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CN107376906B - A kind of tert-butyl hydroperoxide hydrogenation catalyst and its preparation method and application - Google Patents

A kind of tert-butyl hydroperoxide hydrogenation catalyst and its preparation method and application Download PDF

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CN107376906B
CN107376906B CN201710604196.9A CN201710604196A CN107376906B CN 107376906 B CN107376906 B CN 107376906B CN 201710604196 A CN201710604196 A CN 201710604196A CN 107376906 B CN107376906 B CN 107376906B
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catalyst
butyl hydroperoxide
tert
carrier
hours
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CN107376906A (en
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姚志龙
彭素素
周明
孙培永
张胜红
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Beijing Enze Fulai Technology Co ltd
Beijing Institute of Petrochemical Technology
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Beijing Enze Fulai Technology Co ltd
Beijing Institute of Petrochemical Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds

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Abstract

The invention relates to a tert-butyl hydroperoxide hydrogenation catalyst, a preparation method and application thereof. The tert-butyl hydroperoxide hydrogenation catalyst comprises Pd and SnO loaded on a carrier2(ii) a Based on the weight of the carrier, the carrier contains 0.1 to 0.5 percent of Pd and 16 to 19 percent of Sn. The preparation method is simple, the loading amount of the noble metal Pd is low, the catalyst has high tert-butyl hydroperoxide hydrogenation activity (more than or equal to 95 percent and up to 99.99 percent) and high tert-butyl alcohol selectivity (more than or equal to 90 percent and up to more than 99 percent), and high activity stability, and after the catalyst is continuously used for 510 hours, the conversion rate and the selectivity of the tert-butyl hydroperoxide are not obviously reduced.

Description

Tert-butyl hydroperoxide hydrogenation catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of hydrogenation catalysis, and particularly relates to a tert-butyl hydroperoxide hydrogenation catalyst, and a preparation method and application thereof.
Background
With the development of biodiesel technology, fatty acid methyl ester is easier to obtain, and epoxy fatty acid methyl ester as a downstream product of biodiesel also gains more and more attention. Epoxy fatty acid methyl ester is an environment-friendly plasticizer and can replace dioctyl phthalate (DOP) to be used as a polyvinyl chloride plasticizer. The epoxidation process is to convert unsaturated fatty acid ester into ternary oxygen ring functional group, and molecular oxygen, hydrogen peroxide organic acid, hydrogen peroxide, organic hydrogen peroxide are used for providing oxygen source.
Unsaturated fatty acid methyl ester is epoxidized by tert-butyl hydroperoxide, and the epoxy level of the obtained epoxy product is higher. However, t-butyl hydroperoxide is unstable above 75 ℃ and there is a risk of explosion of the excess t-butyl hydroperoxide remaining from the epoxidation reaction. The simplest method for solving the problem is catalytic hydrogenation, tertiary butanol is obtained by coproduction, the tertiary butanol is an important fine chemical product, such as an alkylating agent, an organic reaction solvent, high-purity isobutene preparation and the like, hydrogen is used in the catalytic hydrogenation reaction, the generated by-product is water, and the method is an economic, practical and environment-friendly hydrogenation reaction process.
The prior document CN200910056813 discloses that Pd/carrier is used as a hydrogenation catalyst for hydrogenation reaction of cumene hydroperoxide, the conversion rate of the cumene hydroperoxide is 97-100%, the selectivity of α -dimethyl benzyl alcohol is 99.6-99.8%, and CN200910057816 discloses a hydrogenation method of the cumene hydroperoxide, wherein 0.5% Pd/Al is used2O3As a hydrogenation catalyst, the conversion rate of cumene hydroperoxide is 99.5 percent, the selectivity of α -dimethylbenzyl alcohol is 96 percent, and 0.5 percent of Pd to 2.0 percent of Sn/Al2O3As a hydrogenation catalyst, cumene hydroperoxide conversion is 100%, and α -dimethylbenzyl alcohol selectivity is 98%, and in addition, publication CN201410470601 discloses that Pd/Al is used as a hydrogenation catalyst for the hydrogenation decomposition reaction of cyclohexyl hydroperoxide, the cyclohexyl hydroperoxide conversion reaches 99%, and the cyclohexanol and cyclohexanone selectivity is 100%.
