CN1083415C

CN1083415C - Process for preparing isopropanol by hydrogenation of acetone

Info

Publication number: CN1083415C
Application number: CN98121050A
Authority: CN
Inventors: 马友山; 苏杰; 张跃光; 王春梅
Original assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals; China Petrochemical Corp
Current assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals; China Petrochemical Corp
Priority date: 1998-12-03
Filing date: 1998-12-03
Publication date: 2002-04-24
Anticipated expiration: 2018-12-03
Also published as: CN1255482A

Abstract

The present invention introduces a process for preparing isopropanol by the hydrogenation of acetone, wherein in a fixed bed reactor with a catalyst by adopting tabletting shaped CuO and ZnO mixture, the acetone is hydrogenated to prepare isopropanol. At a certain temperature and pressure, the conversion rate of acetone is 99.9%, and the selectivity of isopropanol is 99.9%.

Description

A kind of processing method by the acetone hydrogenation preparing isopropanol

The present invention relates to a kind of method of producing Virahol by acetone hydrogenation.

The production of Virahol can adopt the method for propylene hydration to make, as adopting the indirect esterification process of vitriolic, the methods such as direct hydration method of solid an acidic catalyst or cation exchange resin catalyst.

Because industrial most of acetone is all obtained by isopropyl benzene peroxidation method, and with the phenol coproduction.Because the increase of the requirement of phenol produces a large amount of acetone, the imbalance of demand occurs, often causes the excessive situation of acetone.So just make and become an economically feasible route by preparing isopropyl alcohol by acetone hydrogenation.

The hydrogenation of acetone can come catalyzed reaction with Ni-based or copper-based catalysts, or adopts the catalysis such as palladium, platinum, rhodium, ruthenium of precious metal.Nickel catalyzator is the best with Raney Ni (Raney Nickel), also can adopt carrier or the composite oxides form of being stated from.Then many and other metal oxide of copper is compound as catalyzer or support on carrier.

Acetone is hydrogenation on the catalyzer of above type, adopts fixed-bed reactor more, and acetone and hydrogen enter the reactor that catalyzer is housed with certain proportioning continuously under liquid phase or gas phase situation, be hydrogenated into Virahol under proper temperature and hydrogen pressure.

Day, the disclosure was speciallyyed permit the method that flat 3-141235 has introduced the employing raney nickel catalyst, and this patent is introduced the transformation efficiency of acetone hydrogenation and the selectivity of Virahol all reaches 99.9%.Flat 2-279643 has introduced employing Ru/ γ-Al ₂O ₃Catalyst hydrogenation technology it is introduced, acetone is through the isopropanol back end hydrogenation, under 9.0MPa pressure, the highlyest can reach 99.9% transformation efficiency, and the selectivity of Virahol is the highest also to reach 99.9%.Though these two kinds of catalyzer have good active and selectivity, the raney nickel catalyst relative price is higher, and complicated when catalyst loading, operation; Noble metal catalyst prices such as platinum, palladium, rhodium are expensive more, moreover are used for acetone hydrogenation condition harshness, and reaction pressure is too high.

Adopt that the advantage of copper-based catalysts is that preparation is simple, low price and easy handling use.The catalyzer of copper base generally is loaded on the carrier or with other metal oxide and makes as the promotor compression molding.The improvement of copper-based catalysts is to select suitable promotor composition to improve its activity and selectivity, can reach and the same good catalytic effect of nickel catalyzator.When adopting the catalyzer of supported carrier such as aluminum oxide, silicon oxide, because the existence of carrier easily causes other side reaction, the selectivity of Virahol is not high.When adopting other metal oxide, require these metal oxide functionals both to can be used as the activeconstituents of hydrogenation, play the effect that supports copper simple substance, dispersion copper crystallite again as promotor.As help catalytic metal oxide usually with cupric oxide through compression molding, the reaction that this kind promotor only requires the hydrogenation to acetone to generate Virahol has activity, is unlikely to reduce the selectivity of Virahol like this.

