WO2021115028A1 - Cascade waste heat recovery apparatus and method for pyrolysis and gasification using solid particle heat carrier - Google Patents

Cascade waste heat recovery apparatus and method for pyrolysis and gasification using solid particle heat carrier Download PDF

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WO2021115028A1
WO2021115028A1 PCT/CN2020/128913 CN2020128913W WO2021115028A1 WO 2021115028 A1 WO2021115028 A1 WO 2021115028A1 CN 2020128913 W CN2020128913 W CN 2020128913W WO 2021115028 A1 WO2021115028 A1 WO 2021115028A1
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gasification
pyrolysis
solid
furnace
particles
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PCT/CN2020/128913
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French (fr)
Chinese (zh)
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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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青岛理工大学
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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

Definitions

  • the invention belongs to the technical field of waste heat recovery and energy saving technology, and specifically relates to a stepped waste heat recovery device and method that utilizes solid particle heat carrier pyrolysis and gasification.
  • metallurgical slag such as blast furnace slag, steel slag, copper slag, nickel slag, etc.
  • Its discharge temperature is high (>1200°C) and contains a lot of sensible heat.
  • the traditional treatment method for metallurgical slag is the water quenching method, which consumes a lot of water resources, and the environmental pollution caused by the slag flushing water is also serious.
  • blast furnace slag discharge temperature is about 1500°C
  • the sensible heat per ton of slag is about 60kg standard coal.
  • the output of blast furnace slag in my country in 2018 can reach 250 million tons, which is about 15 million tons of standard coal. Therefore, the realization of high-efficiency and clean waste heat recovery from solid waste in the metallurgical industry is the key to my country's industrial energy conservation and emission reduction.
  • the metallurgical slag dry granulation and waste heat recovery process do not consume new water.
  • the liquid high-temperature slag is converted into solid high-temperature (about 1100°C) particles through a granulation device (such as a rotating cup, a rotating drum, a rotating drum, a turntable, etc.), and then the high-temperature sensible heat of the particles is recovered through direct or indirect contact with the heat transfer medium .
  • a granulation device such as a rotating cup, a rotating drum, a rotating drum, a turntable, etc.
  • the current waste heat recovery process of high-temperature solid particles is mainly a physical method.
  • the method uses water, air, etc. as the heat exchange medium, and has the characteristics of a large number of energy conversion times and low waste heat recovery efficiency. After recovery, hot water, steam or hot air can be generated, and its quality is difficult to be substantially improved.
  • the thermal efficiency is 76%, The efficiency is 14.4% and 34.2%.
  • the chemical method mainly absorbs the high temperature sensible heat of the particles through a typical endothermic chemical reaction, and produces chemical products with higher product added value. This method converts the thermal energy of the particles into chemical energy and improves the recovery process effectiveness.
  • the purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art, and provide a stepped waste heat recovery device and method using solid particle heat carrier pyrolysis and gasification, which can realize the goal of high-efficiency recovery of high-temperature solid particle waste heat, and solve the problem of high-temperature solid particles.
  • Technical problems of difficult waste heat recovery and low recovery efficiency are to overcome the shortcomings of the above-mentioned prior art, and provide a stepped waste heat recovery device and method using solid particle heat carrier pyrolysis and gasification, which can realize the goal of high-efficiency recovery of high-temperature solid particle waste heat, and solve the problem of high-temperature solid particles.
  • the cascade waste heat recovery device for pyrolysis and gasification using solid particle heat carrier including gasification furnace, pyrolysis furnace, solid separator and flue gas treatment system, including:
  • the gasification furnace, the pyrolysis furnace and the solid separator are connected in sequence, and the gasification furnace and the flue outlet of the pyrolysis furnace are merged and connected to the flue gas treatment system.
  • the flue gas processing system includes a cyclone separator, a gas-liquid separator and a purifier, and each component is connected in sequence.
  • the gasification furnace is a fixed bed or a fluidized bed, and the gasification furnace 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 semi-coke mixture separated by the solid separator provides fuel for the gasifier.
  • the method of using a cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification to perform waste heat recovery includes the following steps:
  • Step 1 Waste heat recovery of high-temperature particles:
  • the high-temperature particles enter the gasification furnace, and the carbon-containing solid waste material A enters the gasification furnace with the gasification agent.
  • the high-temperature particles move from top to bottom in the gasification furnace under the action of their own gravity, and the gasification agent and the carbon-containing solid
  • the waste material A undergoes a gasification reaction in the furnace to generate combustible gas, and at the same time obtain pellets after cooling.
  • the temperature of the high-temperature pellets is 900-1200°C, molar ratio.
  • Step 2 Recovery of waste heat from medium and low temperature particles:
  • the particles and the carbon-containing solid waste material B enter the pyrolysis furnace.
