Method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide

Abstract

The invention discloses a method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide, tert-butyl hydroperoxide is subjected to a decomposition reaction in the presence of a catalyst to obtain tert-butyl alcohol, the catalyst is a metal supported catalyst, metals comprise La, Mo and Ce, and a carrier is one or more of titanium dioxide, carbon black and bentonite. The novel catalyst is adopted, TBHP decomposition can be catalyzed with high selectivity to obtain TBA, the catalyst is high in reaction activity, long in service life and high in reaction speed, and the production efficiency is improved.

Description

Technical Field

[0001] The invention relates to a method for preparing tert-butyl alcohol, in particular to a method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide. Background Art

[0002] As a widely used fine chemical product, tert-butyl alcohol plays an important role in the fields of medicine, fragrance and additives. The industrial production technology of tert-butyl alcohol mainly includes isobutylene hydration method and propylene oxide co-production method. Among them, the isobutylene hydration method includes isobutylene direct hydration method and isobutylene sulfuric acid hydration method.

[0003] Patent CN101293813A discloses a method for preparing tert-butyl alcohol by hydrating isobutylene in C4 component, which includes the steps of hydration reaction under the action of ion exchange resin, C4 distillation, tert-butyl alcohol refining, by-product refining, etc. However, the mutual solubility of isobutylene and water is poor, so the direct hydration method has low conversion rate and the catalyst is easily deactivated.

[0004] Patent CN103553874B discloses a method for preparing alcohols by liquid-solid heterogeneous catalytic disproportionation reaction of alkyl hydrogen peroxide, using manganese oxide as a catalyst. Although the reaction selectivity is high and the conversion rate is greater than 90%, the required reaction time is long, which is not conducive to industrial application. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide. The present invention adopts a new catalyst, which can catalyze the decomposition of TBHP with high selectivity to obtain TBA. The catalyst has high reaction activity, long service life, fast reaction rate, and improved production efficiency.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] The invention discloses a method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide. The tert-butyl hydroperoxide is decomposed in the presence of a catalyst to obtain tert-butyl alcohol. The catalyst is a metal-supported catalyst, wherein the metal includes La, Mo and Ce, and the metal loading is 0.5-20wt%, preferably 1%-10%; and the carrier is one or more of titanium dioxide, carbon black, bentonite and the like, preferably titanium dioxide.

[0008] Preferably, the mass ratio of La, Mo and Ce is 0.2-10:1-5:1, preferably 0.5-2:0.8-1.5:1.

[0009] The catalyst can be loaded by methods known in the art, such as impregnation, etc., which will not be described in detail again.

[0010] Preferably, the tert-butyl hydroperoxide can be tert-butyl hydroperoxide produced by oxidation with oxygen using isobutane as a raw material.

[0011] Preferably, the tert-butyl hydroperoxide is diluted with a diluent, and the diluted tert-butyl hydroperoxide is sent to a reactor for decomposition reaction.

[0012] The diluent is selected from one or more of alcohols, ketones, acetonitrile and water, preferably alcohols and ketones.

[0013] Furthermore, the mass ratio of tert-butyl hydroperoxide to the diluent is 2:1 to 1:20, preferably 1:1 to 1:5;

[0014] Preferably, the reaction temperature is 40 to 160°C, preferably 50 to 100°C, the reaction pressure is 0.5 to 4 MPa, preferably 1 to 2 MPa, and the volume space velocity of tert-butyl hydroperoxide is 0.1 to 5.0 h -1 , preferably 1.0-3.0h -1 .

[0015] The beneficial effects of the present invention are:

[0016] The invention provides a process method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide concentrate, and provides a new technical route for increasing the production of tert-butyl alcohol for a device; the invention has mild and controllable reaction conditions, a long catalyst life, no obvious decrease in catalyst activity after 1000h of recycling, a high tert-butyl hydroperoxide conversion rate, a short reaction time, and high tert-butyl alcohol selectivity. DETAILED DESCRIPTION

[0017] The present invention is further described by means of specific embodiments. The embodiments of the present invention are only used as illustrations of the present invention and do not limit the scope of the present invention.

