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Catalyst for cracking methyl tert-butyl ether, preparation method and application thereof

A technology of methyl tert-butyl ether and catalyst, which is applied in the field of catalyst for cracking of methyl tert-butyl ether and its preparation and application, can solve the problems of increased by-products, high catalyst cost, and high requirements for heating equipment, and achieve Effects of high isobutene and methanol selectivity, catalyst cost reduction, and high equipment utilization

Active Publication Date: 2016-05-18
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The existing niobic acid system, such as JP6210603, uses pure niobic acid as the catalyst, when the LHSV is 4h -1 1. When the reaction temperature is 250°C, the conversion rate of MTBE is 99.2%. The increase of by-products will affect the purity of the product and increase the requirements and costs of product distillation

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 30 g γ-Al 2 o 3 Add to 40ml of 25% ammonia by weight for 2 hours, filter off the ammonia, wash in deionized water until the pH is about 8.5, dry the filter cake in an oven at 200°C for 3 hours; then soak the product in 100ml of 3% niobium oxalate Soak in the solution for 5 hours, filter, dry in an oven at 150°C for 4 hours, and bake at 650°C for 5 hours; then soak the product in 50ml of 3% sodium fluoride solution, soak for 5 hours, filter, and dry at 150°C Dry in an oven for 4 hours, and bake at 800°C for 5 hours.

[0026] The above catalyst was added to 50ml of 2% La(NO 3 ) 3 In the solution, the immersion time is 4 hours, after filtering, drying in an oven at 150°C for 4h, and roasting at 650°C for 5 hours; that is to obtain the multi-component La 2 o 3 / F / Nb 2 o 5 / Al 2 o 3 catalyst;

[0027] Put 20g of catalyst into a fixed-bed reactor with a diameter of Φ20mm, feed methyl tert-butyl ether with a liquid micro-sampling pump, and control the liquid space ve...

Embodiment 2

[0029] 30 g γ-Al 2 o 3 Add it to 40ml of 10% ammonia by weight for 1 hour, filter off the ammonia, wash it in deionized water until the pH is about 8.5, and dry the filter cake in an oven at 200°C for 3 hours; then soak the product in 100ml of 8% ammonium niobium oxalate solution, soaked for 5 hours, filtered, dried in an oven at 150°C for 4 hours, and baked at 650°C for 5 hours; then immersed the product in 50ml of 4% ammonium fluoride solution, soaked for 5 hours, filtered, and dried at 150°C Dry in an oven for 4 hours, and bake at 800°C for 5 hours.

[0030] The above catalyst was added to 50ml2% Ce(NO 3 ) 3 In the solution, the soaking time is 4 hours, after filtering, drying in an oven at 150°C for 4h, and roasting at 650°C for 5 hours, the multi-component Ce for preparing high-purity isobutene of the present invention is obtained 2 o 3 / F / Nb 2 o 5 / Al 2 o 3 catalyst;

[0031] Put 20g of catalyst into a fixed-bed reactor with a diameter of Φ20mm, feed methyl ter...

Embodiment 3

[0033] 30 g γ-Al 2 o 3 Add it to 40ml of ammonia water with a weight concentration of 20% for 0.5h, filter off the ammonia water, wash in deionized water until the pH is about 8.5, and dry the filter cake in an oven at 200°C for 3h; then soak the product in 100ml of 5% fluorinated Immerse in niobium salt solution for 5 hours, filter, dry in an oven at 150°C for 4 hours, and bake at 650°C for 5 hours; then immerse the product in 50ml of 5% hydrogen fluoride solution, soak for 5 hours, and filter Dry in an oven for 4 hours, and bake at 800°C for 5 hours.

[0034] The above catalyst was added to 50ml of 2% Sm(NO 3 ) 3 In the solution, the immersion time is 4 hours, after filtering, drying in an oven at 150°C for 4h, and roasting at 650°C for 5 hours, the multi-component Sm for preparing high-purity isobutene of the present invention is obtained. 2 o 3 / F / Nb 2 o 5 / Al 2 o 3 catalyst;

[0035] Put 20g of catalyst into a fixed-bed reactor with a diameter of Φ20mm, feed met...

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Abstract

The invention discloses a ZxOy / F / Nb2O5 / Al2O3 type solid acid catalyst for cracking methyl tertiary butyl ether to prepare high-purity isobutylene, and a preparation method of the catalyst. According to the preparation method, the catalyst comprises the following components in percentage by weight: 0.1-8 percent of ZxOy, 0.1-25 percent of F, 0.5-30 percent of Nb2O5 and 20-95 percent of Al2O3. Under the condition of ensuring high methyl tertiary butyl ether cracking conversion rate, the selectivity of the isobutylene and methyl alcohol nearly reaches 100 percent; meanwhile, inert matters such as water steam do not need to be added into a methyl tertiary butyl ether cracking reaction system, the reaction liquid space velocity of the catalyst is multiplied compared with the liquid space velocity of catalysts with the same type as that of the catalyst disclosed in the invetion, the energy consumption in the industrial production can be reduced, and the utilization rate of equipment is greatly improved.

Description

technical field [0001] The invention relates to the preparation and application of a catalyst for preparing high-purity isobutylene by cracking methyl tert-butyl ether, and mainly relates to a variety of active components loaded on Al 2 o 3 Z for the production of high-purity isobutene by cracking methyl tert-butyl ether x o y / F / Nb 2 o 5 / Al 2 o 3 type solid acid catalyst. Background technique [0002] Isobutene is widely used as an important chemical raw material. In recent decades, its social demand has been growing rapidly. It can not only be used to make gasoline and lubricating oil additives, but also can be used as an important auxiliary and raw material for other chemical products. For example, low-purity isobutylene is a raw material for antioxidants, pesticides, coatings, stabilizers and other fine chemicals. High-purity isobutylene is a monomer raw material for butyl rubber, isoprene rubber, polybutene resin, methyl methacrylate, etc. At the same time, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/125C07C11/09C07C1/20C07C31/04C07C29/00
CPCY02P20/52
Inventor 卢冠忠王筠松李运运朱耀国陆文龙郭杨龙郭耘王艳芹詹望成
Owner EAST CHINA UNIV OF SCI & TECH
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