Catalyst for producing isopropylbenzene and the production method and use thereof

Patent metadata

Field	Value
Publication number	US-12357975-B2
Application number	US-202017764366-A
Country	US
Kind code	B2
Filing date	Sep 29, 2020
Priority date	Sep 29, 2019
Publication date	Jul 15, 2025
Grant date	Jul 15, 2025

Abstract

Described are a catalyst for producing isopropylbenzene and the production method and use thereof. The catalyst includes a support and an active component supported on the support, wherein the support comprises a support substrate and a modifying auxiliary component supported on the support substrate, wherein the active component includes metal palladium and/or an oxide thereof, and the modifying auxiliary component is phosphorus and/or an oxide thereof; optionally, the active component further includes metal copper and/or an oxide thereof; the catalyst further includes a sulfur-containing compound.

First claim

The invention claimed is:

1. A catalyst for producing isopropylbenzene from α,α-dimethylbenzyl alcohol, comprising a support and an active component supported on the support, wherein the support comprises a support substrate and a modifying auxiliary component supported on the support substrate,
wherein the active component includes metal palladium and/or an oxide thereof, and the modifying auxiliary component includes phosphorus and/or an oxide thereof,
wherein the support substrate is not silica, and said modifying auxiliary component further includes silica, and
wherein a molar ratio of the silicon to phosphorus in the catalyst based on the element is ≤10.

2. The catalyst according to claim 1 , wherein a content of the metal palladium and/or oxide thereof in the catalyst is 0.01-5 wt %, based on a content of the element palladium, and/or
the metal palladium has a dispersity of 5-10%.

3. The catalyst according to claim 2 , wherein the active component further includes an active auxiliary metal and/or an oxide thereof; the active auxiliary metal is at least one selected from the group consisting of metal copper, metal zinc, metal cobalt, metal tin, metal nickel and metal silver;
and a content of the active auxiliary metal and/or oxide thereof in the catalyst is 0.0001-0.2 wt %, based on a content of the auxiliary metal element therein.

4. The catalyst according to claim 1 , wherein a content of the modifying auxiliary component in the catalyst is 0.2-20 wt %, based on a content of element phosphorus.

5. The catalyst according to claim 1 , wherein the support substrate is at least one selected from the group consisting of alumina and activated carbon, and/or the support substrate has a pore size of 10-25 nm and a specific surface area of 50-180 m 2 /g.

6. The catalyst according to claim 1 , wherein the catalyst further includes a co-catalyst of a sulfur-containing compound which is at least one selected from the group consisting of tert-nonyl polysulfides, tert-butyl polysulfides, thiophenes and dimethyl disulfides; and
a content of the co-catalyst in the catalyst is >0-1 wt %, based on an amount of element sulfur.

7. The catalyst according to claim 1 , wherein
a content of silica in the catalyst is >0-60 wt %.

8. The catalyst according to claim 1 , wherein the molar ratio of silicon to phosphorus in the catalyst based on the element is ≤4, wherein, a content of the modifying auxiliary component phosphorus and/or oxide thereof in the catalyst is 0.2-20 wt %, wherein the content of phosphorus and/or oxide thereof is based on a content of element phosphorus therein, and a silica content in the catalyst is >0-60 wt %.

9. The catalyst according to claim 1 , wherein the molar ratio of silicon to phosphorus in the catalyst based on the element is ≤7.60.

10. A method for producing the catalyst according to claim 1 , comprising the following steps:
Step 1: an aqueous solution of a phosphorus-containing compound is mixed with a support substrate, dried and calcined to obtain a phosphorus-containing support;
Step 1′: the phosphorus-containing support is mixed with an aqueous solution of silica gel, dried and calcined to obtain a support containing phosphorus and silicon;
Step 2: the support containing phosphorus and silicon is added to a solution of a palladium-containing compound, dried and calcined to obtain a catalyst precursor in an oxidized state;
Step 3: the catalyst precursor in an oxidized state is subjected to a reduction treatment to obtain the catalyst.

