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A Fischer-Tropsch-oligomerization coupled catalytic conversion of olefin-rich synthesis gas to prepare liquid hydrocarbons

A catalytic conversion and Fischer-Tropsch catalyst technology, which is applied in the preparation of liquid hydrocarbon mixtures and the petroleum industry, can solve the problems that are not conducive to increasing the octane number of fuels, achieve full utilization of green and low-carbon resources, increase the degree of isomerization, The effect of improving the comprehensive carbon utilization rate

Active Publication Date: 2020-03-24
GUANGZHOU INST OF ENERGY CONVERSION - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the products of Fischer-Tropsch synthesis are limited by the distribution of ASF and are mainly straight-chain hydrocarbons, which is not conducive to improving the octane number of fuels.

Method used

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  • A Fischer-Tropsch-oligomerization coupled catalytic conversion of olefin-rich synthesis gas to prepare liquid hydrocarbons

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] In this embodiment, the coupling catalytic system adopts oligomerization molecular sieve catalyst HZSM-5 and Fischer-Tropsch catalyst FeMn, wherein HZSM-5 is a commercially available microporous molecular sieve catalyst, wherein m(Si):m(Al)=20:1, HZSM -5 is calcined at 550°C, pressed into tablets and sieved to obtain finished granules of 40-60 mesh (that is, with a particle size of 0.25-0.38 mm) for future use.

[0028] The FeMn catalyst (m(Fe):m(Mn)=2:1) ​​was prepared by co-precipitation method, and the specific preparation steps were as follows: Fe(NO3 ) 3 9H 2 O and Mn(NO 3 ) 2 Dissolve in deionized water, stir until a homogeneous solution is formed, in which the mass ratio of Fe to Mn is 2:1; heat the solution to 80°C and maintain this temperature, then slowly drop in a mass fraction of 25 % ammonia solution until the pH of the solution is 8.0. With the addition of ammonia water, dark brown precipitates are produced in the solution. After the dark brown precipi...

Embodiment 2

[0033] Catalyst: The preparation method of HZSM-5 and FeMn is the same as that of Example 1. The two kinds of catalyst powders of equal mass are stirred and ground in a mortar and mixed evenly, and the obtained composite catalyst powder is granulated to obtain 40~60 mesh particles, and 1g of the composite catalyst powder is The particles are mixed with 1g of quartz sand and filled into the fixed bed reaction tube.

[0034] Coupled Catalytic Reaction: Pre-reduction of Coupled Catalytic System in Syngas H 2 Carried out in an atmosphere with a molar ratio of 1:1 to CO, pressure 0.1MPa, syngas space velocity 3000mL / g·h, temperature 300°C, reduction for 12h. The reaction raw material gas adopts the simulated mixed gas similar to the olefin-rich syngas produced by the catalytic cracking of bio-oil, and its gas composition is as follows: the volume ratio of each component gas is C 3 h 6 / CO / H 2 / N 2 =20 / 30 / 10 / 40, the reaction conditions are temperature 280°C, pressure 4.0MPa, raw...

Embodiment 3

[0037] Catalyst: The preparation method of HZSM-5 and FeMn is the same as that in Example 1, and the two catalyst particles of equal mass 40-60 mesh are evenly mixed to obtain composite catalyst particles of 40-60 mesh, and 1 g of the composite catalyst particles is mixed with 1 g of quartz sand. Fill the fixed bed reaction tube.

[0038] Coupled catalytic reaction: the reaction conditions are the same as in Example 1, and the final product C 5+ The yield reaches about 59g / (kgcata*h), C 5+ The selectivity reaches about 52%, C 5+ C in the product 5 - C 12 The selectivity of gasoline section is over 95%, while the selectivity of olefins is 97%, and the selectivity of isomeric hydrocarbon is about 70%. Its concrete result is shown in Table 1, and Table 1 is the yield of embodiment 1~8 catalyst coupling mode, reaction condition and product and C 5+ Selective comparison results.

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Abstract

The invention provides a method for preparing liquid hydrocarbons by Fischer-Tropsch oligomerization coupled catalytic conversion of olefin-rich synthesis gas. The method comprises introducing raw material gas into a fixed bed reactor loaded with a composite catalyst, carrying out a Fischer-Tropsch oligomerization coupling catalytic reaction process to obtain a liquid mixture containing liquid hydrocarbons and water, and carrying out standing layering to obtain liquid hydrocarbons in the form of oil in the upper layer. The composite catalyst is a coupled catalyst of a Fischer-Tropsch catalystand an oligomerization catalyst. The method realizes the co-conversion of CO and olefin into high-grade liquid hydrocarbons with relatively concentrated carbon distribution and isomeric olefin as a main component and has the characteristics of mild conversion conditions, concentrated and simple processes, high carbon utilization rate, strong product selectivity and high added value.

Description

Technical field: [0001] The invention belongs to the technical field of preparing hydrocarbons through catalytic conversion of olefin-rich synthesis gas, and in particular relates to a method for preparing liquid hydrocarbons through Fischer-Tropsch-oligomerization coupled catalytic conversion of olefin-rich synthesis gas. Background technique: [0002] The production of fuels worldwide mainly comes from the refining process of petroleum. With the gradual increase in global oil prices, the massive consumption of oil resources, and the increasing emphasis on environmental issues (greenhouse effect and pollutant emissions, such as floating carbon, hydrocarbons, carbon monoxide, nitrogen oxides, sulfides, etc.), the development of non-petrochemical Renewable energy processes have received a lot of attention. At present, biomass resources are the only carbonaceous resources that can be directly converted into liquid fuels and high value-added chemicals due to their cleanliness,...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G2/00
CPCC10G2/332C10G2/334C10G2/341
Inventor 王晨光张浅马隆龙李宇萍徐莹张兴华
Owner GUANGZHOU INST OF ENERGY CONVERSION - CHINESE ACAD OF SCI
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