Preparation method and application of catalyst for solid acid catalysis of C4 alkylation

A technology of acid-catalyzed carbon and catalyst, applied in the direction of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, chemical instrument and method, etc., which can solve the problem of unfavorable separation of alkylated oil products and easy carbon deposition Deactivation, limiting industrial applications and other issues, to achieve the effect of reducing the deactivation rate of catalytic carbon deposition, increasing the hydrogen transfer rate, and increasing the hydrogen transfer rate

Active Publication Date: 2019-06-11
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although it can prolong catalyst life to a certain extent, it is not conducive to the separation of alkylate products
In addition, there are problems such as short catalyst life and small amplification factor, which limit its further industrial application.
[0004] In summary, the existing solid acid catalysts generally have the problem of easy carbon deposition and deactivation, and the selectivity of trimethylpentane is not high enough

Method used

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  • Preparation method and application of catalyst for solid acid catalysis of C4 alkylation

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] 50.7mL tetraethyl orthosilicate, 2.5mL hexadecyl long organosilane quaternary ammonium salt ((CH 3 O) 3 SiC 3 h 6 N(CH 3 ) 2 C 16 h 33 Cl) and 91mL of 0.5mol / L tetrapropylammonium hydroxide aqueous solution were added to a 250mL round bottom flask, stirred and hydrolyzed at 35°C for 2h, then added aluminum nitrate according to Si / Al=50, stirred for another 30 minutes, and then pressed 0.5 Add potassium chloroplatinite at wt% load, add iron porphyrin at 2wt% load, add phosphotungstic acid at 10wt% load, continue stirring for 2 hours, and then transfer to a stainless steel crystallization kettle with a polytetrafluoroethylene liner , crystallized at 250°C for 72h, filtered with suction, dried, and calcined at 500°C to remove tetrapropylammonium hydroxide to obtain Pt-Fe-HPA / ZSM-5 catalyst.

Embodiment 2

[0021] Embodiment 2: heteropoly acid type and load

[0022] 50.7mL tetraethyl orthosilicate, 2.5mL hexadecyl long organosilane quaternary ammonium salt ((CH 3 O) 3 SiC 3 h 6 N(CH 3 ) 2 C 16 h 33 Cl) and 91mL of 0.5mol / L tetrapropylammonium hydroxide aqueous solution were added to a 250mL round bottom flask, stirred and hydrolyzed at 35°C for 2h, then added aluminum nitrate according to Si / Al=50, stirred for another 30 minutes, and then pressed 0.5 Add potassium chloroplatinite at wt% load, add iron porphyrin at 2wt% load, add silicotungstic acid at 40wt% load, continue stirring for 2 hours, and then transfer to a stainless steel crystallization kettle with a polytetrafluoroethylene liner , crystallized at 250°C for 72h, filtered with suction, dried, and calcined at 500°C to remove tetrapropylammonium hydroxide to obtain Pt-Fe-HPA / ZSM-5 catalyst.

Embodiment 3

[0023] Embodiment 3: heteropoly acid type and load

[0024] 50.7mL tetraethyl orthosilicate, 2.5mL hexadecyl long organosilane quaternary ammonium salt ((CH 3 O) 3 SiC 3 h 6 N(CH 3 ) 2 C 16 h 33 Cl) and 91mL of 0.5mol / L tetrapropylammonium hydroxide aqueous solution were added to a 250mL round bottom flask, stirred and hydrolyzed at 35°C for 2h, then added aluminum nitrate according to Si / Al=50, stirred for another 30 minutes, and then pressed 0.5 Add potassium chloroplatinite at wt% load, add iron porphyrin at 2wt% load, add germanium tungstic acid at 5wt% load, continue stirring for 2 hours, and then transfer to a stainless steel crystallization kettle with a polytetrafluoroethylene liner , crystallized at 250°C for 72h, filtered with suction, dried, and calcined at 500°C to remove tetrapropylammonium hydroxide to obtain Pt-Fe-HPA / ZSM-5 catalyst.

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Abstract

The invention provides a preparation method and application of a catalyst for solid acid catalysis of C4 alkylation. In the preparation process of ZSM-5 molecular sieves with multi-stage pores, a certain amount of heteropoly acid compound (HPA) and metal components such as Pt and Fe are introduced in situ to make the heteropoly acid compound and the Pt and Fe nanoparticles grow in situ at the porechannel surfaces of the ZSM-5 molecular sieves with the multi-stage pores. According to the method and application provided by the invention, the catalyst (Pt-Fe-HPA/ZSM-5) provided by the inventionis used, a mixture of isobutane and butene is used as a reaction raw material, and under the conditions of the alkane-alkene ratio of 50, the mass space velocity of 4.5 h<-1>, the pressure of 2.5-6.0MPa and the reaction temperature of 80-150 DEG C, high-selectivity conversion of the isobutane and the butene into target product trimethylpentane can be realized; the preparation method is easy to enlarge; and the catalyst can be applied to the field of acid catalysis of the C4 alkylation, and has better industrial application prospects.

Description

technical field [0001] The invention relates to a solid acid catalyst for C4 alkylation and a preparation method thereof, belonging to the catalyst preparation technology in the technical field of industrial catalysis. Background technique [0002] In recent years, my country has introduced a number of policies to accelerate the upgrading of oil products. Among the many blending components, the main component of alkylated gasoline is isoparaffins with high octane number. It does not contain tetraethyl lead, MTBE, olefins, and aromatics. The octane number is as high as 95-99, and the vapor pressure is relatively high. Low in sulfur, olefins and aromatics, so alkylated gasoline is an ideal blending component of clean commercial gasoline, known as "green gasoline blending component". Compared with liquid acid alkylation, the solid acid alkylation process has no corrosion to equipment and is relatively more friendly to the environment. Therefore, it becomes the future developm...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18B01J27/188C07C2/62C07C9/21
Inventor 王峰李书双
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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