CN109092295B

CN109092295B - Isopropyl benzene catalyst and preparation method thereof

Info

Publication number: CN109092295B
Application number: CN201710473479.4A
Authority: CN
Inventors: 刘仲能; 袁东平; 江兴华; 涂云宝
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2017-06-21
Filing date: 2017-06-21
Publication date: 2020-06-09
Anticipated expiration: 2037-06-21
Also published as: CN109092295A

Abstract

The invention relates to a cumene catalyst and a preparation method thereof, which mainly solve the technical problems of low AMS conversion rate and low cumene selectivity of the catalyst in the prior art.A technical scheme of adopting the cumene catalyst comprises a carrier and active components of (1) metal palladium or an oxide thereof and 0.05-10 g/L and (2) Mo or an oxide thereof and 0-5.00 g/L better solves the technical problems and can be used for the reaction of preparing cumene by hydrogenation of α -methyl styrene.

Description

Isopropyl benzene catalyst and preparation method thereof

Technical Field

The invention relates to a cumene catalyst, a preparation method thereof and application of the catalyst in preparation of cumene from α -methyl styrene through hydrogenation.

Background

At present, the global yield of the cumene is about ten million tons, more than 90 percent of the cumene is used for producing phenol and acetone, a byproduct α -methyl styrene (AMS) is usually generated in the process, the AMS is difficult to separate and remove in the subsequent refining process, but the cumene can be converted into raw material through hydrogenation and then returned to an oxidation process for use, so that the unit consumption of the cumene is reduced, the yield of the phenol is improved, the raw material cost is saved, and the like, so that the consumption of the raw material propylene and benzene can be reduced, and the technical and economic indexes of a device can be improved.

An annual phenol/acetone production apparatus of 1 ten thousand tons can produce 500 tons of AMS as a by-product, and AMS hydrogenation units are arranged in foreign phenol/acetone production apparatuses. The traditional method for preparing cumene through AMS hydrogenation is a slurry method, a Reney nickel catalyst is used, and the method has the defects of complex flow, low catalyst selectivity, short service cycle and the like. Slurry processes are gradually being replaced by fixed bed processes, where the performance of the hydrogenation catalyst is very critical. Many catalysts for preparing isopropylbenzene by AMS hydrogenation have been reported: the experiment of catalytic hydrogenation of AMS with platinum group metal as catalyst was studied in Zhai Teng; west German phenol chemical company adopted Cu₂Cr₂AMS hydrogenation of Ni, high-temp sintering of Pd/alumina catalyst by Chongheng, Pd/C catalyst for α -methyl styrene hydrogenation by Franco C, and Ni, Pt, Pd, Co and Cr by Little₂O₃And AMS selective hydrogenation performance of several metal alloy catalysts; in contrast, the activity and selectivity of a non-palladium catalyst are not high, and in recent years, a catalyst containing palladium as a main or sole component has attracted attention. AMS is active and has poor stability, and thus it is desirable that hydrogenation catalysts have high low temperature activity and selectivity, and adequate impurity resistance to increase the catalyst regeneration cycle and thus prolong the catalyst life.

U.S. Pat. No. 3,3646235 discloses the use of nickel, platinum, palladium, cobalt, chromium oxides and mixed metal catalysts for AMS hydrogenation, preferably Pd catalysts having a metal content of 1 to 5% by weight at 24 to 50 ℃ and 0.17 to 0.45 MPa.

Chinese patent CN1793089A discloses a method for selective hydrogenation of AMS to cumene using a combined catalyst system of nickel-based catalyst and noble metal catalyst. The catalyst combination is filled in a market, 70-95% of AMS conversion is realized in the first reaction zone, and at least 95% of AMS conversion is realized in the second reaction zone.

The catalysts used in the prior art processes have to be improved in terms of AMS conversion and cumene selectivity.

Disclosure of Invention

One of the technical problems to be solved by the invention is to solve the problems of low AMS conversion rate and low cumene selectivity of the catalyst in the prior art, and provide a cumene catalyst which has the characteristics of high AMS conversion rate and high cumene selectivity.

The second technical problem to be solved by the invention is the preparation method of the catalyst.

The third technical problem to be solved by the invention is the application of the catalyst.

