CN110872531B - Step waste heat recovery device and method utilizing pyrolysis gasification of solid particle heat carrier - Google Patents

Step waste heat recovery device and method utilizing pyrolysis gasification of solid particle heat carrier Download PDF

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CN110872531B
CN110872531B CN201911292252.5A CN201911292252A CN110872531B CN 110872531 B CN110872531 B CN 110872531B CN 201911292252 A CN201911292252 A CN 201911292252A CN 110872531 B CN110872531 B CN 110872531B
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gasification
furnace
pyrolysis
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CN110872531A (en
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左宗良
张敬奎
罗思义
于庆波
周恩泽
郭建翔
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Qingdao University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0969—Carbon dioxide
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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Abstract

The invention relates to a step waste heat recovery device and method by utilizing pyrolysis gasification of a solid particle heat carrier. The device comprises a gasification furnace, a pyrolysis furnace, a solid separator and a flue gas treatment system, wherein the gasification furnace, the pyrolysis furnace and the solid separator are sequentially connected, and the gasification furnace is converged with a flue outlet of the pyrolysis furnace and is connected with the flue gas treatment system. The method comprises the following steps: the high-temperature particles enter a gasification furnace, the carbon-containing solid waste material A enters the gasification furnace under the carrying of a gasification agent, combustible gas and particles after primary cooling are generated through gasification reaction, the particles after cooling and the carbon-containing solid waste material B enter a pyrolysis furnace for pyrolysis reaction to generate pyrolysis gas and solid semicoke, and after screening, the yield of the solid semicoke is 20-23%, the content of fixed carbon reaches 77-79.1%, and the solid semicoke is used as a gasification furnace fuel. The invention improves the waste heat recovery efficiency of the solid particles to 80-84%,
Figure DDA0002319584880000011
the efficiency is improved to 70-77%, and the heat value is 5000-3Combustible clean gas and CO reduction2And (4) discharging the amount.

Description

Step waste heat recovery device and method utilizing pyrolysis gasification of solid particle heat carrier
The technical field is as follows:
the invention belongs to the technical field of waste heat recovery and energy conservation, and particularly relates to a step waste heat recovery device and method for pyrolysis gasification by utilizing a solid particle heat carrier.
Background art:
the production process in the industries of metallurgy, building materials, chemical engineering and the like has a large amount of high-temperature solid bulk materials and solid particles, such as sintered ores, pellets, direct reduced iron and the like. In addition, metallurgical slag (such as blast furnace slag, steel slag, copper slag, nickel slag and the like) and the like are byproducts discharged in a metal smelting process, the discharge temperature is high (>1200 ℃), and a large amount of sensible heat is contained. At present, the traditional treatment mode of metallurgical slag is a water quenching method, a large amount of water resources are consumed by the treatment mode, and the environmental pollution caused by slag flushing water is serious. Only taking blast furnace slag as an example, the tapping temperature of the blast furnace slag is about 1500 ℃, and the sensible heat of each ton of slag approximately equals 60kg of standard coal. The annual output of the blast furnace slag 2018 in China can reach 2.5 hundred million tons, and about 1500 million tons of standard coal are met. Therefore, the realization of the high-efficiency clean waste heat recovery of the metallurgical industry solid waste is the key of energy conservation and emission reduction of the industry in China.
In order to realize the high-efficiency recovery of the waste heat of the metallurgical slag, change the current situation of water consumption and serious pollution caused by the traditional method and realize the energy-saving and emission-reduction transformation at the tail end of the process flow, the dry granulation and waste heat recovery process of the metallurgical slag converts liquid high-temperature slag into solid high-temperature (about 1100 ℃) particles through a granulation device (such as a rotating cup, a rotating drum, a rotating disc and the like) on the premise of not consuming new water, and then the high-temperature sensible heat of the particles is recovered through direct or indirect contact with a heat transfer medium. With the development and maturity of the granulation technology and process, the slag particles obtained by dry granulation have good sphericity and high vitreous body content, and are convenient for subsequent waste heat recovery and resource utilization.
The existing waste heat recovery process of high-temperature solid particles is mainly a physical method. The method takes water, air and the like as heat exchange media, has the characteristics of more energy conversion times and low waste heat recovery efficiency, can generate hot water, steam, hot air and the like after recovery, and is difficult to improve the quality essentially. The physical method is adopted to recover the waste heat to generate hot water or hot steam, the thermal efficiency is 76 percent,
Figure BDA0002319584860000011
the efficiency was 14.4%, 34.2%. The chemical method mainly absorbs the high-temperature sensible heat of the particles through a typical endothermic chemical reaction to generate a chemical product with higher added value of the product. The method converts heat energy of the particles into chemical energy, and improves the recovery process
Figure BDA0002319584860000012
Efficiency. In the prior patents, CN 201910236543.6, CN 201910305887.8, CN 200910012471.3, CN 201510283249.2, etc. all use slag as a heat carrier to drive coal gasification reaction to prepare synthesis gas.