However, the inventors of the present application have found that Pd/Al is used2O3As a tert-butyl hydroperoxide (TBHP) hydrogenation catalyst, the conversion rate of tert-butyl hydroperoxide can reach 99.72%, but the conversion rate of di-tert-butyl hydroperoxide (DBHP) is negative, which indicates that tert-butyl hydroperoxide is converted into di-tert-butyl hydroperoxide, and the selectivity of tert-butyl alcohol (TBA) is only 84.95%; with Pd-Sn/Al2O3As a tert-butyl hydroperoxide hydrogenation catalyst, the selectivity of tert-butyl alcohol is remarkably improved, but the conversion rate of tert-butyl hydroperoxide is greatly reduced due to the excessively high or low Sn content, and the conversion rate of di-tert-butyl hydroperoxide is reduced due to the excessively high Sn content.
Therefore, it is desirable to provide a hydrogenation catalyst having high t-butyl hydroperoxide hydrogenation activity and high t-butyl alcohol selectivity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a tert-butyl hydroperoxide hydrogenation catalyst, and a preparation method and application thereof.
A tert-butyl hydroperoxide hydrogenation catalyst which is a carrier loaded with Pd and SnO2(ii) a Based on the weight of the carrier, the carrier contains 0.1 to 0.5 percent of Pd and 16 to 19 percent of Sn.
The support may be alumina, but is not limited thereto.
A preparation method of a tert-butyl hydroperoxide hydrogenation catalyst comprises the following steps: and (3) impregnating the carrier with a Pd-containing solution and a Sn-containing solution, drying, roasting and reducing to obtain the catalyst.
In one embodiment, the carrier is impregnated with a solution containing Sn, dried and then calcined to obtain a catalyst intermediate I; impregnating the catalyst intermediate II with a Pd-containing solution, drying and roasting to obtain a catalyst intermediate II; and reducing the catalyst intermediate II to obtain the catalyst.
In one embodiment, the temperature of the drying is 50 ℃ and the temperature of the firing is 540 ℃.
In one embodiment, H2 is used as a reducing agent in the reduction, and the reduction temperature is 95-200 ℃, preferably 140-185 ℃.
In one embodiment, the Sn-containing solution is immersed in absolute ethyl alcohol as a solvent for 12-24 hours at room temperature by an equal volume.
In one embodiment, the Pd-containing solution is immersed in an equal volume of a 10-20% aqueous solution of nitric acid as a solvent at room temperature for 12-24 hours.
In one embodiment, the support is alumina;
taking Al with required mass2O3And (2) taking a dilute nitric acid solution with the mass fraction of 10-20% as an adhesive, uniformly kneading, extruding into strips, molding, drying and roasting to obtain the alumina carrier. And extruding the strips on a strip extruding machine with a plate hole diameter of 0.5-2.0 mm. The drying temperature is between room temperature and 50 ℃. The roasting temperature is 400-700 ℃.
An application of a tert-butyl hydroperoxide hydrogenation catalyst in preparing tert-butyl alcohol by hydrogenating tert-butyl hydroperoxide.
In one embodiment, a fixed bed reaction device is adopted, the reaction temperature is controlled to be 50-70 ℃, the reaction pressure is controlled to be 0-1.0 MPa, and H is2The mol ratio of the tert-butyl hydroperoxide to the tert-butyl hydroperoxide is (1-12) to 1, and the mass space velocity of the raw material containing the tert-butyl hydroperoxide is 0.1-5 h-1。
In one embodiment, the tert-butyl hydroperoxide is fed as an aqueous tert-butyl hydroperoxide solution, wherein the mass concentration of tert-butyl hydroperoxide is between 60% and 65%.
The invention has the beneficial effects that:
the hydrogenation catalyst provided by the invention is simple in preparation method, low in loading of noble metal Pd, high in tert-butyl hydroperoxide hydrogenation activity (more than or equal to 95% and up to 99.99%), high in tert-butyl alcohol selectivity (more than or equal to 90% and up to more than 99%), and high in activity stability, and after the catalyst is continuously used for 510 hours, the conversion rate and the selectivity of tert-butyl hydroperoxide are not obviously reduced.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
Al described in the following examples2O3The preparation method of the carrier is the same as that of the carrier: 31g of 10 wt% dilute nitric acid solution was weighed and added to 40g of pseudo-boehmite powder, kneaded uniformly, and extruded into a bar. Drying at 50 ℃, then roasting in a muffle furnace at 540 ℃ for 4h, and after roasting, making the roasted material into small sections of 3-10 mm to obtain Al2O3And (3) a carrier.
Example 1
First, catalyst preparation
1) 6.08g of stannous chloride dihydrate are weighed and dissolved in absolute ethyl alcohol, and 20g of Al is added into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.1446g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours at room temperature, dried for 4 hours at 50 ℃, and finally placed into a muffle furnace to be roasted for 4 hours at 540 ℃, so that a catalyst intermediate II is obtained.
