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High-ethylene-selectivity catalyst for preparation of low carbon olefins from methanol

A low-carbon olefin and catalyst technology, applied in the field of special catalysts, can solve problems such as difficult operating conditions

Inactive Publication Date: 2018-01-26
任丘市华北石油科林环保有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, although methanol is currently used in MTO industrial units to produce low-carbon olefins special catalysts can effectively convert methanol into low-carbon olefins (C 2 ＝ ~C 4 ＝ ), but the ethylene / propylene (weight ratio) is only about 1.0
And practice has proved that it is very difficult to increase the ethylene / propylene (weight ratio) by adjusting and optimizing the operating conditions of the MTO industrial unit

Method used

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  • High-ethylene-selectivity catalyst for preparation of low carbon olefins from methanol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] Put de-cationic water and 10 kg of conventional SAPO molecular sieve (dry basis) into the stirred tank, beating and dispersing into a slurry with a solid content of 25% by weight. Sequentially add a zinc acetate aqueous solution containing 0.273 kg of ZnO and 0.54 kg of P to the slurry 2 O 5 Concentrated phosphoric acid, stir and disperse uniformly, heat up to 55°C and keep the temperature constant for 45 minutes, and then flash dry the mixed slurry. The dried product was calcined at 550°C for 60 minutes to obtain 2.5 wt% Zn modifier (calculated as ZnO) and 5.0 wt% P modifier (calculated as P 2 O 5 Calculated) modified silicon aluminum phosphate (SAPO) molecular sieve KSAPO-01.

Embodiment 2

[0065] Put de-cationic water and 10 kg of conventional SAPO molecular sieve (dry basis) into the stirred tank, beating and dispersing into a slurry with a solid content of 25% by weight. Sequentially add a zinc nitrate aqueous solution containing 0.43 kg ZnO and 0.268 kg P to the slurry 2 O 5 Stir and disperse the ammonium dihydrogen phosphate uniformly, raise the temperature to 55°C and keep the temperature constant for 45 minutes, and then flash dry the mixed slurry. The dried product was calcined at 550°C for 60 minutes to obtain 4.0 wt% Zn modifier (calculated as ZnO) and 2.5 wt% P modifier (calculated as P 2 O 5 Calculated) modified silicon aluminum phosphate (SAPO) molecular sieve KSAPO-02.

Embodiment 3

[0068] Take 5 kg (dry basis) of diatomaceous earth (as non-cohesive inorganic oxide or inorganic hydroxide (E)), be beaten with deionized water and dispersed into a slurry with a solid content of 30% by weight, and pumped into a ball mill for grinding , Until the particle size of more than 90% of the solid matter in the slurry <5.5μm.

[0069] Put 1.8 kg of decationized water, 0.05 kg (dry basis) acidic silica sol (as an inorganic binder), 0.4 kg (dry basis) modified silicon aluminum phosphate (SAPO) molecular sieve KSAPO-01, 0.1 kg in the stirred tank. (Dry basis) diatomaceous earth, 0.25 kg (dry basis) kaolin, 0.02 kg (dry basis) Zn(NO 3 ) 2 .6H 2 O and 0.1 kg (dry basis) pseudo-boehmite (as a binder), beating and dispersing for 120 minutes. Add 0.13 kg of concentrated phosphoric acid and continue beating for 60 minutes. Then, the obtained slurry was spray-dried at an inlet temperature of 500°C and an exhaust gas temperature of 180°C to prepare a molecular sieve KSAPO-01 conta...

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Abstract

The invention discloses a catalyst used for conversion of methanol for preparation of low carbon olefins (C2=-C4=). The catalyst is characterized by comprising, on a dry basis, 5 to 95 parts by weightof a modified silicoaluminophosphate (SAPO) molecular sieve, 4 to 50 parts by weight of an inorganic binder, 0.1 to 25 parts by weight of a Zn additive and 0.1 to 25 parts by weight of a phosphorus additive, and may optionally comprises 4 to 50 parts by weight of adhesion-free inorganic oxide or inorganic hydroxide and 1 to 60 parts by weight of clay, wherein the contents of the adhesion-free inorganic oxide or inorganic hydroxide, the inorganic binder, the Zn additive and the phosphorus additive are all calculated on in terms of oxide; and the Zn additive and the phosphorus additive do not contain Zn and P included in the modified silicoaluminophosphate (SAPO) molecular sieve. When the catalyst is applied to the process for preparation of low carbon olefins (C2=-C4=) through conversion of methanol, the catalyst can efficiently convert methanol into low carbon olefins (C2=-C4=), and in particular, the catalyst can greatly improve ethylene selectivity.

Description

Technical field [0001] The present invention relates to a kind of low-carbon olefins (C 2 ＝ ~C 4 ＝ ) The special catalyst for the process, more specifically, is about a kind of molecular sieve containing modified silicon aluminum phosphate (SAPO), non-binding silica, and Zn and P additives, which can effectively convert methanol into low-carbon olefins, especially high Ethylene selective catalyst. Background technique [0002] Light olefin (C 2 -C 4 ) Is an important organic chemical raw material. At present, there are many methods for producing low-carbon olefins. For example, using natural gas as a raw material to produce low-carbon olefins through steam cracking; using low-carbon alkane as a raw material to produce low-carbon olefins and hydrogen through catalytic dehydrogenation; using naphtha or diesel, etc. Light petroleum hydrocarbons are used as raw materials to produce low-carbon olefins through tubular thermal cracking; low-carbon olefins are produced by catalytic crac...

Claims

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Application Information

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IPC IPC(8): B01J29/85C07C1/20C07C11/04C07C11/06
CPCY02P20/52Y02P30/20Y02P30/40
Inventor 郭佳艺刘文香郭子愉郭艳楠闵浩飞
Owner 任丘市华北石油科林环保有限公司
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