Therefore, how to efficiently recover the sensible heat of the high-temperature particles in industrial production and reduce the energy consumption in the production process is an urgent problem to be solved in China. This also draws high attention from universities, research institutes and enterprises at home and abroad, but no report on the popularization and application of related technologies in this field exists at present.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and provides a step waste heat recovery device and method for pyrolysis gasification by using a solid particle heat carrier, which can realize the aim of efficiently recovering waste heat of high-temperature solid particles and solve the technical problems of difficult recovery and low recovery efficiency of the waste heat of the high-temperature solid particles.
In order to achieve the purpose, the invention adopts the following technical scheme:
utilize solid particle heat carrier pyrolysis gasification's step waste heat recovery device, including gasifier, pyrolysis oven, solid separator and flue gas processing system, wherein:
the gasification furnace, the pyrolysis furnace and the solid separator are sequentially connected, and the gasification furnace is converged with a flue outlet of the pyrolysis furnace and is connected with a flue gas treatment system.
The flue gas treatment system comprises a cyclone separator, a gas-liquid separator and a purifier, and all the components are connected in sequence.
The gasification furnace is a fixed bed or a fluidized bed, and is provided with a particle feeding device, a gasification furnace fuel nozzle and a particle outlet.
The pyrolysis furnace is a fixed bed, and a stirring device is arranged in the pyrolysis furnace.
The particle outlet of the gasification furnace is connected with the particle feeding device of the pyrolysis furnace, and the particle outlet of the pyrolysis furnace is connected with the solid separator.
The solid separator is connected with the fuel nozzle of the gasification furnace through a lifting device. The semicoke mixture separated by the solid separator provides fuel for the gasification furnace.
The method for recovering the waste heat by adopting the step waste heat recovery device utilizing the pyrolysis gasification of the solid particle heat carrier comprises the following steps:
step 1, recovering waste heat of high-temperature particles:
the method comprises the following steps that high-temperature particles enter a gasification furnace, carbon-containing solid waste materials A enter the gasification furnace under the carrying of a gasification agent, the high-temperature particles move from top to bottom in the gasification furnace under the action of self gravity, the gasification agent and the carbon-containing solid waste materials A are subjected to gasification reaction in the gasification furnace to generate combustible gas, and particles after primary cooling are obtained, wherein the temperature of the high-temperature particles is 900-1200 ℃, the gasification reaction components in the gasification agent are in a molar ratio: c element (0.2-1) in the carbon-containing solid waste material A is 1, and the mass ratio of the C element to the C element is as follows: c element in the carbon-containing solid waste material A is 1 (0.02-0.05);
step 2, recovering waste heat of medium-low temperature particles:
after primary cooling, the particles and the carbon-containing solid waste material B enter a pyrolysis furnace, and the carbon-containing solid waste material B is prepared by the following steps: and (3) after primary cooling, enabling the particles to move from top to bottom in the pyrolysis furnace, enabling the carbon-containing solid waste material B to perform pyrolysis reaction in the furnace to generate pyrolysis gas and solid semicoke, and obtaining the cooled particles.
Step 3, solid separation:
and feeding the cooled mixture of the particles and the solid semicoke into a solid separator, and screening and separating in the solid separator to obtain the cooled particles and the solid semicoke, wherein the solid semicoke is fed into a gasification furnace and used as fuel to provide heat for the gasification furnace, the yield of the solid semicoke is 20-23%, and the content of fixed carbon in the solid semicoke is 77-79.1%.
In the step 1, the high-temperature particles are blast furnace slag particles or steel slag particles discharged by steel smelting, and the particle size is 1-10 mm, wherein:
the blast furnace slag particles comprise 41.21 percent of CaO, 8.22 percent of MgO and SiO by mass percentage234.38％，Al2O3 11.05％，Fe2O3 2.78％，TiO20.35%, the rest is other;
the steel slag particles comprise, by mass, CaO 41.18%, MgO 9.26%, and SiO220.49％，Al2O3 3.08％，Fe2O320.35%, the rest others.
In the step 1, the gasifying agent is water vapor and CO2Rich in CO2Gas or air, said CO being enriched2The gas is CO-containing gas generated by industrial furnaces or boilers2The gasification reaction component in the waste gas and the gasification agent is H2O、CO2Or O2。
In the step 1, the gasifying agent is rich in CO2Flue gas, CO in flue gas2The content is 10-40%, and the content of N is 60-90%.
In the step 1, the gasification reaction quickly absorbs the heat of the particles and generates combustible gas; meanwhile, the temperature of the high-temperature particles is rapidly cooled, the temperature of the particles after primary cooling is 500-800 ℃, and the particles after primary cooling enter a particle feeding device of the pyrolysis furnace through a particle outlet.