[0018] The tert-butyl hydroperoxide in the embodiment is a tert-butyl hydroperoxide concentrate produced by a co-oxidation method, with a tert-butyl hydroperoxide content of 54.56 wt%, and the remaining components are mainly tert-butyl alcohol. Tert-butyl alcohol: Komel, acetone: Komel, bentonite: Inokite, lanthanum nitrate hexahydrate: Macklin, ammonium molybdate tetrahydrate: Komel, cerium nitrate hexahydrate, Inokite.

[0019] Example 1

[0020] 50g of bentonite was placed in a muffle furnace and roasted at 650°C for 6h. 2.1g of lanthanum nitrate hexahydrate, 8.6g of ammonium molybdate tetrahydrate and 2.5g of cerium nitrate hexahydrate were weighed in a beaker, a certain amount of deionized water was added to dissolve, and heated in a water bath at 70°C for 2h until completely dissolved. After cooling to room temperature, the carrier was impregnated by an equal volume impregnation method, dried at room temperature for 12h, and then dried at 140°C for 4h. The dried catalyst was placed in a muffle furnace and roasted at 550°C for 8h to obtain a decomposition catalyst 1, which used bentonite as a carrier and loaded with 3wt% La, 2wt% Mo and 2% Ce.

[0021] The tert-butyl hydroperoxide concentrate (purity of 55%) from the process of producing propylene oxide by co-oxidation of propylene and isobutane was mixed with diluent acetone at a mass ratio of 1:4 as a reaction liquid; the decomposition catalyst 1 was loaded into the reactor, and the reaction liquid was introduced into the reactor under the conditions of a reaction pressure of 2.0 MPa and a reaction temperature of 70°C. The reaction volume space velocity of tert-butyl hydroperoxide was 2.0 h -1 .

[0022] According to the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butyl alcohol and acetone as a by-product, with a decomposition conversion rate of 99.1% and a tert-butyl alcohol selectivity of 97.5%.

[0023] Example 2

[0024] The catalyst was prepared in the same manner as in Example 1, except that the metal loadings were 1 wt% La, 2 wt% Mo and 2% Ce, and the carrier in this example was titanium dioxide.

[0025] The tert-butyl hydroperoxide concentrate (purity of 55%) from the process of producing propylene oxide by co-oxidation of propylene and isobutane was mixed with tert-butyl alcohol as a diluent, and the catalyst prepared in this example was loaded into the reactor; the reaction liquid was introduced into the reactor under the conditions of reaction pressure of 1.0 MPa and reaction temperature of 70° C., and the volume space velocity of tert-butyl hydroperoxide was 1.0 h -1 .

[0026] According to the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butyl alcohol and acetone as a by-product, with a decomposition conversion rate of 99.5% and a tert-butyl alcohol selectivity of 98.4%.

[0027] Example 3

[0028] The catalyst was prepared by the same method as in Example 1, except that the metal loading was 1 wt% La, 2 wt% Mo and 2% Ce; and the catalyst carrier was carbon black.

[0029] The tert-butyl hydroperoxide concentrate (purity of 55%) from the process of producing propylene oxide by co-oxidation of propylene and isobutane was mixed with diluent tert-butyl alcohol at a mass ratio of 2:1 as a reaction solution; the catalyst prepared in this example was loaded into a reactor, and the reaction solution was introduced into the reactor under the conditions of a reaction pressure of 0.5 MPa and a reaction temperature of 70° C., and the volume space velocity of tert-butyl hydroperoxide was 1.0 h -1 .

[0030] According to the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butyl alcohol and acetone as a by-product, with a decomposition conversion rate of 96.7% and a tert-butyl alcohol selectivity of 95.9%.

[0031] Comparative Example 1

[0032] The catalyst was prepared in the same manner as in Example 1, except that the metal loading was 1 wt % La and the carrier in this comparative example was titanium dioxide.

