Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof

A low-carbon olefin and catalyst technology, which is applied in the field of shaped molecular sieve catalyst and the preparation method of the catalyst, can solve the problems of low propylene selectivity, decreased propylene selectivity, poor catalyst stability and the like

Active Publication Date: 2010-01-20
DATANG INT CHEM TECH RESINST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In the prior art, the fixed-bed MTP process and the ZSM-5 catalyst in the process are disclosed. However, these catalysts generally have the disadvantages of low propylene selectivity, poor catalyst stability, and decreased propylene selectivity after molding.

Method used

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  • Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof
  • Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof
  • Molecular sieve catalyst for preparing low-carbon olefin and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Take 100g of ZSM-5 zeolite raw powder (SAR=200), add 25g of alumina, 2g of methyl cellulose and 3g of scallop powder to it, mix the above raw materials evenly, and adjust the liquid-solid ratio to 1.5mL of nitric acid / 2g of zeolite The mass percentage content is the nitric acid solution of 20% as peptizer, then adds 3.4gLa (NO 3 ) 3 ·6H 2 Heteroelement modifier for O. Other preparation steps were the same as in Comparative Example 1, and the obtained catalyst was marked as S-1, and the catalyst contained 1% La by mass percentage. S-1 was crushed, and 20-40 mesh particles were sieved for activity evaluation, and the reaction was mixed with methanol and water (mass ratio CH 3 OH:H 2 O=2:1), the activity evaluation result of catalyst is shown in table 1. The results of catalyst activity evaluation are shown in Table 1.

[0047] As shown in Table 1, under the same methanol conversion rate, the La modification of ZSM-5 zeolite is beneficial to improve the selectivity o...

Embodiment 2-11

[0052] Weigh 100g of sodium-type ZSM-5 zeolite with SAR of 300, 400, 500, 600 and 700 respectively for molding, add one or several different binders and pore structure regulators, and then add peptizer and heteroelement modification sex agent. The peptizers are respectively nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid or malonic acid, the amount of which is added according to the liquid-solid ratio of 1.5mL / 2g zeolite, the type and concentration of acid used for ion exchange, water vapor concentration and treatment The time is listed in Table 2. The heteroelement modifier is one or more of the soluble precursors containing Mg, P, In, Zn, Cu, Mn, Ga, Sr and Ca. The specific raw material ratio is as shown in Table 2, the other preparation steps of the shaped catalyst are the same as in Example 1. The reaction is mixed feed with dimethyl ether and water (mass ratio CH 3 OCH 3 :H 2 O=2:1), the activity evaluation result of catalyst i...

Embodiment 12

[0058] Take 100 g of ZSM-5 sodium zeolite raw powder (SAR=1000), add 2.0 g of turnip powder and 2.0 g of starch into it, and mix the above raw materials evenly to form a mixture. 3.4g La(NO 3 ) 3 ·6H 2 O was dissolved in 75 g of 33.3% by mass silica sol solution to form a mixed solution. Slowly add this mixed solution into the above mixture, mix evenly, extrude into Φ2×5mm strips, dry at 80°C for 12 hours at a constant temperature in an air atmosphere, and calcinate at 600°C for 5 hours. According to the amount of liquid-solid ratio of 10mL HCl / 1g zeolite, exchange 3 times with 4% HCl solution at 60° C. for 2 hours each time. Wash with deionized water and dry at 120°C to obtain H-ZSM-5 zeolite. The above-mentioned hydrogen-type zeolite was treated with H 2 O with 40% H by volume 2 O / N 2 The gas was treated at 600°C for 8 hours, and the obtained catalyst was crushed, and the reaction was mixed with dimethyl ether and water (mass ratio CH 3 OCH 3 :H 2 O=2:1), sieve out...

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Abstract

The invention provides a molecular sieve catalyst for preparing low-carbon olefin, and the catalyst comprises the following raw materials by parts by weight: 30-93.7 parts of Na-ZSM-5 zeolite, 5-40 parts of bonding agent, 0.1-10 parts of modifier of mixed elements, 1-15 parts of hole structure regulator and 0.1-5 parts of extrusion assistant, and the modifier of the mixed elements is a soluble substance containing one or a plurality of elements of B, P, La, Ca, Mg, Sr, Zn, Cu, Mn, Cd, Ga and In. The invention further provides a prepration method of the catalyst. The molecular sieve catalyst adopts the extrusion assistant and adds an appropriate amount of hole structure regulator, thereby improving product strength and hole structure, effectively improving diffusion performance of the catalyst and further improving selectivity of the low-carbon olefin. The catalyst has the advantages of appropriate strength, high hydrothermal stability, high activity and high selectivity of propylene.

Description

technical field [0001] The invention relates to a molecular sieve catalyst for preparing low-carbon olefins and a preparation method of the catalyst, in particular, the present invention relates to a shaped molecular sieve catalyst for converting methanol and / or dimethyl ether into low-carbon olefins and the preparation of the catalyst The preparation method belongs to the field of coal chemical industry. Background technique [0002] Low-carbon olefins are the most basic raw materials for petrochemical production and the basis for the production of other chemical products. At present, the production of low-carbon olefins is mainly based on petroleum routes and non-petroleum routes. The production of low-carbon olefins (methanol-to-olefins, MTO) such as ethylene and propylene from coal or natural gas via methanol and / or dimethyl ether is the most important non-petroleum resource technology route. In recent years, due to the rising oil price and the rapid growth of propylen...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/48B01J29/46B01J29/40B01J37/04B01J37/08C07C1/20C07C11/02
Inventor 李春启陈爱平梅长松李德炳忻仕河汪靖程晓维龙英才
Owner DATANG INT CHEM TECH RESINST
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