In the step 1, the combustible gas carries semicoke and ash.
In the step 1, the chemical reaction equation of the gasification reaction of the gasification furnace is as follows:
C+CO2(g)＝2CO(g) 173.4kJ/mol (1)
C+H2O(g)＝CO(g)+H2(g) 135.6kJ/mol (2)
in the steps 1 and 2, the carbon-containing solid waste material A or B is coal powder, biomass, sludge, plastics, rubber and other industrial, agricultural and biological carbon-containing waste materials, and the carbon element content of the carbon-containing solid waste material A or B is 20-70%.
In the steps 1 and 2, the carbon-containing solid waste material A or B needs to be dried before entering the pyrolysis furnace or the gasification furnace.
In the steps 1 and 2, the carbon-containing solid waste material is coal powder.
In the step 2, the pyrolysis reaction quickly absorbs the heat of the particles after the primary cooling, the temperature of the particles after the primary cooling is further cooled, and the temperature of the particles after the cooling is less than or equal to 200 ℃. And the cooled particles and solid semicoke generated after pyrolysis enter a solid separator through a particle outlet.
In the step 2, the pyrolysis gas comprises coal gas, and the pyrolysis gas is converged with the combustible coal gas obtained in the step 1 and then treated byThe gas-liquid separator separates out the condensation tar in the pyrolysis gas and the semicoke and ash in the combustible gas, and the purifier separates the smoke dust to obtain clean gas. The heat value of the clean gas is 7000kJ/m3。
The cascade waste heat recovery method for pyrolysis gasification by using solid particle heat carrier has the advantages that after cascade waste heat recovery, the heat efficiency reaches 80-84%,
Figure BDA0002319584860000031
the efficiency is 70-77%.
The invention has the beneficial effects that:
(1) the process system and the method can efficiently recover the solid particle waste heat, improve the solid particle waste heat recovery efficiency to 80-84%,
Figure BDA0002319584860000041
the efficiency is improved to 70-77%;
(2) the method can convert the solid particle waste heat into the heat value of 5000-7000 kJ/based on the standard deviation of the heat value3The combustible clean coal gas, the solid semicoke with the fixed carbon content of 77-79.1 percent and other products with high added value;
(3) the system and the method adopt rich CO while protecting the environment and saving resources2When the flue gas is a gasifying agent, the waste heat of each kg of slag particles is recovered, and the greenhouse gas CO can be reduced2More than 30L.
Description of the drawings:
FIG. 1 is a process flow diagram of a step waste heat recovery method by pyrolysis gasification of a solid particle heat carrier in embodiment 1 of the invention;
fig. 2 is a schematic structural view of a step waste heat recovery device utilizing pyrolysis gasification of a solid particle heat carrier according to embodiment 1 of the present invention;
FIG. 3 is a process flow diagram of a step waste heat recovery method by pyrolysis gasification of a solid particle heat carrier in embodiment 2 of the invention;
fig. 4 is a schematic structural diagram of a step waste heat recovery device utilizing pyrolysis gasification of a solid particle heat carrier according to embodiment 2 of the present invention; wherein:
the method comprises the following steps of 1-a gasification furnace, 2-a pyrolysis furnace, 3-a solid separator, 4-a cyclone separator, 5-a gas-liquid separator, 6-a purifier, 7-a high-temperature particle feeding device, 8-a storage bin, 9-a gasification furnace fuel nozzle, 10-a gasification furnace particle outlet, 11-a medium-low temperature particle feeding device, 12-a pyrolysis furnace fuel nozzle, 13-a stirring device and 14-a pyrolysis furnace particle outlet.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
The following is a calculation of the materials required and the products produced during the gasification and pyrolysis process according to the law of conservation of mass and energy, taking 1kg of slag particles as an example.
The calculation conditions were as follows:
the inlet temperature of high-temperature slag particles in the gasification furnace is 1100 ℃, and the outlet temperature is 700 ℃; the inlet temperature of the medium-low temperature slag particles in the pyrolysis furnace is 700 ℃, the outlet temperature is 100 ℃, and the specific heat capacity of the slag is Cm11.2 kJ/(kg. DEG C.), the mass of slag particles is m1。
The fuels in the gasification furnace and the pyrolysis furnace are coal powder, wherein the coal powder comprises 64.4 percent of C, 4.2 percent of H, 8.8 percent of O, 20 percent of ash content, 44.8 percent of fixed carbon, 32.8 percent of volatile matter, and C, the specific heat capacity of the coal powderm21.1 kJ/(kg. DEG C.), and the coal powder mass m2And (4) showing.
The gasifying agent is rich in CO2Flue gas, the flue gas component being (CO)2＝40％，N260%) specific heat capacity Cm3Is represented by N2Specific heat capacity of 1.03 kJ/(kg. DEG C), CO2Specific heat capacity of 0.84 kJ/(kg. DEG C), and gasification agent mass m3And (4) showing.