[0033] The tert-butyl hydroperoxide concentrate (purity of 55%) from the process of producing propylene oxide by co-oxidation of propylene and isobutane was mixed with tert-butyl alcohol as a diluent, and the catalyst prepared in this example was loaded into the reactor; the reaction liquid was introduced into the reactor under the conditions of reaction pressure of 1.0 MPa and reaction temperature of 70° C., and the volume space velocity of tert-butyl hydroperoxide was 1.0 h -1 .

[0034] According to the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butyl alcohol and acetone as a by-product, with a decomposition conversion rate of 80.5% and a tert-butyl alcohol selectivity of 80.1%.

[0035] Comparative Example 2

[0036] The catalyst was prepared in the same manner as in Example 1, except that the metal loading was 2 wt % Mo and the carrier in this comparative example was titanium dioxide.

[0037] The tert-butyl hydroperoxide concentrate (purity of 55%) from the process of producing propylene oxide by co-oxidation of propylene and isobutane was mixed with tert-butyl alcohol as a diluent, and the catalyst prepared in this example was loaded into the reactor; the reaction liquid was introduced into the reactor under the conditions of reaction pressure of 1.0 MPa and reaction temperature of 70° C., and the volume space velocity of tert-butyl hydroperoxide was 1.0 h -1 .

[0038] According to the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butyl alcohol and acetone as a by-product, with a decomposition conversion rate of 60.5% and a tert-butyl alcohol selectivity of 84.3%.

[0039] Comparative Example 3

[0040] The catalyst was prepared in the same manner as in Example 1, except that the metal loading was 2 wt % Ce and the carrier in this comparative example was titanium dioxide.

[0041] The tert-butyl hydroperoxide concentrate (purity of 55%) from the process of producing propylene oxide by co-oxidation of propylene and isobutane was mixed with tert-butyl alcohol as a diluent, and the catalyst prepared in this example was loaded into the reactor; the reaction liquid was introduced into the reactor under the conditions of reaction pressure of 1.0 MPa and reaction temperature of 70° C., and the volume space velocity of tert-butyl hydroperoxide was 1.0 h -1 .

[0042] According to the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butyl alcohol and acetone as a by-product, with a decomposition conversion rate of 57.4% and a tert-butyl alcohol selectivity of 73.1%.

Claims

1. A method for preparing tert-butyl alcohol by decomposing tert-butyl hydroperoxide, characterized in that: Tert-butyl hydroperoxide is decomposed in the presence of a catalyst to obtain tert-butyl alcohol, wherein the catalyst is a metal-supported catalyst, wherein the metal includes La, Mo and Ce, and the metal loading is 0.5-20wt%, preferably 1%-10%; and the carrier is one or more of titanium dioxide, carbon black and bentonite, preferably titanium dioxide.

2. The method according to claim 1, characterized in that The mass ratio of La, Mo and Ce is 0.2-10:1-5:1, preferably 0.5-2:0.8-1.5:

1.

3. The method according to claim 1 or 2, characterized in that: The tert-butyl hydroperoxide can be tert-butyl hydroperoxide produced by oxidation with oxygen using isobutane as a raw material.

4. The method according to any one of claims 1 to 3, characterized in that: The tert-butyl hydroperoxide is diluted with a diluent, and the diluted tert-butyl hydroperoxide is sent to a reactor for decomposition reaction.

5. The method according to any one of claims 1 to 4, characterized in that: The diluent is selected from one or more of alcohols, ketones, acetonitrile and water, preferably alcohols and ketones; Furthermore, the mass ratio of tert-butyl hydroperoxide to the diluent is 2:1 to 1:20, preferably 1:1 to 1:

5.

6. The method according to any one of claims 1 to 5, characterized in that: The reaction temperature is 40-160°C, preferably 50-100°C, the reaction pressure is 0.5-4MPa, preferably 1-2MPa, and the volume space velocity of tert-butyl hydroperoxide is 0.1-5.0h -1 , preferably 1.0-3.0h -1 .