Catalyst for converting alcohols and ethers into aromatic hydrocarbons as well as preparation method and use method thereof

A technology of catalysts and aromatics, applied in the field of catalysts, can solve the problems of reduced catalyst space velocity, no aromatics process, increased wear rate, etc., and achieve the effects of reduced waste water, increased production intensity, and low carbon deposition

Active Publication Date: 2013-04-03
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The activity of this type of catalyst decreases to less than 90% of the maximum activity within 1 hour, so frequent reaction regeneration is required
Catalyst transport at different temperatures and in different reactors can lead to a decrease in its strength and an increase in attrition rate
If a large amount of structural enhancer is used, the overall strength of the catalyst will be improved, but the ratio of active ingredients (such as molecular sieves and metals) in the catalyst will decrease, the space velocity of the catalyst will decrease, the amount of use will be greatly increased, and the cost will also increase
Although it has been reported to use ZSM-5 molecular sieves into nanoparticles (approximately spherical) for methanol to propylene and other processes, there is no report on the direct production of aromatics from methanol
At the same time, ZSM-5 molecular sieve nanoparticles that are too small are difficult to filter, have a large loss rate, and have high preparation costs

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] (1) Treat kaolin with 0.2 mol / L hydrochloric acid at 120°C for 48 hours, then filter and dry;

[0045] (2) Mix the above-mentioned treated kaolin, ethylenediamine, sodium hydroxide, and water in a mass ratio of 0.5:0.1:0.1:40, and age at room temperature for 48 hours; then transfer it to a hydrothermal kettle in 220°C and 10rpm for 1 day; the obtained precipitate was washed several times, filtered and dried at 110°C for 24 hours; then roasted at 550°C for 6 hours to obtain sodium nano-sized ZSM-5 Molecular sieve;

[0046] (3) The sodium-type nano-sized ZSM-5 molecular sieve obtained in step (2) was mixed with 1mol / L NH at 80°C 4 NO 3 Carry out 3 times of exchange treatment; the time of each exchange treatment is 4 hours, after each exchange treatment, it is dried at 110°C for 14 hours; then it is roasted at 550°C for 6 hours to obtain hydrogen-type needle-shaped nano ZSM-5 molecular sieve, It has a diameter of 5nm, a length of 0.1μm, and a Si / Al ratio of 12.5;

[00...

Embodiment 2

[0051] (1) Treat kaolin with 6mol / L hydrochloric acid at 25°C for 1 hour, then filter and dry;

[0052] (2) After mixing the above-mentioned treated kaolin, ethylenediamine, sodium hydroxide, and water in a mass ratio of 9:4:0.5:40, age at room temperature for 0h; then move it into a hydrothermal kettle, Treated at 150°C and 30rpm for 6 days; washed and filtered the obtained precipitate several times and dried at 110°C for 12 hours; then roasted at 500°C for 3 hours to obtain sodium nano-sized ZSM-5 molecular sieve;

[0053] (3) The sodium-type nano-sized ZSM-5 molecular sieve obtained in step (2) was mixed with 1mol / L NH at 80°C 4 NO 3 Carry out 3 times of exchange treatment; the time of each exchange treatment is 4 hours, and after each exchange treatment, dry at 110 ° C for 24 hours; then roast at 550 ° C for 3 hours to obtain hydrogen-type needle-shaped nano ZSM-5 molecular sieves, It has a diameter of 50nm, a length of 5μm, and a Si / Al ratio of 20;

[0054] (4) Immerse...

Embodiment 3

[0058] (1) Treat kaolin with 1mol / L hydrochloric acid at 50°C for 12 hours, then filter and dry;

[0059] (2) Mix the above-mentioned treated kaolin, n-butylamine, sodium hydroxide, and water in a mass ratio of 1:1:0.2:40, and age at room temperature for 4 hours; Treat at 200°C and 20rpm for 6 days; wash and filter the obtained precipitate several times, and then dry at 110°C for 18 hours; then roast at 450°C for 3 hours to obtain sodium nano-sized ZSM-5 molecular sieve;

[0060] (3) The sodium-type nano-sized ZSM-5 molecular sieve obtained in step (2) was mixed with 1mol / L NH at 80°C 4 NO 3 Carry out 3 times of exchange treatment; the time of each exchange treatment is 4 hours, after each exchange treatment, dry at 110°C for 12 hours; then roast at 550°C for 3 hours to obtain hydrogen-type needle-shaped nano ZSM-5 molecular sieve, It has a diameter of 10nm, a length of 10μm, and a Si / Al ratio of 50;

[0061] (4) Mix and impregnate 1mol / L zinc nitrate solution, 0.02mol / L ce...

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Abstract

The invention discloses a catalyst for converting alcohols and ethers into aromatic hydrocarbons, as well as a preparation method and a use method of the catalyst, and belongs to the technical field of chemical engineering. The preparation method comprises the steps as follows: at first, taking a template agent, kaolin, sodium hydroxide and water as raw materials for preparing a hydrogen type nanoscale ZSM-5 molecular sieve, and then directly preparing the catalyst; or based on the hydrogen type nanoscale ZSM-5 molecular sieve, preparing the two-component, three-component or four-component catalyst with metal and/or a structure enhancer and/or a stabilizing additive. The catalyst comprises the following components in percentage by mass: 30-100% of the needle-like nanoscale ZSM-5 molecular sieve, 0-10% of the metal, 0-50% of the structure enhancer and 0-10% of the stabilizing additive. The invention further provides a method for enabling the catalyst to be used for converting alcohols and ethers into aromatic hydrocarbons. The catalyst is small in particle size, high in catalytic efficiency and low in use cost; the preparation method is simple and efficient; and the use method is reasonable and efficient.

Description

technical field [0001] The invention belongs to the technical field of chemical industry, in particular to a catalyst for converting alcohols and ethers into aromatic hydrocarbons and its preparation and use methods. Background technique [0002] Aromatics are one of the most important basic chemicals. In the traditional chemical route, aromatics are mainly obtained from petroleum refining and coal dry distillation. The aromatic hydrocarbons obtained by the petroleum route have high purity and are suitable for the preparation of various high-quality chemicals. The aromatics obtained by the coal (carbonization) route contain thiophene impurities, the quality is relatively low, and the application is limited. With the increasing shortage of petroleum resources, the supply of aromatics is tense, and the price remains high, which greatly increases the production of subsequent chemicals. costs, affecting sales. The use of natural gas (mainly composed of methane) or petroleum re...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/40B01J29/46B01J29/48C07C1/20C07C15/02
Inventor 骞伟中沈葵张金贵魏飞
Owner TSINGHUA UNIV
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