The outlet temperature of the coal gas generated by the gasification furnace is 800 ℃; the outlet temperature of the pyrolysis gas generated by the pyrolysis furnace is 300 ℃.
The carbon conversion rate and the pyrolysis conversion rate in the gasification process are calculated according to 100 percent.
(1) Gasification furnace
According to the law of conservation of energy: the heat released by the slag is the heat absorbed by the gasification reaction, and the amount of the coal powder required by the gasification reaction is as follows:
the heat revenue terms are as follows:
1) physical heat of slag substitution
Qin-1＝Cm1×1×t1＝1.2×1×(1100)kJ＝1320.0kJ (3)
2) Physical heat brought in by coal dust
Qin-2＝Cm2×m2×t2＝1.1×m2×(20) (4)
3) Physical heat carried in by gasifying agent
Qin-3＝Cm3×m3×t3＝0.954×m3×(20) (5)
The heat removal term is as follows:
4) heat absorbed by gasification reaction
Figure BDA0002319584860000051
5) The particles take away physical heat
Qout-2＝Cm1×1×t1'＝1.2×1×(700)kJ＝840.0kJ (7)
6) Physical heat brought out by coal slag
Qout-3＝Cm2×m2×0.2×t2'＝1.1×m2×0.2×900＝198×m2kJ (8)
7) Physical heat brought out by flue gas
Figure BDA0002319584860000052
According to the coal dust and CO2The gasification reaction mass relationship can be given as:
Figure BDA0002319584860000053
according to the law of conservation of energy, Qin＝QoutSimultaneous equations can calculate the consumption of coal powder for each 1kg of slag particles in the gasifier0.0296kg, CO production 0.089kg (about 71L), gasifier thermal efficiency 57.4%. If the waste heat recovery of the flue gas in the cooler is considered, when the waste heat recovery rate of the flue gas is 60%, the thermal efficiency of the gasification furnace can reach 82%. CO-Rich gasification process2The gasifying agent is CO-containing gas produced by industrial furnace or boiler2Exhaust gases, i.e. with the process according to the invention, can absorb 0.07kg of CO per 1kg of slag treated2The waste gas can absorb CO annually according to the calculation of 2.5 million tons of slag generated annually in China2Up to 1750 ten thousand tons. The results of calculation of the input amount of the materials of the gasification furnace and the output amount of the products are shown in table 1.
TABLE 1 calculation results of input of materials and output of products in gasification furnace
Figure BDA0002319584860000061
TABLE 2 balance of heat budget of gasifier
Figure BDA0002319584860000062
(2) Pyrolysis process
The heat of decomposition of coal is 448kJ/(kg), and the thermal decomposition products of coal are CO and H2Calculating that C element in the coal powder is converted into fixed carbon and CO, and H element is completely converted into H2。
Similarly, the calculation results of the input amount of the material and the output amount of the product in the pyrolysis furnace are shown in table 3.
TABLE 3 calculation results of input of materials and output of products in pyrolysis furnace
Figure BDA0002319584860000063
TABLE 4 pyrolysis furnace heat budget balance table
Figure BDA0002319584860000071
According to the set conditions, 1.263kg of coal powder is consumed to process 1kg of slag particles in the pyrolysis furnace, 0.195kg (about 155L) of CO and H are generated20.053kg (about 590L) to produce 0.818kg of semicoke, and the theoretical thermal efficiency of the pyrolysis furnace is 82.3%.
Figure BDA0002319584860000073
The efficiency is calculated as follows.
Figure BDA0002319584860000072
Through integral calculation, the integral heat efficiency of the process system consisting of the gasification furnace and the pyrolysis furnace can reach 84.7 percent,
Figure BDA0002319584860000074
the efficiency can reach 77.4%.
Theoretical analysis and calculation of the gasification and pyrolysis parts in the step waste heat recovery device and method utilizing pyrolysis and gasification of the solid particle heat carrier can show that the invention provides a brand-new idea for step waste heat recovery of high-temperature particles.
Utilize solid particle heat carrier pyrolysis gasification's step waste heat recovery device, including gasifier, pyrolysis oven, solid separator and flue gas processing system, wherein:
the gasification furnace, the pyrolysis furnace and the solid separator are sequentially connected, and the gasification furnace is converged with a flue outlet of the pyrolysis furnace and is connected with a flue gas treatment system.
The flue gas treatment system comprises a cyclone separator, a gas-liquid separator and a purifier, and all the components are connected in sequence.
The gasification furnace is a fixed bed or a fluidized bed, and is provided with a particle feeding device, a gasification furnace fuel nozzle and a particle outlet.
The pyrolysis furnace is a fixed bed, and a stirring device is arranged in the pyrolysis furnace.
