Method for preparing low-carbon olefins through co-catalytic cracking of Fischer-Tropsch synthesis light oil and methyl alcohol

A technology of Fischer-Tropsch synthesis and catalytic cracking, which is applied in the direction of hydrocarbon cracking to produce hydrocarbons, carbon compound catalysts, chemical instruments and methods, etc. It can solve the problems of low selective yield of low-carbon olefins, economics, and industrial implementation and gaps. , to achieve the effect of efficiently obtaining

Active Publication Date: 2018-07-13
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] In patents CN200710121425 and CN200710121426, Sinopec also proposed methanol (dimethyl ether) and C 4 and C 4+ The co-cracking method of olefins adopts SAPO-34, ZSM-5 or the mixture of the two as a catalyst. Although the purpose of its thermal coupling

Method used

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  • Method for preparing low-carbon olefins through co-catalytic cracking of Fischer-Tropsch synthesis light oil and methyl alcohol
  • Method for preparing low-carbon olefins through co-catalytic cracking of Fischer-Tropsch synthesis light oil and methyl alcohol
  • Method for preparing low-carbon olefins through co-catalytic cracking of Fischer-Tropsch synthesis light oil and methyl alcohol

Examples

Experimental program
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Effect test

Embodiment 1

[0033] This example considers the C in the distillate oil 6 Higher olefin model compound 1-hexene and methanol co-catalyzed cracking reaction. The catalyst is a commercially modified ZSM-5 molecular sieve catalyst (from Nankai Catalyst Factory), with a particle size of 0.28-0.45 mm (corresponding to 40-60 mesh). The catalytic cracking process uses The quartz glass tubular micro-fixed bed reactor adopts electric heating PID temperature control, and the temperature control accuracy is ±0.5°C.

[0034] First mix 0.25g of modified ZSM-5 molecular sieve catalyst (ZSM-5 molecular sieve content is 30wt%) with 1.75g ​​of quartz sand (as a packed bed inert filler) and then load it into the constant temperature section of the reactor, and then fill the catalyst with quartz wool And quartz sand, a thermocouple is inserted into the bed to measure the temperature.

[0035] The catalytic cracking process adopts mixed feeding of hexene and methanol aqueous solution, the concentration o...

Embodiment 2

[0046] This example considers the C in the distillate oil 7 Higher olefin model compound 1-heptene and methanol co-catalyzed cracking reaction. The modified ZSM-5 molecular sieve catalyst is adopted, and the loading amount of the fixed-bed catalyst is also consistent with that of Example 1, which is 0.25 g.

[0047] 1-heptene and methanol aqueous solution are used as mixed feed, the concentration of methanol in the methanol aqueous solution is 16.0 wt%, and 1-heptene is an analytically pure raw material. Liquid phase raw material 1-heptene and aqueous methanol solution are metered with high-pressure constant-flow pump respectively, and 1-heptene feed mass flow rate is 11.76g / hour, and 16.0wt% methanol aqueous solution feed mass flow rate is 12.0g / hour (feeding high The molar ratio of carbon olefins to methanol is 2.0), and at the same time, 3.0L / hour of high-purity nitrogen is introduced as a diluent gas. The catalytic cracking temperature is 500°C.

[0048] One hour afte...

Embodiment 3

[0050] This example considers C 8 Cocatalyzed Cracking Reaction of Higher Olefin 1-Octene and Methanol. The conditions of the modified ZSM-5 molecular sieve catalyst used and the loading amount of the catalyst were the same as in Example 1, and the catalytic cracking reaction temperature was 490°C. 1-heptene and methanol aqueous solution are used as mixed feed, the concentration of methanol in the methanol aqueous solution is 16.0 wt%, and 1-octene is an analytically pure raw material.

[0051] Liquid phase raw material 1-octene and aqueous methanol solution are metered with high-pressure constant-flow pump respectively, and 1-octene feed mass flow rate is 13.44g / hour, and 16.0wt% methanol aqueous solution feed mass flow rate is 12.0g / hour (feeding high The molar ratio of carbon olefins to methanol is 2.0), and at the same time, 3.0L / hour of high-purity nitrogen is introduced as a diluent gas.

[0052] One hour after the start of the reaction, the reaction product was samp...

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Abstract

The invention discloses a method for preparing low-carbon olefins through co-catalytic cracking of Fischer-Tropsch synthesis light oil and methyl alcohol. The method comprises the steps of mixing andfeeding the Fischer-Tropsch synthesis light oil and a methyl alcohol water solution; feeding into a heterogeneous reactor containing a molecular-sieve-based catalysts bed for carrying out catalytic cracking reaction; after the cracking reaction, carrying out gas-phase recovery to obtain C2-C5 low-carbon olefin products. By adopting the method, Fischer-Tropsch synthesis light oil catalytic crackingreaction absorbing heat and methanol conversion reaction releasing heat can be thermally coupled, a heat-supplying problem of a system is simplified; on the other hand, the raw material conversion rate and the product selectivity are improved, and the low-carbon olefin products can be efficiently obtained.

Description

technical field [0001] The invention relates to a method for preparing low-carbon olefins by co-catalyzing cracking of Fischer-Tropsch synthetic light oil and methanol as raw materials. Under the action of the modified ZSM-5 molecular sieve catalyst, the exothermic methanol catalytic conversion reaction and the endothermic high-carbon olefin catalytic cracking reaction are thermally coupled, and low-carbon olefin products are obtained with high selectivity. Background technique [0002] Low carbon olefins, especially ethylene and propylene are very important chemical raw materials. There are two process routes for the production of low-carbon olefins, petroleum and non-petroleum. Petroleum route technologies include: steam thermal cracking process, improved catalytic cracking (FCC) process, catalytic cracking process, propane dehydrogenation process and olefin disproportionation process; non-petroleum route is generally It refers to the indirect conversion of coal or natura...

Claims

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Application Information

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IPC IPC(8): C07C11/04C07C11/06C07C11/08C07C1/20C07C4/06
CPCC07C1/20C07C4/06C07C2529/40C07C11/04C07C11/06C07C11/08Y02P20/52Y02P30/20Y02P30/40
Inventor 成有为邹徽刘未了朱嘉嘉李希王丽军
Owner ZHEJIANG UNIV
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