Method of preparing linear alkylbenzene

Abstract

The invention discloses a synthesizing method of straight-line alkyl benzene, which comprises the following steps: adopting straight-line olefin with carbon atom number between 2 and 20 and benzene as raw material; inputting in the reactor; reacting benzene and olefin with molar rate at 2-100:1 at 290-450 deg. c under 5-15Mpa hypercritical condition; setting the air speed at 0. 1-20h-1; making solid acid as catalyst; adopting one of loaded modified (1) SBA-15 typed molecular sieve, (2) HY typed molecular sieve, (3) USY typed molecular sieve, (4) H beta typed molecular sieve, (5) H-Moderite typed molecular sieve, (6) HZSM-20 typed molecular sieve as composite typed solid acid catalyst. The invention improves transmitting rate of olefin with stable operation, which possesses good using prospect.

Description

(1) Technical field

[0001] The invention relates to a method for preparing linear alkylbenzene, in particular to a method for preparing linear alkylbenzene using solid acid as a catalyst. (2) Background technology

[0002] Linear alkylbenzene is the alkylation product of linear olefins and benzene under the action of a catalyst, and is the sulfonation raw material for the production of linear alkylbenzene sulfonate sodium detergent. The hydrofluoric acid-catalyzed alkylation process is widely used in industry to synthesize linear alkylbenzenes. Because hydrofluoric acid corrodes equipment, pollutes the environment, and is difficult to separate from alkylation products, non-corrosive, non-toxic solid acid catalysts are used instead of hydrofluoric acid catalysts, and linear alkylbenzenes are synthesized by environmentally friendly alkylation processes. become an inevitable development trend.

[0003] CN1072353A discloses the use of Y-type molecular sieve modified by alkalin...

Examples

Embodiment 1～9

[0032] The SBA-15 molecular sieve catalyst synthesized by the invention, or the composite solid acid catalyst prepared by loading and modifying it, is used for the alkylation reaction of benzene and olefin.

[0033] According to the molar ratio of raw materials P123: SiO 2 :HCl:H 2 O is calculated at 1:60:350:9000, weigh 20 grams of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, and 43.1 grams of tetraethyl orthosilicate, 119.1 grams of concentrated hydrochloric acid and 558.9 grams of Ionized water, mix them evenly; crystallize at 100°C for 24 hours, then filter, wash, dry, and bake at 500°C for 5 hours to remove the template agent to obtain SBA-15 molecular sieve, which is ready for use.

[0034]According to the proportion that the molar ratio of silicon to boron is 30, weigh 0.43 grams of boric acid, dissolve it in an acetone solvent 15 times the quality of SBA-15 molecular sieve, dissolve the above-mentioned synthesized SBA-15 molecular sie...

Embodiment 10～13

[0047] 10 grams of the above-mentioned SBA-15 molecular sieves were impregnated with 100 milliliters of phosphotungstic heteropoly acid aqueous solution with a concentration of 0.004mol / L, followed by drying at 110°C and roasting at 400°C to obtain PW 12 Load 10Wt% PW 12 / SBA-15 solid acid catalyst (embodiment 10).

[0048] 10 grams of the above-mentioned SBA-15 molecular sieves were impregnated with 100 milliliters of phosphotungstic heteropoly acid aqueous solution with a concentration of 0.009 mol / L, followed by drying at 110°C and roasting at 400°C to obtain PW 12 Load 20Wt% PW 12 / SBA-15 solid acid catalyst (embodiment 11).

[0049] 10 grams of the above-mentioned SBA-15 molecular sieves were impregnated with 100 milliliters of phosphotungstic heteropoly acid aqueous solution with a concentration of 0.017mol / L, followed by drying at 110°C and roasting at 400°C to obtain PW 12 Load 40Wt% PW 12 / SBA-15 solid acid catalyst (embodiment 12).

[0050] 10 grams of the above...

Embodiment 14～23

[0055] The molecular sieve used in the invention and the molecular sieve solid acid catalyst modified by phosphorus or fluorine are used to carry out the alkylation reaction of benzene and olefin.

[0056] The HY, USY, Hβ, H-Moderite, and HZSM-20 molecular sieves used were purchased from Wenzhou Huahua Group Co., Ltd.

[0057] 10 grams of HY molecular sieves were impregnated with 100 milliliters of phosphoric acid aqueous solution with a concentration of 0.007 mol / L, then dried at 110°C and calcined at 400°C to obtain P 2 o 5 P / HY solid acid catalyst with a loading of 0.5 wt% (Example 19).