The particle outlet of the gasification furnace is connected with the particle feeding device of the pyrolysis furnace, and the particle outlet of the pyrolysis furnace is connected with the solid separator.
The solid separator is connected with the fuel nozzle of the gasification furnace through a lifting device. The semicoke mixture separated by the solid separator provides fuel for the gasification furnace.
The method for recovering the waste heat by adopting the step waste heat recovery device utilizing the pyrolysis gasification of the solid particle heat carrier comprises the following steps:
step 1, recovering waste heat of high-temperature particles:
the method comprises the following steps that high-temperature particles enter a gasification furnace, carbon-containing solid waste materials A enter the gasification furnace under the carrying of a gasification agent, the high-temperature particles move from top to bottom in the gasification furnace under the action of self gravity, the gasification agent and the carbon-containing solid waste materials A are subjected to gasification reaction in the gasification furnace to generate combustible gas, and particles after primary cooling are obtained, wherein the temperature of the high-temperature particles is 900-1200 ℃, the gasification reaction components in the gasification agent are in a molar ratio: c element (0.2-1) in the carbon-containing solid waste material A is 1, and the mass ratio of the C element to the C element is as follows: c element in the carbon-containing solid waste material A is 1 (0.02-0.05);
step 2, recovering waste heat of medium-low temperature particles:
after primary cooling, the particles and the carbon-containing solid waste material B enter a pyrolysis furnace, and the carbon-containing solid waste material B is prepared by the following steps: and (3) after primary cooling, enabling the particles to move from top to bottom in the pyrolysis furnace, enabling the carbon-containing solid waste material B to perform pyrolysis reaction in the furnace to generate pyrolysis gas and solid semicoke, and obtaining the cooled particles.
Step 3, solid separation:
and feeding the cooled mixture of the particles and the solid semicoke into a solid separator, and screening and separating in the solid separator to obtain the cooled particles and the solid semicoke, wherein the solid semicoke is fed into a gasification furnace and used as fuel to provide heat for the gasification furnace, the yield of the solid semicoke is 20-23%, and the content of fixed carbon in the solid semicoke is 77-79.1%.
In the step 1, the high-temperature particles are blast furnace slag particles or steel slag particles discharged by steel smelting, and the particle size is 1-10 mm, wherein:
the blast furnace slag particles comprise components and substancesThe weight percentage content of CaO is 41.21 percent, MgO is 8.22 percent, and SiO234.38％，Al2O3 11.05％，Fe2O3 2.78％，TiO20.35%, the rest is other;
the steel slag particles comprise, by mass, CaO 41.18%, MgO 9.26%, and SiO220.49％，Al2O3 3.08％，Fe2O320.35%, the rest others.
In the step 1, the gasifying agent is water vapor and CO2Rich in CO2Gas or air, said CO being enriched2The gas is CO-containing gas generated by industrial furnaces or boilers2The gasification reaction component in the waste gas and the gasification agent is H2O、CO2Or O2。
In the step 1, the gasifying agent is rich in CO2Flue gas, CO in flue gas2The content is 10-40%, and the content of N is 60-90%.
In the step 1, the gasification reaction quickly absorbs the heat of the particles and generates combustible gas; meanwhile, the temperature of the high-temperature particles is rapidly cooled, the temperature of the particles after primary cooling is 500-800 ℃, and the particles after primary cooling enter a particle feeding device of the pyrolysis furnace through a particle outlet.
In the step 1, the combustible gas carries semicoke and ash.
In the step 1, the chemical reaction equation of the gasification reaction of the gasification furnace is as follows:
C+CO2(g)＝2CO(g) 173.4kJ/mol (1)
C+H2O(g)＝CO(g)+H2(g) 135.6kJ/mol (2)
in the steps 1 and 2, the carbon-containing solid waste material A or B is coal powder, biomass, sludge, plastics, rubber and other industrial, agricultural and biological carbon-containing waste materials, and the carbon element content of the carbon-containing solid waste material A or B is 20-70%.
In the steps 1 and 2, the carbon-containing solid waste material A or B needs to be dried before entering the pyrolysis furnace or the gasification furnace.
In the steps 1 and 2, the carbon-containing solid waste material is coal powder.
In the step 2, the pyrolysis reaction quickly absorbs the heat of the particles after the primary cooling, the temperature of the particles after the primary cooling is further cooled, and the temperature of the particles after the cooling is less than or equal to 200 ℃. And the cooled particles and solid semicoke generated after pyrolysis enter a solid separator through a particle outlet.
In the step 2, the pyrolysis gas comprises coal gas, the pyrolysis gas is converged with the combustible coal gas obtained in the step 1, the condensable tar in the pyrolysis gas and the semicoke and ash in the combustible coal gas are separated through a gas-liquid separator, and the smoke dust is separated through a purifier to obtain clean coal gas. The heat value of the clean gas is 7000kJ/m3。
The cascade waste heat recovery method for pyrolysis gasification by using solid particle heat carrier has the advantages that after cascade waste heat recovery, the heat efficiency reaches 80-84%,
Figure BDA0002319584860000092
the efficiency is 70-77%.
