂6H ₂o, 22.39g5%MgO-95%Al ₂o ₃be positioned in 100.0g distilled water, under magnetic agitation, form mixture Ι; Take 7.56gNaBH ₄be dissolved in 20.g distilled water, form solution I; Solution I be slowly added drop-wise in mixture I, after dropwising, after continuing magnetic agitation 1.0h, make to be washed with distilled water to pH to about 7.0, Yu Shuizhong and preserve, catalyzer 1 consists of: 20.0%Ni-3.7%B-3.8%MgO-72.5%Al ₂o ₃;

The preparation feedback of Virahol: with 300ml batch reactor for reactor, adds this catalyzer 3.0g, at 180 DEG C, hydrogen pressure 3.0MPa, add 150ml by weight percentage 25% acetone-75% isopropanol mixture carry out hydrogenation reaction;

The preparation feedback result of Virahol: the acetone conversion of reaction 2h is 42.5%, and the selectivity of Virahol is 92.6%; The acetone conversion of reaction 4h is 73.5%, and the selectivity of Virahol is 91.6%.