In order to solve one of the above technical problems, the technical solution of the present invention is as follows:

the cumene catalyst comprises a carrier and the following active components:

(1) 0.05-10 g/L of metal palladium or oxide thereof;

(2) mo or an oxide thereof in an amount of 0 to 5.00 g/L.

In the above technical solutions, it is preferable that the content of the component (2) is more than 0g/L and not more than 5.00g/L, in which case the component (1) and the component (2) have a synergistic effect in improving the AMS conversion and the selectivity to cumene.

In the above technical scheme, the carrier is not particularly limited, and those well known in the art can be selected, for example, but not limited to, the carrier is selected from at least one of alumina, silica, titania and activated carbon.

In the technical scheme, the BET specific surface area of the carrier is preferably 60-200 m²Per gram, more preferably 80 to 150 m²Per gram.

In the above technical scheme, the pore volume of the carrier is preferably 0.2-0.7 ml/g, and more preferably 0.3-0.5 ml/g.

In the technical scheme, the content of the component (1) is preferably 0.5-5.0 g/L.

In the technical scheme, the content of the component (2) is further preferably 0.05-5.00 g/L.

In the above-mentioned embodiment, the catalyst further preferably contains the component (3), an alkali metal or an oxide thereof in an amount of more than 0g/L and not more than 60 g/L. At this time, in the presence of the component (1), the component (2) and the component (3) have a synergistic effect in enhancing the conversion of AMS and the selectivity of cumene.

In the above technical solution, the alkali metal is preferably at least one of Li, Na, and K, and more preferably K.

In the technical scheme, the content of the component (3) is preferably 0.1-5.0 g/L.

To solve the second technical problem, the technical solution of the present invention is as follows:

the method for preparing the catalyst according to any of the preceding technical solutions, comprising the steps of:

(i) mixing a solution containing a molybdenum compound with a carrier, and roasting to obtain a catalyst precursor I;

(ii) the solution of the palladium compound is mixed with the catalyst precursor I and calcined.

In the technical scheme, the roasting temperature in the step (i) and the roasting temperature in the step (ii) are independently selected from 400-600 ℃.

In the technical scheme, the roasting time of the step (i) and the step (ii) is 3-8 hours.

In the technical scheme, the roasting atmosphere is not particularly limited, and the comparable technical effect can be achieved, so that the air atmosphere is used for economic consideration. For convenience, the air atmosphere is adopted in the specific embodiment of the invention.

When the catalyst of the present invention contains the component (3), it is preferred that the solution of the molybdenum-containing compound in the step (i) is a solution of a molybdenum-containing compound and an alkali metal compound.

As will be appreciated by those skilled in the art, in order to obtain a catalyst with better strength, it is preferable to dry the catalyst before the calcination step in step (i) and/or step (ii), and the drying conditions are not particularly limited, for example, but not limited to, the drying temperature in step (i) and/or step (ii) is 80 to 120 ℃, and the drying time in step (i) and/or step (ii) is 2 to 6 hours.

In the above technical scheme, the alkali metal compound is not particularly limited, such as but not limited to an alkali metal salt or an alkali metal hydroxide. Alkali metal salts such as carbonates, nitrates, and carboxylates of C1-C4.

In the above technical solution, the palladium compound may be palladium chloride, palladium nitrate, chloropalladic acid, ammonium chloropalladate, and a soluble complex of palladium.

In the above-mentioned embodiment, any solvent that can dissolve the compound may be used for the solution preparation of the catalyst, but water is preferred as the solvent in view of economic efficiency, environmental protection, and the like. Wherein the pH of the solution of step (ii) is preferably 2.0-4.0.

The Pd in the catalyst can be reduced to be simple substance and directly used in the reaction of α -methyl styrene hydrogenation to prepare isopropylbenzene, or can also exist in the form of Pd oxide, so that the catalyst is stable for storage and transportation, but needs to be activated by a reducing agent before use, and the reducing agent for activation can be hydrogen or a material containing hydrogen.

To solve the third technical problem, the technical scheme of the invention is as follows:

the application of the catalyst in the technical scheme of one of the technical problems in the preparation of the isopropylbenzene by the hydrogenation of α -methyl styrene.

