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An n-butylene isomerization catalyst and a preparing method thereof

A catalyst and isomerization technology, which is applied in the field of n-butene isomerization catalyst and its preparation, can solve the problem that the output of isobutene cannot meet the industrial demand, etc., and achieve the effects of shortening the crystallization time, high catalytic activity, and simple preparation method

Active Publication Date: 2014-12-03
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In recent years, due to the sharp increase in the demand for isobutene, especially for the production of MTBE, an environmentally friendly gasoline additive, the demand for isobutene has grown rapidly around the world, and the isobutene output obtained by the traditional petroleum catalytic cracking process is far from meeting industrial needs. Therefore, Research and development of new technologies for isobutene production have been carried out extensively at home and abroad

Method used

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  • An n-butylene isomerization catalyst and a preparing method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] 1) Preparation of SAPO-11 / SAPO-46 composite molecular sieve

[0032] Weigh 9.52g (0.07mol) of pseudo-boehmite, dissolve it in 10g of deionized water to prepare a pseudo-boehmite aqueous solution, and stir for 0.5h. 16.14g (0.14mol) of H 3 PO 4 (85% by weight aqueous solution), and stirred for 1h. Measure 4.78ml (0.035mol) of di-n-propylamine and add it dropwise to the above solution, and stir for 1h. Next, 10.08 g (0.042 mol) of silica sol was weighed and added to the above solution. Add water and stir for 1h to obtain a colloidal mixture, in which the number of moles of Al 2 o 3 :R:P 2 o 5 :SiO2 2 :H 2 O=1:0.5:1:0.6:50, wherein R is di-n-propylamine.

[0033] The colloidal mixture prepared above was aged at 80°C for 4h, then heated to 180°C, and hydrothermally crystallized under autogenous pressure for 22h. The crystallized product was cooled, washed by centrifugation, and then dried at 120°C for 12h. Obtain SAPO-11 / SAPO-46 composite molecular sieve, its X-...

Embodiment 2

[0040] 1) Preparation of SAPO-11 / SAPO-46 composite molecular sieve

[0041] Weigh 9.52g (0.07mol) of pseudo-boehmite, dissolve it in 10g of deionized water to prepare a pseudo-boehmite aqueous solution, and stir for 0.5h. 16.14g (0.14mol) of H 3 PO 4 (85% by weight aqueous solution), and stirred for 1h. Measure 7.64ml (0.056mol) of di-n-propylamine and add it dropwise to the above solution, and stir for 1h. Next, 10.08 g (0.042 mol) of silica sol was weighed and added to the above solution. Add water and stir for 1h to obtain a colloidal mixture, in which the number of moles of Al 2 o 3 :R:P 2 o 5 :SiO2 2 :H 2 O=1:0.8:1:0.6:40, wherein R is di-n-propylamine.

[0042] The colloidal mixture prepared above was aged at 100°C for 3h, then heated to 180°C, and hydrothermally crystallized under autogenous pressure for 12h. The crystallized product was cooled, washed by centrifugation, and then dried at 110° C. for 12 hours to obtain a SAPO-11 / SAPO-46 composite molecular si...

Embodiment 3

[0049] 1) Preparation of SAPO-11 / SAPO-46 composite molecular sieve

[0050] Weigh 9.52g (0.07mol) of pseudo-boehmite, dissolve it in 10g of deionized water to prepare a pseudo-boehmite aqueous solution, and stir for 0.5h. 16.14g (0.14mol) of H 3 PO 4 (85% by weight aqueous solution), and then stirred for 1 h; measure 14.3 ml (0.105 mol) of di-n-propylamine and added dropwise to the above solution, and stirred for 1 h. Then weigh 13.44 g (0.056 mol) of silica sol and add it into the above solution. Add water and stir for 1h to obtain a colloidal mixture, in which the number of moles of Al 2 o 3 :R:P 2 o 5 :SiO2 2 :H 2 O=1:1.5:1:0.8:50, wherein R is di-n-propylamine.

[0051] The colloidal mixture prepared above was aged at 110°C for 4h, then heated to 180°C, and hydrothermally crystallized under autogenous pressure for 8h. The crystallized product was cooled, washed by centrifugation, and then dried at 120° C. for 6 hours to obtain a SAPO-11 / SAPO-46 composite molecula...

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Abstract

An n-butylene isomerization catalyst is provided. An SAPO-11 / SAPO-46 composite molecular sieve with multistage pore channels is adopted as a carrier. A VIB-group metal is adopted as an active component. A preparing method of the catalyst is also provided. The method includes: controlling a raw material ratio in a synthetic process, preparing the SAPO-11 / SAPO-46 composite molecular sieve by adoption of a proper crystallization manner and a proper crystallization temperature, and loading the VIB-group metal (such as chromium or molybdenum) to make the catalyst a bifunctional catalyst with the metal and an acid center. The preparing method is simple, low in cost and suitable for industrial production. The catalyst is high in catalytic activity and isobutylene selectivity when the catalyst is used for isobutylene preparation by n-butylene skeletal isomerization.

Description

technical field [0001] The invention relates to the field of olefin isomerization catalysts, in particular to a n-butene isomerization catalyst and a preparation method thereof. Background technique [0002] Isobutylene is an important organic chemical raw material, mainly used to produce methyl tert-butyl ether (MTBE), tert-butanol, butyl rubber, polyisobutylene, methyl methacrylate, tert-butyl mercaptan and other organic Chemical Products. In recent years, due to the sharp increase in the demand for isobutene, especially for the production of MTBE, an environmentally friendly gasoline additive, the demand for isobutene has grown rapidly around the world, and the isobutene output obtained by the traditional petroleum catalytic cracking process is far from meeting industrial needs. Therefore, Research and development of new technologies for isobutylene production have been carried out extensively at home and abroad. [0003] In the 1970s and 1980s, the n-butene isomerizati...

Claims

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Application Information

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IPC IPC(8): B01J29/85C07C5/27C07C11/09
Inventor 张利霞任行涛刘艳惠杨光裴庆君
Owner CHINA PETROLEUM & CHEM CORP
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