[0058] With 100 milliliters of concentration, be that the hydrofluoric acid aqueous solution of 0.026mol / L carries out impregnation treatment to 10 grams of USY molecular sieves, then carry out 110 ℃ of drying and 400 ℃ of roasting treatments, obtain the F / USY solid acid catalyst ( Example 20).

[0059] Be that 0.079mol / L hydrofluoric acid aqueous solution with 100 milliliters of concen...

(1) Technical field

[0001] The invention relates to a method for preparing linear alkylbenzene, in particular to a method for preparing linear alkylbenzene using solid acid as a catalyst. (2) Background technology

[0002] Linear alkylbenzene is the alkylation product of linear olefins and benzene under the action of a catalyst, and is the sulfonation raw material for the production of linear alkylbenzene sulfonate sodium detergent. The hydrofluoric acid-catalyzed alkylation process is widely used in industry to synthesize linear alkylbenzenes. Because hydrofluoric acid corrodes equipment, pollutes the environment, and is difficult to separate from alkylation products, non-corrosive, non-toxic solid acid catalysts are used instead of hydrofluoric acid catalysts, and linear alkylbenzenes are synthesized by environmentally friendly alkylation processes. become an inevitable development trend.

[0003] CN1072353A discloses the use of Y-type molecular sieve modified by alkalin...

Examples

Embodiment 1～9

[0032] The SBA-15 molecular sieve catalyst synthesized by the invention, or the composite solid acid catalyst prepared by loading and modifying it, is used for the alkylation reaction of benzene and olefin.

[0033] According to the molar ratio of raw materials P123: SiO 2 :HCl:H 2 O is calculated at 1:60:350:9000, weigh 20 grams of polyethylene glycol-polypropylene glycol-polyethylene glycol triblock polymer, and 43.1 grams of tetraethyl orthosilicate, 119.1 grams of concentrated hydrochloric acid and 558.9 grams of Ionized water, mix them evenly; crystallize at 100°C for 24 hours, then filter, wash, dry, and bake at 500°C for 5 hours to remove the template agent to obtain SBA-15 molecular sieve, which is ready for use.

[0034]According to the proportion that the molar ratio of silicon to boron is 30, weigh 0.43 grams of boric acid, dissolve it in an acetone solvent 15 times the quality of SBA-15 molecular sieve, dissolve the above-mentioned synthesized SBA-15 molecular sie...

Embodiment 10～13

[0047] 10 grams of the above-mentioned SBA-15 molecular sieves were impregnated with 100 milliliters of phosphotungstic heteropoly acid aqueous solution with a concentration of 0.004mol / L, followed by drying at 110°C and roasting at 400°C to obtain PW 12 Load 10Wt% PW 12 / SBA-15 solid acid catalyst (embodiment 10).

[0048] 10 grams of the above-mentioned SBA-15 molecular sieves were impregnated with 100 milliliters of phosphotungstic heteropoly acid aqueous solution with a concentration of 0.009 mol / L, followed by drying at 110°C and roasting at 400°C to obtain PW 12 Load 20Wt% PW 12 / SBA-15 solid acid catalyst (embodiment 11).

[0049] 10 grams of the above-mentioned SBA-15 molecular sieves were impregnated with 100 milliliters of phosphotungstic heteropoly acid aqueous solution with a concentration of 0.017mol / L, followed by drying at 110°C and roasting at 400°C to obtain PW 12 Load 40Wt% PW 12 / SBA-15 solid acid catalyst (embodiment 12).

[0050] 10 grams of the above...

Embodiment 14～23

[0055] The molecular sieve used in the invention and the molecular sieve solid acid catalyst modified by phosphorus or fluorine are used to carry out the alkylation reaction of benzene and olefin.

[0056] The HY, USY, Hβ, H-Moderite, and HZSM-20 molecular sieves used were purchased from Wenzhou Huahua Group Co., Ltd.

[0057] 10 grams of HY molecular sieves were impregnated with 100 milliliters of phosphoric acid aqueous solution with a concentration of 0.007 mol / L, then dried at 110°C and calcined at 400°C to obtain P 2 o 5 P / HY solid acid catalyst with a loading of 0.5 wt% (Example 19).

[0058] With 100 milliliters of concentration, be that the hydrofluoric acid aqueous solution of 0.026mol / L carries out impregnation treatment to 10 grams of USY molecular sieves, then carry out 110 ℃ of drying and 400 ℃ of roasting treatments, obtain the F / USY solid acid catalyst ( Example 20).

[0059] Be that 0.079mol / L hydrofluoric acid aqueous solution with 100 milliliters of concen...