The technical key of the invention is the selection of the catalyst, and under the condition of determining the catalyst, the technical personnel of the invention know how to reasonably select the applied process conditions. For example, the specific application method may be:

the method for preparing the isopropylbenzene comprises the steps of taking hydrocarbon material containing α -methyl styrene and hydrogen as raw materials in a fixed bed reactor, contacting the raw materials with a catalyst, and reacting to generate the isopropylbenzene.

In the technical scheme, the reaction pressure is preferably 0.2-1.0 MPa, and more preferably 0.3-0.8 MPa.

In the technical scheme, the reaction temperature is preferably 30-100 ℃, and more preferably 35-90 ℃.

The preferred volume airspeed of hydrocarbon material among the above-mentioned technical scheme is 0.3 ~ 3.0 hours^-1More preferably 0.5 to 2.5 hours^-1。

In the technical scheme, the molar ratio of the hydrogen to the α -methylstyrene is preferably 1.0-5.0, and more preferably 1.2-3.0.

In the technical scheme, the hydrocarbon material containing α -methylstyrene contains 1-25% of α -methylstyrene and 75-99% of cumene by weight.

The catalyst of the invention has higher activity and selectivity when being used for preparing cumene. When the catalyst is used for preparing the cumene, the conversion rate of AMS can reach 99.97%, the selectivity of the cumene can reach 99.60%, and the effect is good.

The invention is further illustrated by the following examples. These examples are not intended to limit the scope of the present invention in any way.

Detailed Description

[ example 1 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²G, pore volume 0.46 ml/g) 1L, with 500 ml of potassium carbonate aqueous solution containing 0.30 g of K, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, then mixed with 500 ml of aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the desired catalyst (Pd content 2.7 g/L, K content 0.30 g/L).

2. Catalyst evaluation

40ml of the catalyst was charged in a fixed bed reactor, activated at 50 ℃ for 4 hours in a hydrogen atmosphere of 0.4MPa, and then reacted. The reaction conditions were as follows: the reaction temperature was 45 ℃ and the reaction pressure was 0.3MPa, the molar ratio of hydrogen to AMS in the reaction feed was 1.2, and the liquid space velocity of the reaction feed (containing 21% AMS and 79% cumene) was 1.0h^-1And the reaction was carried out for 72 hours.

The composition of the catalyst and the evaluation results are shown in Table 1 for convenience of comparison.

[ example 2 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume of 0.46 ml/g) 1L, and 500 ml of an ammonium molybdate aqueous solution containing 0.30 g of Mo, drying at 80 ℃ for 4 hours, calcining at 450 ℃ for 4 hours, then mixing with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusting the pH to 3 with hydrochloric acid, drying at 80 ℃ for 4 hours, and calcining at 450 ℃ for 4 hours to obtain the desired catalyst (the Pd content is 2.7 g/L, and the Mo content is 0.30 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 3 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume of 0.46 ml/g) 1L, and potassium carbonate containing 0.24 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.06 g of Mo, drying at 80 ℃ for 4 hours, calcining at 450 ℃ for 4 hours, then mixing with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, drying at 80 ℃ for 4 hours, and calcining at 450 ℃ for 4 hours to obtain the desired catalyst (Pd content of 2.7 g/L, K content of 0.24 g/L, and Mo content of 0.06 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 4 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume of 0.46 ml/g) 1L, and potassium carbonate containing 0.18 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.12 g of Mo, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, then mixed with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the desired catalyst (Pd content of 2.7 g/L, K content of 0.18 g/L, and Mo content of 0.12 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 5 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume 0.46 ml/g), with potassium carbonate containing 0.15 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.15 g of Mo, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, then mixed with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ and driedRoasting for 4 hours at 450 ℃ to obtain the required catalyst (the Pd content is 2.7 g/L, the K content is 0.15 g/L, and the Mo content is 0.15 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 6 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume of 0.46 ml/g) 1L, and potassium carbonate containing 0.12 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.18 g of Mo, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, then mixed with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the desired catalyst (Pd content of 2.7 g/L, K content of 0.12 g/L, Mo content of 0.18 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 7 ]

