CN112831351B - Method for in-situ resource utilization of high-temperature carbon dioxide of power plant - Google Patents

Method for in-situ resource utilization of high-temperature carbon dioxide of power plant Download PDF

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CN112831351B
CN112831351B CN202011629677.3A CN202011629677A CN112831351B CN 112831351 B CN112831351 B CN 112831351B CN 202011629677 A CN202011629677 A CN 202011629677A CN 112831351 B CN112831351 B CN 112831351B
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carbon dioxide
carbonate
molten carbonate
temperature
slurry bed
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CN112831351A (en
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曹鹏飞
范娟
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Xian Jiaotong University
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Xian Jiaotong University
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/48Apparatus; Plants
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60Processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60Processes
    • C10J3/64Processes with decomposition of the distillation products
    • C10J3/66Processes with decomposition of the distillation products by introducing them into the gasification zone
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0969Carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983Additives
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a method for in-situ resource utilization of high-temperature carbon dioxide of a power plant, which comprises the following steps: selecting monobasic or polybasic mixed carbonate, and adding the carbonate into a reactor; inputting flue output gas rich in carbon dioxide in a power plant into a reactor, stirring carbonate, and forming a molten carbonate-slurry bed by using the high temperature of flue gas; the method has the advantages that coal gasification can be combined to realize in-situ recovery and resource utilization of high-temperature carbon dioxide of a power plant, and the method has the characteristics of low energy consumption, large treatment capacity and high conversion utilization efficiency.