3) And (3) reducing the catalyst intermediate II at 180 ℃ for 1H by H2, wherein the flow rate of H2 is 30ml/min, and reducing at normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows by taking a dry-based alumina carrier as a reference: 16% of tin and 0.3% of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Example 2
First, catalyst preparation
1) 6.84g of stannous chloride dihydrate are weighed and dissolved in absolute ethyl alcohol, and 20g of Al is added into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.1446g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours at room temperature, dried for 4 hours at 50 ℃, and finally placed into a muffle furnace to be roasted for 4 hours at 540 ℃, so that a catalyst intermediate II is obtained.
3) Catalyst intermediate II H at 180 DEG C2Reducing for 1H, wherein the flow rate of H2 is 30ml/min, reducing under normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows based on a dry-based alumina carrier: 18 percent of tin and 0.3 percent of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein tert-butyl hydroperoxide65 wt.%, a concentration of di-tert-butyl hydroperoxide of 10 wt.%, a hydrogen/tert-butyl hydroperoxide molar ratio of 2, a reaction time of 4h, the results are given in Table 1.
Example 3
First, catalyst preparation
1) Weighing 7.22g of stannous chloride dihydrate, dissolving in absolute ethyl alcohol, and adding 20g of Al into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.1446g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours at room temperature, dried for 4 hours at 50 ℃, and finally placed into a muffle furnace to be roasted for 4 hours at 540 ℃, so that a catalyst intermediate II is obtained.
3) And (3) reducing the catalyst intermediate II at 180 ℃ for 1H by H2, wherein the flow rate of H2 is 30ml/min, and reducing at normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows by taking a dry-based alumina carrier as a reference: 19% of tin and 0.3% of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Example 4
First, catalyst preparation
1) 6.46g of stannous chloride dihydrate are weighed and dissolved in absolute ethyl alcohol, and 20g of Al is added into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.0723g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours under the room temperature condition, the solution is dried for 4 hours at 50 ℃, and finally the catalyst intermediate II is roasted for 4 hours at 540 ℃ in a muffle furnace.
3) Catalyst intermediate II H at 180 DEG C2Reducing for 1H, wherein the flow rate of H2 is 30ml/min, reducing under normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows based on a dry-based alumina carrier: 17% of tin and 0.15% of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Example 5
First, catalyst preparation
1) 6.84g of stannous chloride dihydrate are weighed and dissolved in absolute ethyl alcohol, and 20g of Al is added into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.0723g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours under the room temperature condition, the solution is dried for 4 hours at 50 ℃, and finally the catalyst intermediate II is roasted for 4 hours at 540 ℃ in a muffle furnace.
3) Catalyst intermediate II H at 180 DEG C2Reducing for 1H, wherein the flow rate of H2 is 30ml/min, reducing under normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows based on a dry-based alumina carrier: 18 percent of tin and 0.15 percent of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide is 65 wt%, di-t-butyl hydroperoxideThe hydrogen concentration was 10 wt%, the hydrogen/tert-butyl hydroperoxide molar ratio was 2, and the reaction time was 4h, the results are shown in Table 1.
Example 6
First, catalyst preparation
1) Weighing 7.22g of stannous chloride dihydrate, dissolving in absolute ethyl alcohol, and adding 20g of Al into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.0723g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours under the room temperature condition, the solution is dried for 4 hours at 50 ℃, and finally the catalyst intermediate II is roasted for 4 hours at 540 ℃ in a muffle furnace.
3) Catalyst intermediate II H at 180 DEG C2Reducing for 1H, wherein the flow rate of H2 is 30ml/min, reducing under normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows based on a dry-based alumina carrier: 19% of tin and 0.15% of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Example 7
First, catalyst preparation
1) 6.84g of stannous chloride dihydrate are weighed and dissolved in absolute ethyl alcohol, and 20g of Al is added into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.0964g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours at room temperature, dried for 4 hours at 50 ℃, and finally placed in a muffle furnace to be roasted for 4 hours at 540 ℃, so that a catalyst intermediate II is obtained.