In the following examples, coal dust having a C of 64.4%, H of 4.2%, O of 8.8%, ash content of 20%, fixed carbon content of 44.8%, volatile matter content of 32.8%, specific heat capacity C of coal dust was usedm21.1 kJ/(kg. multidot. C.).
Example 1
The slag adopted by the implementation of the invention is derived from the slag discharge of a blast furnace of a certain domestic iron and steel enterprise, and the main components are shown in Table 5.
TABLE 5 slag granule chemical composition%
Figure BDA0002319584860000091
The schematic structural diagram of the step waste heat recovery device utilizing pyrolysis gasification of solid particle heat carriers is shown in fig. 2, and the step waste heat recovery device comprises a gasification furnace 1, a pyrolysis furnace 2, a solid separator 3 and accessory equipment thereof, wherein the pyrolysis furnace 2 and the gasification furnace 1 mainly comprise a furnace body, a feeding device system and a flue gas treatment device system. The feeding device system is provided with a high-particle feeding device 7, a medium-low temperature particle feeding device 11, a gasifier fuel nozzle 9, a pyrolysis furnace fuel nozzle 12, a gasifier particle outlet 10 and a pyrolysis furnace particle outlet 14; the flue gas treatment system is provided with a cyclone separator 4, a gas-liquid separator 5 and a purifier 6. Further, a stirring device 13 is provided in the pyrolysis furnace. The gasification furnace 1, the pyrolysis furnace 2 and the solid separator 3 are connected in sequence. The gasification furnace particle outlet 10 is connected with a low-temperature particle feeding device 11 in the pyrolysis furnace, and the pyrolysis furnace particle outlet 14 is connected with the solid separator 3. The gasification furnace 1 is converged with the flue outlet of the pyrolysis furnace 2 and is connected with the cyclone separator 4, the gas-liquid separator 5 and the purifier 6 in sequence.
The gasification furnace 1 is a fluidized bed, and the type of the pulverized coal in the fluidized bed 1 is anthracite; the pyrolysis furnace 2 is a fixed bed, and the pulverized coal in the pyrolysis furnace 2 is lignite. In both devices the coal dust needs to be dried and ground to below 100 mesh before entering.
After the combustible gas passes through the cyclone separator, the incompletely combusted solid is obtained, and the incompletely combusted solid is collected by a bin. The feed bin is collected in a funnel shape and then is conveyed to the gasification furnace through the conveying device, and the feed bin enters the gasification furnace through the gasification furnace fuel nozzle.
The gasifying agent in the gasification furnace 1 is rich CO in certain lime kiln2The waste gas contains CO2 32.2％，N2 59.6，O21.8％，CO 2.6％，H2O3% and the other 2.6%.
The method for recycling cascade waste heat by adopting the device is shown in a process flow chart in figure 1. The process mainly comprises three parts of gasification, pyrolysis and separation. The main raw materials of the gasification furnace are coal powder and a gasification agent, and the product is synthesis gas. The main raw material of the pyrolysis furnace is coal powder, and the product is pyrolysis gas. The high-temperature particles respectively flow through the gasification furnace and the pyrolysis furnace, and are cooled in two steps through two chemical reactions, namely a gasification reaction and a pyrolysis reaction, and the method comprises the following specific steps:
(1) high temperature particle waste heat recovery
High-temperature particles (the particle diameter is 1 mm-10 mm) at 1100 ℃ enter the gasification furnace 1 through the high-temperature particle feeding device 7, pulverized coal is dried and then enters the gasification furnace 1 through the gasification furnace fuel nozzle 9 under the carrying of a gasification agent, and the inside of the high-temperature particle feeding device 7 is cooled by water cooling. The high-temperature particles move from top to bottom in the gasification furnace 1, and the gasification reaction quickly absorbs the heat of the particles and generates coal gas; the high temperature pellet temperature rapidly decreased to 700 ℃. And then, the particles and the generated coal slag after primary temperature reduction enter a medium-low temperature particle feeding device 11 of the pyrolysis furnace 2 through a particle outlet 10 of the gasification furnace.
CO in gasifying agent2The molar ratio of the carbon to the C element in the coal powder is CO2The ratio of/C is 1: 1. The mass ratio of the high-temperature particles to the C element in the coal powder is 1: 0.02.
