A method for preparing t-butyl alcohol by decomposing t-butyl hydroperoxide
By using metal-supported catalysts (La, Mo, and Ce) to catalyze the decomposition of tert-butyl hydroperoxide to prepare tert-butanol, the problems of low conversion rate and long reaction time in the prior art are solved, and efficient and selective tert-butanol production is achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2025-01-02
- Publication Date
- 2026-07-10
AI Technical Summary
In existing tert-butanol production technologies, the direct hydration method for isobutylene has a low conversion rate and the catalyst is prone to deactivation, while the alkyl hydrogen peroxide liquid-solid heterogeneous catalytic disproportionation reaction has a long reaction time, which is not conducive to industrial application.
The decomposition of tert-butyl hydroperoxide to prepare tert-butanol was catalyzed by metal-supported catalysts (La, Mo, and Ce). The catalysts were supported by titanium dioxide, carbon black, or bentonite. The reaction conditions were mild and controllable, the catalyst lifetime was long, and the reaction rate was fast.
It improves the production efficiency of tert-butanol, with high conversion rate, good selectivity, high catalyst activity, long service life, and short reaction time.
Abstract
Description
Technical Field
[0001] This invention relates to a method for preparing tert-butanol, specifically a method for preparing tert-butanol by decomposition of tert-butyl hydroperoxide. Background Technology
[0002] tert-Butanol, a widely used fine chemical, plays an important role in pharmaceuticals, fragrances, and additives. Industrially, tert-butanol production technologies mainly include isobutylene hydration and propylene oxide co-production methods. The isobutylene hydration method includes direct isobutylene hydration and isobutylene sulfuric acid hydration.
[0003] Patent CN101293813A discloses a method for preparing tert-butanol from isobutylene in a C4 fraction by hydration, including steps such as hydration reaction under the action of ion exchange resin, C4 distillation, tert-butanol purification, and by-product purification. However, isobutylene has poor miscibility with water, resulting in low conversion rate and easy catalyst deactivation in the direct hydration method.
[0004] Patent CN103553874B discloses a method for preparing alcohols from a liquid-solid heterogeneous catalytic disproportionation reaction of alkyl hydrogen peroxide, using manganese oxides as catalysts. 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 purpose of this invention is to provide a method for preparing tert-butanol by decomposition of tert-butyl hydroperoxide. This invention uses a novel catalyst that can selectively catalyze the decomposition of TBHP to TBA. The catalyst has high reactivity, long service life, and fast reaction rate, thereby improving production efficiency.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0007] A method for preparing tert-butanol by decomposition of tert-butyl hydroperoxide, wherein tert-butyl hydroperoxide undergoes a decomposition reaction in the presence of a catalyst to obtain tert-butanol, wherein the catalyst is a metal-supported catalyst, wherein the metal includes La, Mo and Ce, and the metal loading is 0.5-20 wt%, preferably 1%-10%; the support is one or more of titanium dioxide, carbon black, bentonite, etc., preferably titanium dioxide.
[0008] Preferably, the mass ratio of La, Mo and Ce is 0.2 to 10:1 to 5:1, and more preferably 0.5 to 2:0.8 to 1.5:1.
[0009] The catalyst can be loaded using methods known in the art, such as impregnation, which will not be described again.
[0010] Preferably, the tert-butyl hydrogen peroxide can be tert-butyl hydrogen peroxide produced by oxidation of isobutane using oxygen.
[0011] Preferably, the tert-butyl hydrogen peroxide is diluted with a diluent, and the diluted tert-butyl hydrogen peroxide is sent to a reactor for decomposition reaction.
[0012] The diluent is selected from one or more of alcohols, ketones, acetonitrile, and water, with alcohols and ketones being preferred.
[0013] Furthermore, the mass ratio of tert-butyl hydrogen peroxide to diluent is 2:1 to 1:20, preferably 1:1 to 1:5;
[0014] Preferably, the reaction temperature is 40–160°C, more preferably 50–100°C; the reaction pressure is 0.5–4 MPa, more preferably 1–2 MPa; and the volume hourly space velocity (VHSV) of tert-butyl hydroperoxide is 0.1–5.0 h⁻¹. -1 Preferably 1.0-3.0h -1 .