  • the cooled mixture of particles and solid semi-coke enters the solid separator, where it is screened and separated to obtain cooled particles and solid semi-coke, wherein the solid semi-coke enters the gasification furnace and is used as fuel
  • the gasifier provides heat, the yield of the solid semi-coke is 20-23%, and the fixed carbon content in the solid semi-coke is 77-79.1%.
  • the high-temperature particles are blast furnace slag particles or steel slag particles discharged from iron and steel smelting, with a particle size of 1-10 mm, where:
  • the blast furnace slag particles include components and mass percentages: CaO 41.21%, MgO 8.22%, SiO 2 34.38%, Al 2 O 3 11.05%, Fe 2 O 3 2.78%, TiO 2 0.35%, the balance is others;
  • the steel slag particles include components and mass percentages of CaO 41.1 8%, MgO 9.26%, SiO 2 20.49%, Al 2 O 3 3.08%, Fe 2 O 3 20.35%, and the balance is others.
  • Step 1 the gasifying agent is steam, CO 2, CO 2 rich gas or air, CO 2 -containing flue gas of the CO 2 rich gas generated as boiler or industrial furnace, gasification agent in the gasification reaction components It is H 2 O, CO 2 / or O 2 .
  • the gasification agent is CO 2 rich flue gas
  • the CO 2 content in the flue gas is 10-40%
  • the N content is 60-90%.
  • the gasification reaction quickly absorbs the heat of the particles and produces combustible gas; at the same time, the temperature of the high-temperature particles is rapidly cooled, and the temperature of the particles after a cooling is 500-800°C, and the particles enter through the particle outlet after a cooling. Pyrolysis furnace pellet feeding device.
  • the combustible gas carries semi-coke and ash.
  • the carbon-containing solid waste material A or B is industrial, agricultural and biological carbon-containing waste materials such as coal powder or biomass or sludge or plastic or rubber, and its carbon content is 20-70%.
  • the carbon-containing solid waste material A or B needs to be dried before entering the pyrolysis furnace or gasification furnace.
  • the carbon-containing solid waste material is pulverized coal.
  • the pyrolysis reaction quickly absorbs the heat of the particles after a cooling, and the temperature of the particles is further cooled after the cooling, and the temperature of the particles after cooling is less than or equal to 200°C.
  • the cooled particles and the solid semi-coke produced after pyrolysis enter the solid separator through the particle outlet.
  • the pyrolysis gas includes coal gas
  • the pyrolysis gas is combined with the combustible gas obtained in step 1
  • the condensable tar in the pyrolysis gas and the semi-coke and ash in the combustible gas are separated by a gas-liquid separator.
  • the smoke and dust are separated by the purifier to obtain clean gas.
  • the calorific value of clean gas is 5000-7000kJ/m 3 .
  • the use of the process system and method can efficiently recover the waste heat of solid particles, and increase the waste heat recovery efficiency of solid particles to 80-84%, and the efficiency to 70-77%;
  • This method can convert the waste heat of solid particles into flammable clean gas with a calorific value of 5000-7000kJ/3 , solid semi-coke with a fixed carbon content of 77-79.1% and other high value-added products;
  • FIG. 1 is a process flow diagram of a stepped waste heat recovery method using solid particle heat carrier pyrolysis and gasification according to Embodiment 1 of the present invention
  • FIG. 2 is a schematic structural diagram of a cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification according to Embodiment 1 of the present invention
  • FIG. 3 is a process flow diagram of a stepped waste heat recovery method using solid particle heat carrier pyrolysis and gasification according to Embodiment 2 of the present invention
  • FIG. 4 is a schematic structural diagram of a stepped waste heat recovery device using solid particle heat carrier pyrolysis and gasification according to Embodiment 2 of the present invention; among them:
  • the following takes 1kg slag particles as an example, and calculates the required materials and products in the process of gasification and pyrolysis according to the law of conservation of mass and energy.
  • the fuel in the gasification and pyrolysis furnace is pulverized coal.
  • the specific heat capacity C m2 of pulverized coal is 1.1kJ/(kg ⁇ °C), and the mass of pulverized coal is expressed in m 2 .
  • the outlet temperature of the coal gas produced by the gasifier is 800°C; the outlet temperature of the pyrolysis gas produced by the pyrolysis furnace is 300°C.
  • the carbon conversion rate and pyrolysis conversion rate in the gasification process are calculated as 100%.
  • the calorie income items are as follows:
  • the calorie expenditure items are as follows:
  • the decomposition heat of coal is calculated according to 448kJ/(kg), and the thermal decomposition products of coal are calculated according to CO and H 2.
  • the C element in the pulverized coal is transformed into fixed carbon and CO, and the H element is completely transformed into H 2 .
  • the overall thermal efficiency of the process system composed of gasifier and pyrolysis furnace can reach 84.7%.