Description

Method for in-situ resource utilization of high-temperature carbon dioxide of power plant
Technical Field
The invention belongs to the technical field of carbon dioxide capture and utilization and coal gasification, and relates to a method for in-situ resource utilization of high-temperature carbon dioxide in a power plant.
Background
The basic national conditions of China determine that the main status of coal in a primary energy structure can not be changed in a long time in the future. However, the conventional utilization of coal can cause severe problems of environmental pollution and the like, so that the conversion of coal into clean and high-added-value liquid fuel and chemical products is one of important ways for solving the safety problem of the current chemical strategy in China, and has important engineering application prospects. The coal gasification technology at present mainly faces the difficulty of gasification of coking products and CO2Large amount of discharge and the like.
In addition, the coal-fired power plant is currently a large-scale household for carbon dioxide emission in China, and large-scale and efficient resource utilization of high-temperature carbon dioxide is an important link for realizing the carbon dioxide emission reduction target in China. Currently, the control and recycling of carbon dioxide emission sources is currently the most effective way. The capture of carbon dioxide in coal-fired power plants is mainly focused on post-combustion capture technologies such as high-temperature physical adsorption and low-temperature chemical absorption methods. Although the technology is mature, the following technical drawbacks also exist: although the high-temperature physical adsorption method has simple process flow, the adsorption quantity is limited, and the energy consumption in the processes of pressure reduction and temperature rise is overhigh; although the low-temperature chemical absorption method has fast absorption and large absorption capacity, the organic absorbent is greatly influenced by temperature and is easy to degrade to cause the reduction of the absorption efficiency, in addition, the method also needs to pre-cool the carbon dioxide gas, and the utilization rate of the high-temperature waste heat of the gas is insufficient.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for in-situ resource utilization of high-temperature carbon dioxide of a power plant, the method can realize recovery and resource utilization of the high-temperature carbon dioxide of the power plant by utilizing a molten carbonate catalytic coal gasification reaction, and has the characteristics of low energy consumption, large adsorption capacity and high utilization and conversion efficiency.
In order to achieve the aim, the method for utilizing the high-temperature carbon dioxide of the power plant in the in-situ resource manner comprises the following steps:
selecting monobasic or polybasic mixed carbonate, and adding the carbonate into a reactor;
inputting flue output gas rich in carbon dioxide in a power plant into a reactor from the bottom, stirring carbonate, and forming a molten carbonate-slurry bed by utilizing the high temperature of the flue gas;
adding coal powder into the reactor, stirring to uniformly mix the coal powder and molten carbonate, firstly carrying out heat desorption on the coal powder at a high temperature to obtain a volatile gas product and a solid product coke, reacting the coke with carbon dioxide under the catalysis of the molten carbonate, and deeply gasifying to form coal gas. Meanwhile, the organic volatile gas and the carbon dioxide are subjected to in-situ catalytic reforming to generate synthesis gas with higher energy density. In the long-time continuous reaction process, the residue is driven to move to the upper surface of the molten carbonate-slurry bed by utilizing the lifting force of gas in a reaction system and the density difference between the residue and the molten carbonate-slurry bed, and then scraping is carried out to reduce the problem of bed pressure rise caused by blockage of the reactor.
The carbonate is K2CO3、Na2CO3、Li2CO3、GaCO3、MgCO3、SrCO3And BaCO3One or more of (a) and (b) are mixed to form a mixture.
The reactor comprises a shell, a coal feeding device, a stirrer and a scraper device, wherein the stirrer is arranged in the shell and used for stirring the molten carbonate-slurry bed, the scraper device is used for scraping residual residues on the surface of the molten carbonate-slurry bed, the molten carbonate-slurry bed is positioned in the shell, the bottom of the shell is provided with a gas injection nozzle, and the coal feeding device is communicated with a coal inlet on the side surface of the top of the shell.
The reactor also comprises a gas pretreatment device and a dispersing gas inlet device which are arranged in the shell; the dispersing gas inlet device is positioned below the molten carbonate-slurry bed, and the outlet of the gas pretreatment device is communicated with the inlet of the dispersing gas inlet device.
Calculating the reaction temperature of coal and carbon dioxide gasification in the molten carbonate-slurry bed according to the temperature of the flue gas rich in carbon dioxide in the power plant, and selecting one or more mixed carbonates with the melting points of corresponding temperatures according to the reaction temperature of the molten carbonate-slurry bed.
The invention has the following beneficial effects:
in the method for utilizing the high-temperature carbon dioxide of the power plant in the in-situ resource manner, during specific operation, the carbonate is heated by utilizing the high-temperature flue gas which is output from the power plant and is rich in carbon dioxide, so as to form a molten carbonate-slurry bed, and then the 'salt boiling coal' method is utilized, namely, the coke generated after the pyrolysis of the coal is catalyzed by the molten carbonate, the carbon dioxide and the deep gasification are coupled with the volatile organic gas and the carbon dioxide in-situ reforming mode, so that the large-scale high-efficiency and high-value utilization of the carbon dioxide are realized in situ, the problem that the coking product generated in the coal gasification process is difficult to gasify is solved, and the energy consumption of the system in operation is reduced.
Drawings
FIG. 1 is a schematic view of the structure of a reactor.
Wherein, 1 is a shell, 2 is a coal feeding device, 3 is a scraper device, 4 is a molten carbonate-slurry bed, 5 is a stirrer, 6 is a dispersing air inlet device, and 7 is a gas premixing device.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, the method for in-situ resource utilization of high-temperature carbon dioxide in a power plant according to the present invention includes the following steps:
selecting one or more carbonates, fully and uniformly mixing, and adding the carbonates into a reactor;
specifically, the reaction temperature of the molten carbonate-slurry bed 4 is calculated according to the temperature of the flue gas rich in carbon dioxide in the power plant, the melting point of the mixed carbonate is determined according to the reaction temperature of the molten carbonate-slurry bed 4, and the carbonate with the corresponding proportion is selected.
High-temperature flue gas which is discharged from a power plant and rich in carbon dioxide is filtered and premixed through a gas pretreatment device 7, then is input into a reactor from the bottom through a spray nozzle 6, and a carbonate bed layer is stirred to form a molten carbonate-slurry bed 4;
coal dust is added to the reactor while stirring to thoroughly mix the coal dust with the molten carbonate. During operation, the pulverized coal is firstly subjected to heat desorption at high temperature to obtain volatile gas products and solid product coke, and then the coke is reacted with carbon dioxide under the catalysis of molten carbonate to carry out deep gasification to form coal gas. Meanwhile, the intermediate metal simple substance in the catalysis process promotes the volatile gas generated by pyrolysis and carbon dioxide to carry out reforming reaction to generate synthesis gas. Wherein the reaction between coke, carbon dioxide and carbonate is:
c+M2CO3→3CO+2M
2CO2+2M→M2CO3+CO
the lift force of gas in the reaction system and the density difference between the residue and the molten carbonate-slurry bed 4 are utilized to drive the residue to move to the upper surface of the molten carbonate-slurry bed 4, and then the residue is scraped to solve the problem of bed pressure rise caused by blockage, which is common in coal gasification.
The carbonate is K2CO3、Na2CO3、Li2CO3、GaCO3、MgCO3、SrCO3And BaCO3One or more of (a) and (b) are mixed to form a mixture.
The reactor comprises a shell 1, a coal feeding device 2, a stirrer 5 arranged in the shell 1 and used for stirring a molten carbonate-slurry bed 4 and a scraper device 3 used for scraping residues on the surface of the molten carbonate-slurry bed 4, wherein the molten carbonate-slurry bed 4 is positioned in the shell 1, the bottom of the shell 1 is provided with a gas inlet, and the coal feeding device 2 is communicated with a coal inlet on the side surface of the top of the shell 1; the reactor also comprises a gas premixing device 7 and an injection gas inlet device 6 which are arranged in the shell 1; the jet gas inlet device 6 is positioned below the molten carbonate-slurry bed 4, and the outlet of the gas premixing device 7 is communicated with the inlet of the jet gas inlet device 6.
During actual operation, through setting for scraper means 3's scraping frequency, effectively avoid present formula of sinking to arrange sediment because the pressure drop in the stove that easily blocks up the cause risees the influence problem to coal gasification to adapt to long period, large-scale industrial requirement.