Introduced the method for hydrotreating that adopts the Cu-Cr catalyzer as russian patent SU1051055A, SU1118632A and the flat 3-41038 of Japanese Patent, Russ P RU2047590 adopts and contains NiO (weight percentage 25～65%), CuO (weight percentage 10～35%), Cr ₂O ₃The catalyzer of (weight percentage 15～40%) comes shortening.Adopt this kind catalyst hydrogenation, shortcoming is that the selectivity of the transformation efficiency of acetone and Virahol is not high, generally is lower than 99.5%, and promptly the yield of Virahol is not high.And, adopt Cr ₂O ₃As helping catalyst component, the toxicity of chromium cpd make Preparation of catalysts and with after the processing trouble, easily produce the problem of environment aspect.

The objective of the invention is in the preparing isopropyl alcohol by acetone hydrogenation process, adopt a kind of copper-based catalysts that helps catalyst component that contains, by adopting this kind catalyzer, the selectivity that makes acetone hydrogenation generate Virahol is improved, and promptly the yield of Virahol is improved; With the original chromium compound catalyst that contains of this catalyst replaced, avoided the toxic action in chromium-containing catalyst production and the use simultaneously.

It is when helping the copper catalyst of catalyst component that this patent find to adopt ZnO, the result when acetone conversion and Virahol selectivity all help catalysis greater than other metal oxide of employing of above patent introduction; Near in addition reach the catalytic effect of Raney Ni.In this kind catalyzer, ZnO itself promptly has the hydrogenation catalyst effect, can play the effect that disperses the copper crystallite, supports CuO again.

According to the present invention, the weight percentage of the CuO-ZnO catalyzer of employing is formed (later catalyzer composition all by weight percentage) and is: contain CuO 25～75%, ZnO 20～70%, and the best is CuO 40～60%, and ZnO 35～55%.Lubricant such as graphite and binding agent such as mineral binder bond aluminum oxide, silicon sol etc. or compositions such as organic binder bond such as polyvinyl alcohol, polyoxyethylene glycol that all the other add during for moulding.CuO content increases, the transformation efficiency of reaction and generation Virahol selectivity increase, at CuO content is 50% o'clock, the transformation efficiency of acetone and generation Virahol selectivity are the highest, at CuO content greater than 50% o'clock, the transformation efficiency of acetone and generate the Virahol selectivity and no longer increase, and the physical strength of catalyzer decreases when containing too many CuO, and life of catalyst shortens.

This catalyzer is the aqueous solution by soluble copper salt and zinc salt, adds the alkali co-precipitation, obtains oxide mixture after throw out drying, the roasting, adds binding agent again and the lubricant compression molding makes.

Catalyzer copper in catalysis acetone hydrogenation process is to play main katalysis with the copper simple substance of going back ortho states, and catalyzer at first adopts hydrogen-nitrogen mixed gas that catalyzer is reduced behind the reactor of packing into, also can adopt Virahol to reduce.

This reaction process adopts fixed-bed reactor, and reactant acetone and hydrogen enter catalyst bed reaction continuously with gas phase and is converted into acetone.The hydrogen that reacts excessive loops back reactor after low temperature separation process, the reaction liquid product separates the back and obtains the product Virahol.

The hydrogen that enters reactor is big more then favourable more to reaction to the mol ratio of acetone, but greater than 4.5 o'clock, it is not obvious that effect becomes, and as to this reaction, the mol ratio of hydrogen and acetone is the best between 1.5-4.5.

Acetone hydrogenation becomes the isopropanol reaction temperature to carry out between 150～250 ℃, and the pressure of reaction is between 1.0～5.0MPa; Volume space velocity is at 0.5～4.0h during the liquid of acetone feed ^-1Between.

Adopt technology involved in the present invention, CuO-ZnO catalyzer particularly involved in the present invention can reach optionally simultaneously in the assurance activity, reduces the manufacturing cost of catalyzer, avoids original toxic action that contains in chromium compound catalyst production and the use.

