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Composite mould plate agent synthesized silicon-aluminum phosphate molecular sieve, production and uses thereof

A composite template, silicoaluminophosphate technology, applied in the field of molecular sieves, can solve the problems of fast catalyst deactivation rate, low selectivity of low-carbon olefins, low conversion rate of raw materials, etc., and achieves excellent catalytic performance, high selectivity, and easy industrialization. production effect

Active Publication Date: 2009-07-29
YANKUANG ENERGY R&D CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] CN1590295A In order to solve the problems of high synthesis cost of SAPO-34 molecular sieve in the prior art or the molecular sieve crystal grains obtained by synthesis are relatively large, and the relative crystallinity is low, SAPO-34 is prepared by using tetraethylammonium hydroxide and morpholine as a composite template Molecular sieve, and used in the reaction of methanol conversion to light olefins
[0008] However, these catalysts have many problems in the reaction of methanol to light olefins, such as low conversion rate of raw materials, fast catalyst deactivation rate, short life, low selectivity to light olefins, etc.

Method used

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  • Composite mould plate agent synthesized silicon-aluminum phosphate molecular sieve, production and uses thereof
  • Composite mould plate agent synthesized silicon-aluminum phosphate molecular sieve, production and uses thereof
  • Composite mould plate agent synthesized silicon-aluminum phosphate molecular sieve, production and uses thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～4 and comparative example 1～2

[0031] Composite template agent synthesizes the preparation of silicoaluminophosphate molecular sieve (SAPO-34 molecular sieve), specifically as follows:

[0032] (1) According to the ratio: 0.4Al 2 o 3 : 0.4P 2 o 5 : 0.2SiO2 2 :2xTEAOH:2(1-x)DEA:53H 2 O takes raw material, and x value is as shown in table 1:

[0033] Table 1 Molecular sieve synthesis experiment results

[0034]

[0035] (2) Mix pseudo-boehmite, phosphoric acid, and deionized water, and fully stir for a certain period of time until uniform;

[0036] (3) Add 30% silica sol, and after fully stirring, slowly add the composite template agent 20% TEAOH and diethylamine into the mixture successively, and then fully stir for a certain period of time to form a gel;

[0037] (4) Move the prepared gel into a high-pressure titanium alloy reactor, seal it, and keep stirring under its own pressure to crystallize with temperature programming, crystallize at 110°C for 24 hours, and crystallize at 200°C for 72 hours...

Embodiment 5

[0044] SAPO-34 molecular sieve is used as a catalyst in the reaction of methanol to olefins, as follows:

[0045] (1) Preparation of SAPO-34 molecular sieve catalyst

[0046]The silicoaluminophosphate molecular sieve raw powders S01, S02, S03, S04, S05, and S06 synthesized in Examples 1 to 4 and Comparative Examples 1 to 2 were roasted at 550° C. for 4.0 hours to remove the template agent, cooled to room temperature, and respectively After tableting and crushing, molecular sieve particles with a particle size of 80-100 mesh are sieved, and they are sequentially numbered as C01, C02, C03, C04, C05, and C06 catalysts, pending evaluation;

[0047] (2) Evaluation reaction of SAPO-34 molecular sieve catalyst

[0048] A fixed-bed catalytic reaction device is adopted, and the reactor is a stainless steel tube. The catalysts C01, C02, C03, C04, C05, and C06 prepared by the above steps are respectively evaluated for MTO reactivity. The process conditions used for the evaluation are: c...

Embodiment 6

[0054] The preparation of SAPO-34 molecular sieve is as follows:

[0055] (1) According to the ratio: 0.005Al 2 o 3 : 0.005P 2 o 5 : 0.01SiO2 2 : 0.2xTEAOH : 0.2(1-x)DEA : 10H 2 O takes the raw material, x=0.5;

[0056] (2) Mix aluminum isopropoxide, phosphoric acid, and deionized water, and stir thoroughly for a certain period of time until uniform;

[0057] (3) Add active silicon dioxide, after fully stirring, slowly add the composite template agent 20% TEAOH and diethylamine into the mixture successively, and then fully stir for a certain period of time to form a gel;

[0058] (4) Move the prepared gel into a high-pressure titanium alloy reactor, seal it, and keep stirring under its own pressure to crystallize with temperature programming, crystallize at 70°C for 24 hours, and crystallize at 150°C for 100 hours;

[0059] (5) Take out the solid product, wash it repeatedly with deionized water to neutrality, place it in a drying oven and dry it at 50°C for 8 hours to o...

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Abstract

The invention relates to a silicon-aluminium phosphate molecular sieve synthesized by a composite template agent, and a preparation method and application thereof. The structural formula of the molecular sieve is (0.2-3.0)R: (Si0.1-0.3Al0.1-1P0.01-0.9): (10-400)H2O, wherein R is a tetraethyl ammonium hydroxide / diethylamine composite template agent, and the composite template agent is x tetraethyl ammonium hydroxide+(1-x) diethylamine, wherein x is equal to between 0 and 1. Compared with the prior art, the composite template agent (tetraethyl ammonium hydroxide / diethylamine) has low synthesis cost for synthesizing the silicon-aluminium phosphate molecular sieve and is easy for industrial production, and when used as a catalyst in the preparation of low-carbon olefin from methanol, the template agent has slow reaction cocking rate and deactivation rate, and long activity time and service life, and has the advantages of high feed stock conversion, high selectivity for low-carbon alkene such as ethylene, propylene, and the like.

Description

technical field [0001] The invention relates to molecular sieves, in particular to a composite template agent for synthesizing silicoaluminophosphate molecular sieves and a preparation method and application thereof. Background technique [0002] Low-carbon olefins, especially ethylene and propylene, as basic organic chemical raw materials, play a pivotal role in modern petroleum and chemical industries. The production methods of olefins can be divided into two categories: one is the petroleum route, and the other is the non-petroleum route. However, for the oil route, the price of oil has continued to rise for a long time, the supply is unstable, and the resource reserves are limited. Therefore, it is not enough to increase the production of ethylene and propylene by relying on the traditional oil route. [0003] Methanol-to-Olefins (MTO for short) is a process in which coal or natural gas is used as raw material to produce ethylene, propylene and other low-carbon olefins ...

Claims

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Application Information

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IPC IPC(8): C01B39/54C01B37/08B01J29/85C07C1/20C07C11/02
CPCY02P20/52Y02P30/20Y02P30/40
Inventor 孙启文应卫勇张宗森曹发海刘继森李涛房鼎业叶丽萍胡浩王义君
Owner YANKUANG ENERGY R&D CO LTD
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