11. The method according to claim 10 , wherein the support substrate is at least one selected from the group consisting of alumina and activated carbon, and/or
the palladium-containing compound is at least one selected from the group consisting of palladium chloride, palladium nitrate and chloropalladic acid, and/or
the phosphorus-containing compound is at least one selected from the group consisting of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate and ammonium hydrogen phosphate, and/or
the solution in step 2 further comprises a compound containing an active auxiliary metal which is at least one selected from the group consisting of active auxiliary metal chlorides, compounds of active auxiliary metal nitrates and compounds of active auxiliary metal acetates; wherein the active auxiliary metal is at least one selected from the group consisting of metal copper, metal zinc, metal cobalt, metal tin, metal nickel and metal silver.

12. The method according to claim 10 , wherein in step 1 and step 2, a calcining temperature is 400-700° C., and/or
in step 3, a reduction treatment is carried out with hydrogen; a reduction temperature is 40-300° C.; and a volume space velocity of hydrogen is 50-500h −1 .

13. The method according to claim 10 , wherein the method further comprises step 4:
Step 4: the catalyst according to step 3 is added to a co-catalyst-containing solution and dried to obtain a further catalyst, wherein the co-catalyst is a sulfur-containing compound.

14. The method according to claim 10 , wherein, based on 1 L of the support substrate,
an amount of the palladium-containing compound is 0.06 g/L-30 g/L, based on an amount of element palladium therein, and/or
an amount of the compound containing an active auxiliary metal is 0.0006 g/L-1.2 g/L, based on an amount of the element of the active auxiliary metal therein, and/or
an amount of the phosphorus-containing compound is 2 g/L-100 g/L, based on an amount of element phosphorus therein, and/or
an amount of the co-catalyst is 0.0001 g/L-3 g/L, based on an amount of element sulfur therein, and/or
an amount of silica gel is 6-300 g/L, based on an amount of silica therein.

15. A method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol, wherein the method comprises: bringing a α,α-dimethylbenzyl alcohol-containing raw material in contact with hydrogen to react in the presence of the catalyst according to claim 1 to obtain isopropylbenzene.

16. The method according to claim 15 , wherein the raw material comprises a hydrocarbon material comprising α,α-dimethylbenzyl alcohol, wherein the hydrocarbon material optionally comprises isopropylbenzene, acetophenone, α-methylstyrene, dimerized isopropyl benzene, and isopropylbenzene hydroperoxide; and/or the method is a liquid phase thermal cycle process.

17. The method according to claim 16 , wherein a pressure is 0.1-4.0 MPa, a temperature is 130-220° C., a liquid hourly space velocity is 1-20 h −1 , and a molar ratio of hydrogen to α,α-dimethylbenzyl alcohol is >4.

18. The method according to claim 15 , comprising obtaining the isopropylbenzene from a raw material of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol and hydrogen through a first catalyst bed and a second catalyst bed in series, by a liquid phase thermal cycle process;
wherein,
a catalyst loading of the first catalyst bed is greater than or equal to that of the second catalyst bed; an inlet temperature of the first catalyst bed is not higher than an inlet temperature of the second catalyst bed; the first catalyst bed has a reaction temperature of 130-190° C., a reaction pressure of 0.1-SMPa, and a liquid hourly space velocity of 1.0-20 h −1 , and/or the second catalyst bed has a reaction temperature of 150-230° C., a reaction pressure of 0.1-5 MPa, and a liquid phase volume space velocity of 2.0-10 h −1 ,
a liquid phase thermal cycle ratio of the first catalyst bed is 1-10; and
a liquid phase thermal cycle ratio of the second catalyst bed is 0-2.

Assignees

• China Petroleum & Chem Corp
• Shanghai Res Inst Petrochemical Tech Sinopec

Inventors

• Liu Zhongneng
• Zhao Duo
• Lv Yuhao
• Ma Wendi
• Gu Guoyao

Classifications

• C07C2527/182

  with silicon · CPC title

• C07C2527/18

  with metals · CPC title

• C07C2523/89

  combined with noble metals · CPC title

• C07C2523/755

  Nickel · CPC title

• C07C2523/72

  Copper · CPC title