A molecular sieve catalyst for preparing low-carbon olefins and its preparation method

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: 2011-12-14
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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  • A molecular sieve catalyst for preparing low-carbon olefins and its preparation method
  • A molecular sieve catalyst for preparing low-carbon olefins and its preparation method
  • A molecular sieve catalyst for preparing low-carbon olefins and its preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Take 100g of ZSM-5 zeolite powder (SAR=200), add 25g alumina, 2g methylcellulose and 3g sesame powder to it, mix the above raw materials uniformly, and set the liquid-solid ratio to 1.5mL nitric acid / 2g zeolite The mass percentage of 20% nitric acid solution is used as peptizer, and then 3.4g La(NO 3 ) 3 ·6H 2 O's miscellaneous element modifier. The other preparation steps are the same as in Comparative Example 1, and the obtained catalyst is labeled S-1, and the catalyst contains 1% La by mass percentage. S-1 was crushed, and particles of 20-40 mesh were screened out for activity evaluation. The reaction was fed with a mixture of methanol and water (mass ratio CH 3 OH: H 2 O=2:1), the catalyst activity evaluation results are shown in Table 1. The catalyst activity evaluation results are shown in Table 1.

[0047] As shown in Table 1, under the conditions of the same methanol conversion rate, the La modification of ZSM-5 zeolite is beneficial to increase 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 more different binders and pore structure modifiers, and then add peptizer and miscellaneous element modification Sex agent. The peptizer is nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid or malonic acid, and the amount added is based on 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 specifically listed in Table 2. The miscellaneous element modifier is one or more of soluble precursors containing Mg, P, In, Zn, Cu, Mn, Ga, Sr and Ca. As shown in 2, the other preparation steps of the shaped catalyst are the same as in Example 1. The reaction is fed with a mixture of dimethyl ether and water (mass ratio CH 3 OCH 3 : H 2 O=2:1), the catalyst activity evaluation results are shown in Table 2.

[0053] Table 2 The ra...

Embodiment 12

[0057] Take 100g of ZSM-5 sodium zeolite powder (SAR=1000), add 2.0g sesame powder and 2.0g starch to it, mix the above raw materials uniformly to form a mixture. Put 3.4g La(NO 3 ) 3 ·6H 2 O is dissolved in 75 g of a silica sol solution with a mass percentage of 33.3% to form a mixed solution. This mixed solution was slowly added to the above mixture, mixed uniformly, and extruded into a Φ2×5mm strip, dried at 80°C under constant temperature in air atmosphere for 12h, and calcined at 600°C for 5h. According to the liquid-to-solid ratio of 10mLHCl / 1g zeolite, the HCl solution with a mass percentage of 4% was exchanged 3 times at 60°C, each for 2h. Wash with deionized water and dry at 120°C to obtain H-ZSM-5 zeolite. Use H 2 O volume percentage of H is 40% 2 O / N 2 The gas is treated at 600°C for 8 hours, the catalyst obtained is broken, and the reaction is mixed with dimethyl ether and water as feed (mass ratio CH 3 OCH 3 : H 2 O=2:1), sieving out 20-40 mesh particles for activ...

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Abstract

The invention provides a molecular sieve catalyst for preparing low-carbon olefins. In parts by weight, the catalyst is made of raw materials comprising the following components: 30-93.7 parts of sodium ZSM-5 zeolite, 5-40 parts of Adhesive, 0.1-10 parts of heteroelement modifier, 1-15 parts of pore structure modifier and 0.1-5 parts of extrusion aid, and the heteroelement modifier contains B, P, La , Ca, Mg, Sr, Zn, Cu, Mn, Cd, Ga and In the soluble matter of one or more elements. The invention also provides a preparation method of the catalyst. In the present invention, the extrusion aid is used and an appropriate amount of pore structure regulator is added to improve the strength and pore structure of the product, effectively improve the diffusion performance of the catalyst, and thereby increase the selectivity of low-carbon olefins. The catalyst of the invention has suitable strength and high hydrothermal stability, and exhibits high activity and selectivity to propylene.

Description

Technical field [0001] The present invention relates to a molecular sieve catalyst for preparing low-carbon olefins and a method for preparing such catalysts. Specifically, the present invention relates to a shaped molecular sieve catalyst that converts methanol and / or dimethyl ether into low-carbon olefins and the preparation method of such catalysts. The preparation method belongs to the field of coal chemical industry. Background technique [0002] Low-carbon olefins are the most basic raw material for petrochemical production and the basis for the production of other chemical products. At present, low-carbon olefins are mainly produced through petroleum routes and non-petroleum routes. The production of ethylene, propylene and other low-carbon olefins (methanol-to-olefin, MTO) from coal or natural gas through methanol and / or dimethyl ether is the most important non-oil resource technology route. In recent years, due to the continuous increase in oil prices and the rapid inc...

Claims

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Application Information

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Patent Type & Authority Patents(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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