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Catalyst for producing light olefins through methanol and preparation method thereof

A low-carbon olefin and catalyst technology, which is applied in the field of catalyst and its preparation, can solve the problems of increasing catalyst wear, reducing service life, poor olefin selectivity, etc., and achieves the effects of improving methanol conversion rate, long service life and high catalytic activity

Inactive Publication Date: 2010-06-23
BEIJING UNIV OF CHEM TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, there are mainly three types of catalysts suitable for the MTO process: 1) SAPO-34 molecular sieve (model MTO-100), but because the catalyst needs frequent regeneration, the MTO process must use a continuous reaction-regeneration fluidized bed reactor to increase the catalyst 2) ZSM-5 zeolite catalyst, low coking, no need for continuous regeneration, long life, but relatively poor olefin selectivity; 3) DO-123 catalyst, the main raw material is dimethyl ether, the Catalysts have problems such as short service life and high preparation costs

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1) Weigh 5g of ZSM-5 carrier, degas and dehydrate, and evacuate for 3h, the vacuum degree reaches 650mm between the two ends of the U-shaped pressure gauge;

[0020] 2) Prepare 10.5ml 1g / L NiNO 3 Solution, prepare 3ml 10g / L Zn(NO 3 ) 2 Solution, prepare 2.5ml 10g / L LiNO 3 After the solution, prepare 1ml H 3 PO 4 Solution, mix the four;

[0021] 3) Add the mixed solution prepared in step 2) to the carrier vacuumed in step 1), stir for 18 hours, then shake to dryness in a water bath at 50°C, and then calcinate at 600°C for 2 hours to obtain a low-carbon olefin from methanol. catalyst.

[0022] The catalyst is used in the reaction of methanol conversion to low-carbon olefins: the methanol conversion rate is 98.87%, and the carbon-based selectivity of each product in the gas phase product is C 1 0 2.87%, C 2 0 0.05%, C 2 ＝ 36.44%, C 3 0 2.10%, C 3 ＝ 35.07%, C 4 ＝ 6.10%, C 4 ＝ 17.36%, C 2 ＝ ~C 4 ＝ 88.87%, C in the liquid product 5 + Accounts for 3.05%, the rest is water.

Embodiment 2

[0024] 1) Weigh 5g of SAPO-34 carrier, degas and dehydrate, and vacuum for 2h, the vacuum degree reaches 720mm between the two ends of the U-shaped pressure gauge;

[0025] 2) Prepare 4.1ml 10g / L Ca(NO 3 ) 2 Solution, prepare 1.2ml 1g / L Na 2 CO 3 Solution, prepare 9.86ml 1g / L LiNO 3 After the solution, prepare 3.1ml 10g / L Mn(NO 3 ) 2 The solution mixes the four;

[0026] 3) Add the mixed solution prepared in step 2) to the carrier vacuumed in step 1), stir for 24 hours, then shake to dryness in a water bath at 45°C, and then calcinate at 500°C for 3 hours to obtain a low-carbon olefin from methanol. catalyst.

[0027] The catalyst is used in the reaction of methanol conversion to low-carbon olefins: the methanol conversion rate is 97.25%, and the carbon-based selectivity of each product in the gas phase product is C 1 0 2.57%, C 2 0 0.04%, C 2 ＝ 39.63%, C 3 0 1.88%, C 3 ＝ 35.34%, C 4 0 6.61%, C 4 ＝ 13.93%, C 2 ＝ ~C 4 ＝ 88.90%, C in the liquid product 5 + Accounts for 2.24%, the rest ...

Embodiment 3

[0029] 1) Weigh 5g of MCM-41 carrier, degas and dehydrate, vacuum for 4h, and the vacuum degree reaches 600mm between the two ends of the U-shaped pressure gauge;

[0030] 2) Prepare 7.3ml 10g / L Cu(NO 3 ) 2 Solution, prepare 8.8ml 10g / L K 2 CO 3 After the solution, prepare 10.8ml 20g / L Fe(NO 3 ) 3 Solution, mix the three;

[0031] 3) Add the mixed solution prepared in step 2) to the carrier vacuumed in step 1), stir for 12 hours, shake in a water bath at 50°C to dryness, and then calcinate at 400°C for 3 hours to obtain a methanol-to-low-carbon olefin catalyst.

[0032] The catalyst is used in the reaction of methanol conversion to low-carbon olefins: the methanol conversion rate is 94.89%, and the carbon-based selectivity of each product in the gas phase product is C 1 0 2.04%, C 2 0 0.26%, C 2 ＝ 35.79%, C 3 0 1.87%, C 3 ＝ 36.26%, C 4 0 6.34%, C 4 ＝ 17.43%, C 2 ＝ ~C 4 ＝ 89.48%, C in the liquid product 5 + Accounted for 2.04%, the rest is water.

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Abstract

The invention discloses a catalyst for producing light olefins through methanol and preparation method thereof which belongs to the field of coal chemical industry. The current catalyst for producing light olefins through methanol needs to be frequently regenerated under a reaction temperature, and has the disadvantages of short service life, high cost of manufacture and complex preparation process. The catalyst proposed in the invention consists of 95-99.99 wt percent of carrier and 0.01-5wt percent of active components. The invention adopts a vacuum impregnation method to load metal components and solid acid onto the carrier, dry and calcine to obtain the catalyst for producing light olefins through methanol. The invention has the advantages of high catalytic activity, high selection onlight olefins, gentle reaction conditions, low coking, long service life, simple preparation process, being suitable for forming carrier beneficial to industrialization, and low cost, etc.

Description

Technical field [0001] The invention belongs to the field of coal chemical industry, and specifically relates to a catalyst for preparing low-carbon olefins from methanol and a preparation method thereof. Background technique [0002] As important basic raw materials in modern chemical industry, ethylene and propylene are in great demand. Ethylene is mainly obtained through steam cracking of light hydrocarbons and naphtha. Propylene is mainly obtained from steam cracking units for ethylene production and catalytic cracking units for oil refining. However, because oil is a non-renewable resource, countries around the world have begun to devote themselves to the development of non-petroleum routes to produce ethylene and propylene low-carbon olefins. Among them, the process route of converting coal or natural gas into methanol via synthesis gas and then converting methanol into low-carbon olefins has received extensive attention. For the methanol to light olefin (MTO) process, th...

Claims

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Application Information

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IPC IPC(8): B01J29/064B01J29/85B01J29/46B01J23/06B01J23/78C07C1/20
CPCY02P20/52
Inventor 张敬畅张雷杨秀英佟春梅曹维良
Owner BEIJING UNIV OF CHEM TECH
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