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A kind of preparation method of solid superacid catalyst for alkylation of isobutane and butene

A solid superacid, butene alkyl technology, applied in physical/chemical process catalysts, chemical instruments and methods, organic chemistry, etc., can solve problems such as one-step improvement, easy loss of active components, and unstable catalytic activity. To achieve the effect of prolonging the service life, good catalytic performance and not easy to deactivate

Active Publication Date: 2017-11-07
NINGBO HAIYUE NEW MATERIAL
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The Chinese invention patent "A Method for Catalyzed Isobutane / N-Butene Alkylation with Solid Acid" (Application No.: 200910200242.4) with the authorized announcement number 101717321B discloses a method for preparing Nafion functionalized hydrophobic SBA-15 solid acid The preparation method of catalyzer, and it is applied to the alkylation reaction of isobutane and n-butene, and this catalyzer can obtain higher selectivity of trimethylpentane, but, in the reaction process, the conversion rate of butene needs further The improvement of the reaction stability also needs to be further strengthened
The Chinese invention patent application with publication number 1230463 "Solid Superacid Catalyst for Alkylation of Isobutane and Butene" (application number: 98116429.3) provides a kind of oxide with Ti, Zr, Hf and as the first auxiliary agent MoO 3 or WO 3 Four oxides composed of one of the oxides are used as supports, and transition metals Pt, Co, Fe, Mn, and Ni are introduced as active components by impregnation. The activity of the prepared catalyst is higher than that of SO 4 2- / ZrO 2 high, and C 8 The saturated hydrocarbon content can reach 75%, but the catalyst has the problems of easy loss of active components and unstable catalytic activity

Method used

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] The preparation method of the solid superacid catalyst for the alkylation of isobutane and butene of the present embodiment comprises the following steps:

[0021] (1) According to the molar ratio of Sc and Sn is 1:1, take Sc(NO 3 ) 3 Dissolve in deionized water, add SnSO to the system after complete dissolution 4 And stir evenly, then dropwise in this system successively 1-dodecyl-3-methylimidazolium bisulfate ionic liquid and the hydrogen peroxide solution whose mass concentration is 25wt%, and the pH that is regulated system with the ammoniacal liquor of 25wt% with concentration When the value reaches 8, put it aside for 10 hours for later use;

[0022] Among them, Sc(NO 3 ) 3 with SnSO 4 The molar ratio of the total amount to the amount of ionic liquid added is 1:0.1, Sc(NO 3 ) 3 with SnSO 4 The molar ratio of the total amount and the amount of hydrogen peroxide added is 1:0.8;

[0023] (2) Transfer the system obtained in step (1) to a hydrothermal reaction...

Embodiment 2

[0026] The preparation method of the solid superacid catalyst for the alkylation of isobutane and butene of the present embodiment comprises the following steps:

[0027] (1) According to the molar ratio of Sc to Sn of 1:5, take Sc(NO 3 ) 3 Dissolve in deionized water, add SnSO to the system after complete dissolution 4 and stir evenly, then sequentially add 1-butylpyridinium bisulfate ionic liquid and hydrogen peroxide solution with a mass concentration of 35wt% to the system dropwise, and adjust the pH value of the system to 10 with ammonia water with a concentration of 25wt%, and let it stand for 5h reserve;

[0028] Among them, Sc(NO 3 ) 3 with SnSO 4 The molar ratio of the total amount to the amount of ionic liquid added is 1:0.3, Sc(NO 3 ) 3 with SnSO 4 The molar ratio of the total amount of hydrogen peroxide to the added amount of hydrogen peroxide is 1:1.5;

[0029] (2) Transfer the system obtained in step (1) to a hydrothermal reaction kettle, and conduct cry...

Embodiment 3

[0032] The preparation method of the solid superacid catalyst for the alkylation of isobutane and butene of the present embodiment comprises the following steps:

[0033] (1) According to the molar ratio of Sc to Sn is 1:3, take Sc(NO 3 ) 3 Dissolve in deionized water, add SnSO to the system after complete dissolution 4and stir evenly, and then successively add 4-methylmorpholine bisulfate ionic liquid and a hydrogen peroxide solution with a mass concentration of 30wt% to the system dropwise, and adjust the pH value of the system to 9 with a mass concentration of 20wt% ammonia, and statically Set aside after 2h;

[0034] Among them, Sc(NO 3 ) 3 with SnSO 4 The molar ratio of the total amount to the amount of ionic liquid added is 1:0.2, Sc(NO 3 ) 3 with SnSO 4 The molar ratio of the total amount to the amount of hydrogen peroxide added is 1:1.0;

[0035] (2) Transfer the system obtained in step (1) to a hydrothermal reaction kettle, conduct crystallization treatment a...

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PUM

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Abstract

The invention relates to a method for preparing a solid superacid catalyst for the alkylation of isobutane and butene. The catalyst uses Sc2O3-SnO2 composite oxide with a mesoporous structure as a carrier and SO42-as an active component. The molar ratio of Sc and Sn in the catalyst is 1:(1-5). The present invention adopts bisulfate type ionic liquid when preparing catalyst, and the cation in this ionic liquid plays the effect of surfactant in water, forms strong interaction force with nanoparticle, induces nanoparticle to form morphology as template agent Regular and uniform mesoporous structure; the anion in the ionic liquid can be used as a precursor to provide SO42‑, and the addition of hydrogen peroxide ensures that the Sn in the product remains in the +4 valence state to form a solid superacid with SO42‑, and at the same time with the ionic liquid Work together and form complexes with metal ions, thereby strengthening the uniform distribution of SO42 on the catalyst, making the active components of the catalyst difficult to deactivate.

Description

technical field [0001] The invention relates to a preparation method of a solid superacid catalyst used for the alkylation of isobutane and butene. Background technique [0002] Alkylation of isobutane and butene to produce high-octane alkylated gasoline production process is one of the most important industrial applications of alkylation. Concentrated sulfuric acid and hydrofluoric acid are mainly used as catalysts in the alkylation process, which has the advantages of high yield of alkylated oil, good selectivity, good adaptability to various butenes, and mature process technology. Both of them have problems such as serious equipment corrosion and environmental pollution that are difficult to solve, which greatly limits their popularization and application. The discharge of waste acid in sulfuric acid alkylation process can reach 100Kg acid / t oil, and it is difficult to handle, causing serious damage to the environment; hydrofluoric acid in hydrofluoric acid alkylation pr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/053C07C2/62C07C9/21C07C9/16
Inventor 钱进张荣仿
Owner NINGBO HAIYUE NEW MATERIAL