3) Catalyst intermediate II H at 180 DEG C2Reduction for 1H, wherein H2The flow is 30ml/min, the tert-butyl hydroperoxide hydrogenation catalyst is prepared by normal pressure reduction, and the weight percentage content is as follows by taking a dry-based alumina carrier as a reference: 18 percent of tin and 0.2 percent of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Example 8
The tert-butyl hydroperoxide hydrogenation catalyst which is the same as that in the example 5 is adopted to carry out the tert-butyl hydroperoxide hydrogenation reaction in a fixed bed reactor, the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 1h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 6, and the reaction time was 4 hours, the results are shown in Table 1.
Example 9
The tert-butyl hydroperoxide hydrogenation catalyst which is the same as that in the example 5 is adopted to carry out the tert-butyl hydroperoxide hydrogenation reaction in a fixed bed reactor, the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is 0.2 MPa, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 1h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 6, and the reaction time was 4 hours, the results are shown in Table 1.
Example 10
The same tert-butyl hydroperoxide hydrogenation catalyst as in example 5 was used to conduct the hydrogenation of tert-butyl hydroperoxide in a fixed bed reactor with a catalyst loading of 6gThe reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 6, and the reaction time was 4 hours, the results are shown in Table 1.
Example 11
The tert-butyl hydroperoxide hydrogenation catalyst which is the same as that in the example 5 is adopted to carry out the tert-butyl hydroperoxide hydrogenation reaction in a fixed bed reactor, the loading amount of the catalyst is 6g, the reaction temperature is 55 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 1h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 6, and the reaction time was 4 hours, the results are shown in Table 1.
Example 12
The tert-butyl hydroperoxide hydrogenation catalyst which is the same as that in the example 5 is adopted to carry out the tert-butyl hydroperoxide hydrogenation reaction in a fixed bed reactor, the loading amount of the catalyst is 6g, the reaction temperature is 60 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 1h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 6, and the reaction time was 4 hours, the results are shown in Table 1.
Comparative example 1
First, catalyst preparation
1) 0.0723g of palladium nitrate is weighed and dissolved in 10 wt% dilute nitric acid solution, and 20g of Al is added to the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate.
2) Catalyst intermediate H at 180 deg.C2Reduction for 1H, wherein H2The flow is 30ml/min, the tert-butyl hydroperoxide hydrogenation catalyst is prepared by normal pressure reduction, and the weight percentage content is as follows by taking a dry-based alumina carrier as a reference: 0.15 percent of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Comparative example 2
First, catalyst preparation
6.84g of stannous chloride dihydrate are weighed and dissolved in absolute ethyl alcohol, and 20g of Al is added into the obtained solution2O3The carrier is dipped for 24 hours at room temperature, dried for 4 hours at 50 ℃, and finally put into a muffle furnace for roasting at 540 ℃ for 4 hours to obtain the catalyst, wherein the dry-based alumina carrier is taken as a reference, and the weight percentage content is as follows: 18 percent of tin.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Comparative example 3
First, catalyst preparation
1) Weighing 4.56g of stannous chloride dihydrate, dissolving in absolute ethyl alcohol, and adding 20g of Al into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.0723g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours under the room temperature condition, the solution is dried for 4 hours at 50 ℃, and finally the catalyst intermediate II is roasted for 4 hours at 540 ℃ in a muffle furnace.
3) Reduction of catalyst intermediate two at 180 deg.C with H2 for 1H, where H2Reducing at a flow rate of 30ml/min under normal pressure to obtain tert-butylThe hydrogen peroxide hydrogenation catalyst takes a dry-based alumina carrier as a reference, and comprises the following components in percentage by weight: 12% of tin and 0.15% of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
Comparative example 4
First, catalyst preparation
1) Weighing 7.6g of stannous chloride dihydrate, dissolving in absolute ethyl alcohol, and adding 20g of Al into the obtained solution2O3And (3) soaking the carrier for 24 hours at room temperature, drying the carrier for 4 hours at 50 ℃, and finally roasting the carrier for 4 hours at 540 ℃ in a muffle furnace to obtain a catalyst intermediate I.
2) 0.0723g of palladium nitrate is weighed and dissolved in 10 wt% of dilute nitric acid solution, the obtained solution is added with the catalyst intermediate I, the catalyst intermediate I is soaked for 24 hours under the room temperature condition, the solution is dried for 4 hours at 50 ℃, and finally the catalyst intermediate II is roasted for 4 hours at 540 ℃ in a muffle furnace.
3) And (3) reducing the catalyst intermediate II at 180 ℃ for 1H by H2, wherein the flow rate of H2 is 30ml/min, and reducing at normal pressure to obtain the tert-butyl hydroperoxide hydrogenation catalyst, wherein the weight percentage content of the tert-butyl hydroperoxide hydrogenation catalyst is as follows by taking a dry-based alumina carrier as a reference: 20% of tin and 0.15% of palladium.