Related concept definition is as follows in the following example:

Acetone conversion=react the total amounts of acetone of amounts of acetone/charging

The amounts of acetone of the selectivity of Virahol=be converted into Virahol/react amounts of acetone embodiment 1

To contain CuO 50%, ZnO 45%, all the other catalyzer 200ml by what above illustration method made for polyvinyl alcohol and graphite, in the fixed-bed reactor of the internal diameter 20mm that packs into, in the Thermal couple casing pipe of Φ 6 is arranged.After hydrogen-nitrogen mixed gas reduction, advance acetone, fed with acetone LHSV=1.0h ^-1, hydrogen and acetone mol ratio are 3: 1, and 180 ℃ of temperature of reaction, under the 4.0MPa condition, the transformation efficiency of acetone is 99.8%, and the Virahol selectivity is 99.8%, and by product is micro-isopropyl ether and 5-methyl-2-amylalcohol.Example 2-5

Adopt the catalyzer of different CuO and ZnO content, press the reaction conditions of embodiment 1, must be as the table 1 as a result of table 1

Example	Content CuO%ZnO% in the catalyzer	Reaction conditions	Acetone conversion %	Virahol selectivity %
Example	Content CuO%ZnO% in the catalyzer	Reaction conditions	Acetone conversion %	Virahol selectivity %	2	30 65	With example 1	98.9	98.8
3	40 55	With example 1	99.1	99.6	2	30 65	With example 1	98.9	98.8
3	40 55	With example 1	99.1	99.6	4	60 35	With example 1	99.7	99.8
5	70 25	With example 1	99.7	99.8	4	60 35	With example 1	99.7	99.8

Embodiment 6-13

The catalyzer 200ml that will contain CuO50%, ZnO45% in the reactor of the internal diameter 20mm that packs into, after the hydrogen nitrogen mixed gas reduction, changes the reaction result table 2 that different reaction conditionss draws table 2

Example	Reaction conditions	Acetone conversion	The Virahol selectivity
Example	Reaction conditions	Acetone conversion	The Virahol selectivity		Temperature, ℃ pressure, MPa air speed, h ^-1Hydrogen/ketone mol ratio	％	％
6	230 4.0 1.0 3	97.5	98.5			％	％
6	230 4.0 1.0 3	97.5	98.5	7	200 4.0 1.0 3	99.1	99.0
8	160 4.0 1.0 3	93.5	99.6	7	200 4.0 1.0 3	99.1	99.0
8	160 4.0 1.0 3	93.5	99.6	9	180 2.0 1.0 3	85.5	99.2
10	180 3.0 1.0 3	99.4	99.5	9	180 2.0 1.0 3	85.5	99.2
10	180 3.0 1.0 3	99.4	99.5	11	180 4.0 1.0 1.9	99.3	99.3
12	180 4.0 1.0 4.5	99.9	99.9	11	180 4.0 1.0 1.9	99.3	99.3
12	180 4.0 1.0 4.5	99.9	99.9	13	180 4.0 3.0 3	85.6	99.9

Claims

1. processing method by the acetone hydrogenation preparing isopropanol, it is characterized by and adopt a kind of CuO-ZnO oxide mixture catalyst, wherein the CuO weight percentage is 25-75%, and the ZnO weight percentage is 20-70%, lubricant and binding agent composition that all the other add during for moulding.

2. in accordance with the method for claim 1, it is characterized in that the CuO weight percentage is 40～60% in the said catalyzer composition, the ZnO weight percentage is 35-55%.

3. in accordance with the method for claim 1, the processing condition that it is characterized in that hydrogenation reaction are temperature: 150-250 ℃, the pressure of hydrogenation reaction: 1.0-5.0MPa, the volume space velocity when mol ratio of feed hydrogen and interior ketone: 1.5-4.5, the liquid of acetone feed.0.5～4.0h ^-1。