Claims (3)

1. A method for in-situ resource utilization of high-temperature carbon dioxide of a power plant is characterized by comprising the following steps:
selecting a monobasic or polybasic mixed carbonate, and adding the monobasic or polybasic mixed carbonate into a reactor;
introducing flue gas rich in carbon dioxide in a power plant into a reactor from the bottom, stirring carbonate, and heating the carbonate to a melting point by utilizing the temperature of the flue gas to form a molten carbonate-slurry bed (4);
adding coal powder into the reactor, stirring to uniformly mix the coal powder and molten carbonate, promoting gasification and reforming reactions of coke and volatile organic gas after coal pyrolysis with carbon dioxide by using the molten carbonate in a high-temperature reaction, and driving reaction residues to move to the upper surface of the molten carbonate-slurry bed (4) to be scraped by using the lifting force of gas in a reaction system and the density difference between the residues and the molten carbonate-slurry bed (4);
the reactor comprises a shell (1), a coal feeding device (2), a stirrer (5) arranged in the shell (1) and used for stirring the molten carbonate-slurry bed (4), and a scraper device (3) used for scraping residues on the surface of the molten carbonate-slurry bed (4), wherein the molten carbonate-slurry bed (4) is positioned in the shell (1), the bottom of the shell (1) is provided with a gas injection nozzle, and the coal feeding device (2) is communicated with a coal inlet on the side surface of the top of the shell (1);
the reactor also comprises a gas pretreatment device (7) and a dispersion gas inlet device (6) which are arranged in the shell (1); the dispersing gas inlet device (6) is positioned below the molten carbonate-slurry bed (4), and the outlet of the gas pretreatment device (7) is communicated with the inlet of the dispersing gas inlet device (6).
2. The method for in-situ resource utilization of high-temperature carbon dioxide from power plants according to claim 1, wherein the carbonate is K2CO3、Na2CO3、Li2CO3、GaCO3、MgCO3、SrCO3And BaCO3One or more of (a) and (b) are mixed to form a mixture.
3. The method for in-situ resource utilization of high-temperature carbon dioxide from a power plant according to claim 1, characterized by calculating the reaction temperature of coal and carbon dioxide gasification in the molten carbonate-slurry bed (4) according to the temperature of flue gas rich in carbon dioxide from the power plant, and selecting the mono-or multi-component carbonate with the melting point of corresponding temperature according to the reaction temperature of the molten carbonate-slurry bed (4).
CN202011629677.3A 2020-12-30 2020-12-30 Method for in-situ resource utilization of high-temperature carbon dioxide of power plant Active CN112831351B (en)

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US4017271A (en) * 1975-06-19 1977-04-12 Rockwell International Corporation Process for production of synthesis gas
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CN103289751A (en) * 2013-06-17 2013-09-11 昆明理工大学 Method and device for preparing combustible gas by utilizing biomass
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CN111718757A (en) * 2019-03-19 2020-09-29 赫普能源环境科技有限公司 Thermal power plant coal pyrolysis gas hydrogen production system and method

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