(2) Middle and low temperature particle waste heat recovery
After the primary cooling, the particles and the coal dust at 700 ℃ enter the pyrolysis furnace 2 through the medium-low temperature particle feeding device 11 and the pyrolysis furnace fuel nozzle 12 respectively. In the pyrolysis furnace, pulverized coal: the mass ratio of the particles after primary temperature reduction is 0.8: 1. The particles move from top to bottom in the pyrolysis furnace, and the stirring device 13 fully stirs and mixes the coal powder and the particles inside. The coal powder rapidly absorbs the heat of the particles through pyrolysis reaction to generate solid semicoke and pyrolysis gas. At the same time, the pellet temperature was further cooled and the temperature was reduced to 120 ℃. The cooled particles and the semicoke produced after pyrolysis enter the solid separator 3 through a particle outlet.
After gas produced in the pyrolysis and gasification processes is mixed, semicoke and ash carried out by the gas are separated by the cyclone separator 4, the gas-liquid separator 5 separates condensation tar in the gas by cooling, the gas is further purified into clean gas by the gas purifier 6, the yield of the clean gas is 32%, and the calorific value of the clean gas is about 7000kJ/m3。
(3) Solids separation
And (4) screening and separating the cooled particle and semicoke mixture in a solid separator 3 according to different particle sizes. The yield of the solid semicoke is 21 percent, the semicoke components and the mass percentage content are 0.79 percent of water, 12.2 percent of volatile components, 78.2 percent of fixed carbon and 8.8 percent of ash.
In this example, the thermal efficiency was 84%,
Figure BDA0002319584860000112
the efficiency was 77%.
Example 2
The schematic structural diagram of the cascade waste heat recovery device utilizing pyrolysis and gasification of the solid particle heat carrier is shown in fig. 4, the method for cascade waste heat recovery by adopting the device is shown in fig. 3, and the process flow diagram is shown in fig. 3.
Compared with the embodiment 1, the difference is that:
(1) in the technical method, the fuel in the gasification furnace 1 in the embodiment 2 is the semicoke generated in the pyrolysis furnace 2, and the device structure is that the outlet material of the solid separator 3 enters the gasification furnace fuel nozzle 9 through the lifting device.
(2) In example 2, the products in the gasification furnace 1 were combustible gas and porous coke, and the specific surface area of the porous coke was 1100m2More than g. The combustible gas passes through a cyclone separator, a gas-liquid separator and a purifier to remove volatile components and condensable tar to obtain clean gas, the yield of the clean gas is 30%, and the calorific value of the clean gas is 5000kJ/m3。
(3) Example 2 the gasifying agent is boiler flue gas, and the components and contents thereof are CO2 12.8％，N2 77.1％，O26.1％，CO 0.06％，H2O3%, and the other 0.04%.
(4) Example 2 CO in flue gas in gasifier 12The molar ratio of the carbon to the C element in the coal powder is CO2C0.2: 1. The mass ratio of the high-temperature particles in the gasification furnace to the element C of the pulverized coal is 1: 0.05.
(6) The temperature of the particles after primary cooling is 600 ℃, the mass ratio of the particles after primary cooling to the C element in the coal powder in the pyrolysis furnace is 0.5: 1.
the cooled mixture of the particles and the semicoke is screened and separated in a solid separator 3 according to different particle sizes, the temperature of the cooled particles is 100 ℃, the yield of the solid semicoke is 23%, the content of the semicoke components and the content of the semicoke components by mass are 0.82%, the volatile matter is 11.7%, the fixed carbon is 77.1%, and the ash content is 10.3%.
In this example, the thermal efficiency was 80%,
Figure BDA0002319584860000113
the efficiency was 70%.
Example 3
The difference from example 1 is that:
(1) in example 3, the high-temperature particles were steel slag having a temperature of 1200 ℃ and the main components thereof are shown in Table 6.
TABLE 6 Steel slag particles chemical composition%
Figure BDA0002319584860000111
(2) In example 3, the clean gas yield was 33%, and the clean gas calorific value was about 6000kJ/m3；
(4) In example 3, the gasifying agent was flue gas of a certain kiln, and the components and content thereof were CO2 30.8％，N2 60.1％，O20.6％，CO 3.2％，H2O 5％，SO20.26% and the other 0.04%.
(5) In example 3, CO in flue gas of the gasification furnace 12The molar ratio of the carbon to the C element in the coal powder is CO2C1: 1. The mass ratio of the high-temperature particles to the coal powder C element is 1:0.05, and the temperature of the particles is 800 ℃ after the primary cooling.
In the pyrolysis furnace, the mass ratio of the particles after primary cooling to the C element in the coal powder is 0.8: 1-;
the obtained cooled particles and the semi-coke mixture are screened and separated in a solid separator 3 according to different particle sizes. After cooling, the particle temperature is 150 ℃, the yield of the solid semicoke is 20%, the semicoke components and the mass percentage content are 0.69% of moisture, 12.5% of volatile components, 79.1% of fixed carbon and 7.8% of ash.
In this example, the thermal efficiency was 82%,
Figure BDA0002319584860000121
the efficiency was 74%.