[0015] The beneficial effects of this invention are as follows:
[0016] This invention provides a process for preparing tert-butanol by decomposing tert-butyl hydrogen peroxide concentrate, providing a new technical route for increasing the production of tert-butanol in the equipment. The reaction conditions of this invention are mild and controllable, the catalyst has a long lifespan, the catalyst activity does not decrease significantly after 1000 hours of recycling, the conversion rate of tert-butyl hydrogen peroxide is high, the reaction time is short, and the selectivity of tert-butanol is high. Detailed Implementation
[0017] The present invention will be further illustrated by specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.
[0018] In the examples, the tert-butyl hydrogen peroxide was a concentrated solution of tert-butyl hydrogen peroxide produced by the co-oxidation method, with a tert-butyl hydrogen peroxide content of 54.56 wt%. The remaining components were mainly tert-butanol. Tert-butanol: Comio, Acetone: Comio, Bentonite: Inokai, Lanthanum nitrate hexahydrate: Maclean, Ammonium molybdate tetrahydrate: Comio, Cerium nitrate hexahydrate: Inokai.
[0019] Example 1
[0020] 50g of bentonite was calcined in a muffle furnace at 650℃ for 6h. 2.1g of lanthanum nitrate hexahydrate, 8.6g of ammonium molybdate tetrahydrate, and 2.5g of cerium nitrate hexahydrate were weighed into a beaker, dissolved in a certain amount of deionized water, and heated in a water bath at 70℃ for 2h until completely dissolved. After cooling to room temperature, the support was impregnated using an equal-volume impregnation method. After drying at room temperature for 12h, the catalyst was dried at 140℃ for 4h. The dried catalyst was then calcined in a muffle furnace at 550℃ for 8h to obtain decomposition catalyst 1. Decomposition catalyst 1 used bentonite as a support and was loaded with 3wt% La, 2wt% Mo, and 2% Ce.
[0021] A tert-butyl hydrogen peroxide concentrate (55% purity) from the propylene-isobutane co-oxidation process for producing propylene oxide was mixed with acetone at a mass ratio of 1:4 as the reaction solution. Decomposition catalyst 1 was loaded into the reactor, and the reaction solution was introduced into the reactor under the conditions of a reaction pressure of 2.0 MPa and a reaction temperature of 70 °C. The volume hourly space velocity (VHSV) of the tert-butyl hydrogen peroxide was 2.0 h⁻¹. -1 .
[0022] Under the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butanol and acetone as a byproduct, with a decomposition conversion rate of 99.1% and a tert-butanol selectivity of 97.5%.
[0023] Example 2
[0024] The catalyst was prepared using the same method as in Example 1, except that the metal loading was 1 wt% La, 2 wt% Mo and 2% Ce, and the support in this example was titanium dioxide.
[0025] A concentrated tert-butyl hydrogen peroxide solution (55% purity) from the propylene-isobutane co-oxidation process for producing propylene oxide was mixed with tert-butanol as a diluent. The reactor contained a catalyst prepared in this embodiment. The reaction solution was introduced into the reactor at a reaction pressure of 1.0 MPa and a reaction temperature of 70°C, with a tert-butyl hydrogen peroxide volume hourly space velocity (HHSV) of 1.0 h⁻¹. -1 .
[0026] Under the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butanol and acetone as a byproduct, with a decomposition conversion rate of 99.5% and a tert-butanol selectivity of 98.4%.
[0027] Example 3
[0028] The catalyst was prepared using the same method as in Example 1, except that the metal loadings were 1 wt% La, 2 wt% Mo and 2% Ce; and the catalyst support was carbon black.
[0029] A concentrated tert-butyl hydrogen peroxide solution (55% purity) from the propylene-isobutane co-oxidation process for producing propylene oxide was mixed with tert-butanol as a diluent at a mass ratio of 2:1 as the reaction solution. The reactor was loaded with the catalyst prepared in this embodiment. 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, with a tert-butyl hydrogen peroxide volume hourly space velocity (HHSV) of 1.0 h⁻¹. -1 .
[0030] Under the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butanol and acetone as a byproduct, with a decomposition conversion rate of 96.7% and a tert-butanol selectivity of 95.9%.
[0031] Comparative Example 1
[0032] The catalyst was prepared using the same method as in Example 1, except that the metal loading was 1 wt% La and the support was titanium dioxide in this comparative example.