Second, catalyst evaluation
Carrying out hydrogenation reaction of tert-butyl hydroperoxide in a fixed bed reactor, wherein the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is normal pressure, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of t-butyl hydroperoxide was 65 wt%, the concentration of di-t-butyl hydroperoxide was 10 wt%, the molar ratio of hydrogen/t-butyl hydroperoxide was 2, and the reaction time was 4 hours, the results are shown in Table 1.
TABLE 1
Figure BSA0000147976960000131
Figure BSA0000147976960000141
As can be seen from Table 1, the Sn-Pd/Al of the present invention2O3The tert-butyl hydroperoxide hydrogenation catalyst has high catalytic activity and selectivity, the conversion rate of tert-butyl hydroperoxide can reach more than 95%, and the selectivity of tert-butyl alcohol can reach more than 90%.
Example 13
In a fixed bed reactor to 18% Sn-0.15% Pd/Al2O3The long-period stability evaluation is carried out on the tert-butyl hydroperoxide hydrogenation catalyst, the loading amount of the catalyst is 6g, the reaction temperature is 65 ℃, the reaction pressure is 0.4 MPa, and the mass space velocity of the aqueous solution of the tert-butyl hydroperoxide is 2h-1Wherein the concentration of the tert-butyl hydroperoxide is 65 wt%, the concentration of the di-tert-butyl hydroperoxide is 10 wt%, the molar ratio of hydrogen to the tert-butyl hydroperoxide is 6, the conversion rate of the tert-butyl hydroperoxide still reaches more than 99% after the reaction is continuously carried out for 510 hours, and the selectivity of the tert-butyl alcohol reaches more than 95%. Therefore, the catalyst of the invention can maintain high conversion rate and selectivity for a long time and has high stability.

Claims (11)

1. A method for preparing tert-butyl alcohol by hydrogenation of tert-butyl hydroperoxide is characterized in that Pd and SnO are loaded on a carrier2The catalyst of (1); the catalyst contains 0.1-0.5% of Pd and 16-19% of Sn based on the weight of the carrier.
2. The method of claim 1, wherein a fixed bed reaction apparatus is used, the reaction temperature is controlled to be 50-70 ℃, the reaction pressure is controlled to be 0-1.0 MPa, and H is controlled to be H2The mol ratio of the tert-butyl hydroperoxide to the tert-butyl hydroperoxide is (1-12) to 1, and the mass space velocity of the raw material containing the tert-butyl hydroperoxide is 0.1-5 h-1。
3. The process according to claim 1 or 2, wherein the tert-butyl hydroperoxide is fed as an aqueous tert-butyl hydroperoxide solution, wherein the concentration by mass of tert-butyl hydroperoxide is between 60% and 65%.
4. The method of claim 1, wherein the support is alumina.
5. The method of claim 1, wherein the catalyst is prepared by the following method: and (3) impregnating the carrier with a Pd-containing solution and a Sn-containing solution, drying, roasting and reducing to obtain the catalyst.
6. The method according to claim 5, characterized in that in the preparation process of the catalyst:
impregnating a carrier with a Sn-containing solution, drying and roasting to obtain a catalyst intermediate I; impregnating the catalyst intermediate II with a Pd-containing solution, drying and roasting to obtain a catalyst intermediate II; and reducing the catalyst intermediate II to obtain the catalyst.
7. The method according to claim 5 or 6, wherein the drying temperature and the calcination temperature are both 50 ℃ and 540 ℃ in the preparation method of the catalyst.
8. The method according to claim 5 or 6, wherein in the preparation method of the catalyst, the reduction is performed with H2Is a reducing agent, and the reduction temperature is 95-200 ℃.
9. The method according to claim 6, wherein in the preparation method of the catalyst, the Sn-containing solution is immersed in absolute ethyl alcohol for 12-24 hours at room temperature by adopting equal volume immersion.
10. The method according to claim 6 or 9, wherein in the preparation method of the catalyst, the Pd-containing solution is impregnated at room temperature for 12-24 hours by using a dilute aqueous nitric acid solution with a mass fraction of 10-20% as a solvent and using an equal volume.
11. The method of claim 5, wherein the support is alumina;
the carrier is prepared by the following method: taking Al with required mass2O3And (2) taking a dilute nitric acid aqueous solution with the mass fraction of 10-20% as an adhesive, uniformly kneading, extruding into strips, molding, drying and roasting to obtain the alumina carrier.
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