Claims (3)

1. The method for recovering the cascade waste heat by utilizing the pyrolysis gasification of the solid particle heat carrier is characterized by adopting a cascade waste heat recovery device utilizing the pyrolysis gasification of the solid particle heat carrier, wherein the cascade waste heat recovery device comprises a gasification furnace, a pyrolysis furnace, a solid separator and a flue gas treatment system, and the method comprises the following steps of: the gasification furnace, the pyrolysis furnace and the solid separator are sequentially connected, the gasification furnace is converged with a flue outlet of the pyrolysis furnace and is connected with a flue gas treatment system, and the solid separator is connected with a gasification furnace fuel nozzle through a lifting device;
the method comprises the following steps:
step 1, recovering waste heat of high-temperature particles:
the method comprises the following steps that high-temperature particles enter a gasification furnace, carbon-containing solid waste materials A enter the gasification furnace under the carrying of a gasification agent, the high-temperature particles move from top to bottom in the gasification furnace, the gasification agent and the carbon-containing solid waste materials A are subjected to gasification reaction in the furnace to generate combustible gas, and particles after primary cooling are obtained, wherein the temperature of the high-temperature particles is 900-1200 ℃, and the gasification reaction components in the gasification agent are as follows according to the mol ratio: c element =1:1 in the carbon-containing solid waste material A, and the mass ratio of the high-temperature particles is as follows: the carbon-containing solid waste material A contains C element =1:0.02, the high-temperature particles are blast furnace slag particles or steel slag particles discharged from steel smelting, the particle size is 1-10 mm, and the carbon-containing solid waste material A comprises the following components in parts by weight: the blast furnace slag particles comprise 41.21 percent of CaO, 8.22 percent of MgO and SiO by mass percentage2 34.38%，Al2O3 11.05%，Fe2O3 2.78%，TiO2 0.35%, the rest is other; the steel slag particles comprise, by mass, CaO 41.18%, MgO 9.26%, and SiO2 20.49%，Al2O3 3.08%，Fe2O3 20.35%, the balance others; the gasification agent is rich in CO2Flue gas, said CO being rich2The flue gas is CO-containing gas generated by industrial furnaces or boilers2CO in exhaust gas and flue gas2The content is 10-40%, and the content of N is 60-90%; the carbon element content of the carbon-containing solid waste material A is 20-70%;
step 2, recovering waste heat of medium-low temperature particles:
after primary cooling, the particles and the carbon-containing solid waste material B enter a pyrolysis furnace, and the carbon-containing solid waste material B is prepared by the following steps: 1, moving the particles in a pyrolysis furnace from top to bottom, and carrying out pyrolysis reaction on the carbon-containing solid waste material B in the furnace to generate pyrolysis gas and solid semicoke and obtain the cooled particles, wherein the temperature of the particles after primary cooling is 500-800 ℃, and the content of carbon elements in the carbon-containing solid waste material A is 20-70%;
the carbon-containing solid waste material A or B is coal powder, biomass, sludge or plastics;
the pyrolysis gas comprises coal gas, the pyrolysis gas is converged with the combustible coal gas obtained in the step 1, the condensable tar in the pyrolysis gas and the semicoke and ash in the combustible coal gas are separated through a gas-liquid separator, the smoke and dust are separated through a purifier, the clean coal gas is obtained, and the heat value of the clean coal gas is 5000-7000kJ/m3；
Step 3, solid separation:
the cooled mixture of the particles and the solid semicoke enters a solid separator, the solid separator is used for screening and separating to obtain the cooled particles and the cooled solid semicoke, wherein the solid semicoke enters a gasification furnace and is used as fuel to provide heat for the gasification furnace, the yield of the solid semicoke is 20-23%, the content of fixed carbon in the solid semicoke is 77-79.1%, the step waste heat recovery method for carrying out pyrolysis gasification by utilizing a solid particle heat carrier has the advantages that after the step waste heat recovery, the heat efficiency reaches 84%, and the exergy efficiency is 77%.
2. The method for the step waste heat recovery by the pyrolysis and gasification of the solid particle heat carrier according to claim 1, wherein the method comprises the following steps: the flue gas treatment system comprises a cyclone separator, a gas-liquid separator and a purifier, and all the components are connected in sequence;
the gasification furnace is a fixed bed or a fluidized bed, and is provided with a particle feeding device, a gasification furnace fuel nozzle and a particle outlet;
the pyrolysis furnace is a fixed bed, and a stirring device is arranged in the pyrolysis furnace;
the particle outlet of the gasification furnace is connected with the particle feeding device of the pyrolysis furnace, and the particle outlet of the pyrolysis furnace is connected with the solid separator.
3. The method for the step waste heat recovery of the pyrolysis gasification by using the solid particle heat carrier, according to claim 1, wherein the carbon-containing solid waste material A or B needs to be dried before entering a pyrolysis furnace or a gasification furnace.
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