[0033] A concentrated tert-butyl hydrogen peroxide solution (55% purity) from the propylene-isobutane co-oxidation process for producing propylene oxide was mixed with tert-butanol as a diluent. The reactor contained a catalyst prepared in this embodiment. The reaction solution was introduced into the reactor at a reaction pressure of 1.0 MPa and a reaction temperature of 70°C, with a tert-butyl hydrogen peroxide volume hourly space velocity (HHSV) of 1.0 h⁻¹. -1 .
[0034] Under the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butanol and acetone as a byproduct, with a decomposition conversion rate of 80.5% and a tert-butanol selectivity of 80.1%.
[0035] Comparative Example 2
[0036] The catalyst was prepared using the same method as in Example 1, except that the metal loading was 2 wt% Mo and the support was titanium dioxide in this comparative example.
[0037] A concentrated tert-butyl hydrogen peroxide solution (55% purity) from the propylene-isobutane co-oxidation process for producing propylene oxide was mixed with tert-butanol as a diluent. The reactor contained a catalyst prepared in this embodiment. The reaction solution was introduced into the reactor at a reaction pressure of 1.0 MPa and a reaction temperature of 70°C, with a tert-butyl hydrogen peroxide volume hourly space velocity (HHSV) of 1.0 h⁻¹. -1 .
[0038] Under the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butanol and acetone as a byproduct, with a decomposition conversion rate of 60.5% and a tert-butanol selectivity of 84.3%.
[0039] Comparative Example 3
[0040] The catalyst was prepared using the same method as in Example 1, except that the metal loading was 2 wt% Ce and the support was titanium dioxide in this comparative example.
[0041] A concentrated tert-butyl hydrogen peroxide solution (55% purity) from the propylene-isobutane co-oxidation process for producing propylene oxide was mixed with tert-butanol as a diluent. The reactor contained a catalyst prepared in this embodiment. The reaction solution was introduced into the reactor at a reaction pressure of 1.0 MPa and a reaction temperature of 70°C, with a tert-butyl hydrogen peroxide volume hourly space velocity (HHSV) of 1.0 h⁻¹. -1 .
[0042] Under the above reaction conditions, tert-butyl hydroperoxide decomposes to produce tert-butanol and acetone as a byproduct, with a decomposition conversion rate of 57.4% and a tert-butanol selectivity of 73.1%.
Claims
1. A method for preparing tert-butanol by decomposition of tert-butyl hydroperoxide, characterized in that, Tert-butyl hydroperoxide undergoes a decomposition reaction in the presence of a catalyst to obtain tert-butanol. The catalyst is a metal-supported catalyst, wherein the metal includes La, Mo, and Ce, and the metal loading is 0.5-20 wt%. The support is one or more of titanium dioxide, carbon black, and bentonite.
2. The method according to claim 1, characterized in that, The carrier is titanium dioxide.
3. The method according to claim 1, characterized in that, The metal loading is 1%-10%.
4. The method according to claim 1, characterized in that, The mass ratio of La, Mo and Ce is 0.2 to 10:1 to 5:
1.
5. The method according to claim 4, characterized in that, The mass ratio of La, Mo and Ce is 0.5-2:0.8-1.5:
1.
6. The method according to claim 1, characterized in that, The tert-butyl hydrogen peroxide is produced by oxidizing isobutane with oxygen.
7. The method according to claim 1, characterized in that, The tert-butyl hydrogen peroxide is diluted with a diluent, and the diluted tert-butyl hydrogen peroxide is sent to the reactor for decomposition reaction.
8. The method according to claim 7, characterized in that, The diluent is selected from one or more of alcohols, ketones, acetonitrs, and water.
9. The method according to claim 8, characterized in that, The diluent is an alcohol or a ketone.
10. The method according to claim 1, characterized in that, The mass ratio of tert-butyl hydrogen peroxide to diluent is 2:1 to 1:
20.
11. The method according to claim 10, characterized in that, The mass ratio of tert-butyl hydrogen peroxide to diluent is 1:1 to 1:
5.
12. The method according to claim 1, characterized in that, The reaction temperature is 40~160°C. o C, reaction pressure 0.5~4 MPa, volume hourly space velocity of tert-butyl hydroperoxide 0.1~5.0 h⁻¹ -1 .
13. The method according to claim 12, characterized in that, The reaction temperature is 50~100℃ o C, the reaction pressure is 1-2 MPa, and the volume hourly space velocity (VHSV) of tert-butyl hydroperoxide is 1.0-3.0 h⁻¹. -1 .