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume of 0.46 ml/g) 1L, and potassium carbonate containing 0.06 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.24 g of Mo, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, then mixed with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the desired catalyst (Pd content of 2.7 g/L, K content of 0.06 g/L, Mo content of 0.24 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 8 ]

1. Catalyst preparation

A cylindrical titanium dioxide support (specific surface area: 129 m) having a length of 5mm and a diameter of 2mm was placed²G, pore volume 0.41 ml/g) 1L, and was mixed with potassium carbonate containing 0.18 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.12 g of Mo, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, and then mixed with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours, to obtain the desired catalyst (Pd content 2.7 g/L, K content 0.18 g/L, Mo content 0.12 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

[ example 9 ]

1. Catalyst preparation

A cylindrical silica support 5mm in length and 2mm in diameter (specific surface area 130 m)²Pore volume of 0.43 ml/g) was added to 1L, mixed with potassium carbonate containing 0.18 g of K and 500 ml of an aqueous ammonium molybdate solution containing 0.12 g of Mo, dried at 80 ℃ for 4 hours, calcined at 450 ℃ for 4 hours, then mixed with 500 ml of an aqueous solution containing 2.7 g of Pd and adjusted to pH 3 with hydrochloric acid, dried at 80 ℃ for 4 hours, and calcined at 450 ℃ for 4 hours to obtain the desired catalyst (Pd content of 2.7 g/L, K content of 0.18 g/L, Mo content of 0.12 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

Comparative example 1

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²Pore volume 0.46 ml/g) 1L, with 500 ml of an aqueous solution containing 3.00 g of Pd in palladium chloride adjusted to pH 3 with hydrochloric acid, and dried at 80 ℃ for 4 hoursThen, the catalyst is roasted for 4 hours at the temperature of 450 ℃, and the required catalyst (the content of Pd is 3.00 g/L) is obtained.

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

Comparative example 2

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²G, pore volume of 0.46 ml/g) 1L, and is mixed with 500 ml of potassium carbonate aqueous solution containing 3.00 g of K, dried for 4 hours at 80 ℃, and roasted for 4 hours at 450 ℃, thus obtaining the required catalyst (the K content is 3.00 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

Comparative example 3

1. Catalyst preparation

A cylindrical alumina carrier (specific surface of 125 m) having a length of 5mm and a diameter of 2mm was prepared²G, pore volume of 0.46 ml/g) 1L, and is mixed with 500 ml of ammonium molybdate aqueous solution containing 3.00 g of Mo, dried for 4 hours at 80 ℃, and roasted for 4 hours at 450 ℃, thus obtaining the required catalyst (the Mo content is 3.00 g/L).

2. Catalyst evaluation

The catalyst evaluation method is shown in example 1.

TABLE 1 catalyst composition and evaluation results

Claims

1. The application of a cumene catalyst in the reaction of α -methyl styrene hydrogenation to prepare cumene, the cumene catalyst comprises a carrier and the following active components:

(1) 0.05-10 g/L of metal palladium or oxide thereof;

(2) mo or an oxide thereof, more than 0g/L and not more than 5.00 g/L;

(3) an alkali metal or an oxide thereof in an amount of more than 0g/L and not more than 60 g/L.

2. The method of claim 1, wherein the carrier is at least one selected from the group consisting of alumina, silica, titania and activated carbon.

3. The method according to claim 1, wherein the carrier has a BET specific surface area of 60 to 200 m²Per gram.

4. The use according to claim 1, wherein the carrier has a pore volume of 0.2 to 0.7 ml/g.

5. Use according to claim 1, characterized in that the content of component (1) is 0.5 to 5.0 g/L.

6. Use according to claim 1, characterized in that the content of component (2) is 0.05 to 5.0 g/L.

7. Use according to any one of claims 1 to 6, characterized in that the cumene catalyst is prepared by a process comprising the steps of:

(i) mixing a solution containing a molybdenum compound and an alkali metal compound with a carrier, and roasting to obtain a catalyst precursor I;

8. The method according to claim 7, wherein the calcination temperature in step (i) and step (ii) is selected from 400 to 600 ℃.

9. The method as claimed in claim 7, wherein the calcination time in step (i) and step (ii) is 3-8 hours.