  • the efficiency can reach 77.4%.
  • the cascade waste heat recovery device for pyrolysis and gasification using solid particle heat carrier including gasification furnace, pyrolysis furnace, solid separator and flue gas treatment system, including:
  • the gasification furnace, the pyrolysis furnace and the solid separator are connected in sequence, and the gasification furnace and the flue outlet of the pyrolysis furnace are merged and connected to the flue gas treatment system.
  • the flue gas processing system includes a cyclone separator, a gas-liquid separator and a purifier, and each component is connected in sequence.
  • the gasification furnace is a fixed bed or a fluidized bed, and the gasification furnace 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 semi-coke mixture separated by the solid separator provides fuel for the gasifier.
  • the method of using a cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification to perform waste heat recovery includes the following steps:
  • Step 1 Waste heat recovery of high-temperature particles:
  • the high-temperature particles enter the gasification furnace, and the carbon-containing solid waste material A enters the gasification furnace with the gasification agent.
  • the high-temperature particles move from top to bottom in the gasification furnace under the action of their own gravity, and the gasification agent and the carbon-containing solid
  • the waste material A undergoes a gasification reaction in the furnace to generate combustible gas, and at the same time obtain pellets after cooling.
  • the temperature of the high-temperature pellets is 900-1200°C, molar ratio.
  • Step 2 Recovery of waste heat from medium and low temperature particles:
  • the particles and the carbon-containing solid waste material B enter the pyrolysis furnace.
  • the cooled mixture of particles and solid semi-coke enters the solid separator, where it is screened and separated to obtain cooled particles and solid semi-coke, wherein the solid semi-coke enters the gasification furnace and is used as fuel
  • the gasifier provides heat, the yield of the solid semi-coke is 20-23%, and the fixed carbon content in the solid semi-coke is 77-79.1%.
  • the high-temperature particles are blast furnace slag particles or steel slag particles discharged from iron and steel smelting, with a particle size of 1-10 mm, where:
  • the blast furnace slag particles include components and mass percentages: CaO 41.21%, MgO 8.22%, SiO 2 34.38%, Al 2 O 3 11.05%, Fe 2 O 3 2.78%, TiO 2 0.35%, the balance is others;
  • the steel slag particles include components and mass percentages of CaO 41.1 8%, MgO 9.26%, SiO 2 20.49%, Al 2 O 3 3.08%, Fe 2 O 3 20.35%, and the balance is others.
  • Step 1 the gasifying agent is steam, CO 2, CO 2 rich gas or air, CO 2 -containing flue gas of the CO 2 rich gas generated as boiler or industrial furnace, gasification agent in the gasification reaction components It is H 2 O, CO 2 / or O 2 .
  • the gasification agent is CO 2 rich flue gas
  • the CO 2 content in the flue gas is 10-40%
  • the N content is 60-90%.
  • the gasification reaction quickly absorbs the heat of the particles and produces combustible gas; at the same time, the temperature of the high-temperature particles is rapidly cooled, and the temperature of the particles after a cooling is 500-800°C, and the particles enter through the particle outlet after a cooling. Pyrolysis furnace pellet feeding device.
  • the combustible gas carries semi-coke and ash.
  • the carbon-containing solid waste material A or B is industrial, agricultural and biological carbon-containing waste materials such as coal powder or biomass or sludge or plastic or rubber, and its carbon content is 20-70%.
  • the carbon-containing solid waste material A or B needs to be dried before entering the pyrolysis furnace or gasification furnace.
  • the carbon-containing solid waste material is pulverized coal.
  • the pyrolysis reaction quickly absorbs the heat of the particles after a cooling, and the temperature of the particles is further cooled after the cooling, and the temperature of the particles after cooling is less than or equal to 200°C.
  • the cooled particles and the solid semi-coke produced after pyrolysis enter the solid separator through the particle outlet.
  • the pyrolysis gas includes coal gas
  • the pyrolysis gas is combined with the combustible gas obtained in step 1
  • the condensable tar in the pyrolysis gas and the semi-coke and ash in the combustible gas are separated by a gas-liquid separator.
  • the dust is separated by the purifier to obtain clean gas.
  • the calorific value of clean gas is 5000-7000kJ/m 3 .
  • the slag used in the implementation of the present invention comes from the slag discharge of a domestic iron and steel enterprise blast furnace, and the main components are shown in Table 5.
  • the schematic diagram of the cascade waste heat recovery device using solid particle heat carrier pyrolysis gasification is shown in Figure 2, including gasification furnace 1, pyrolysis furnace 2, solid separator 3 and its auxiliary equipment, pyrolysis furnace 2, gasification furnace 1 Mainly composed of furnace body, feeding device system and flue gas processing device system.
  • the feeding device system is provided with a high particle feeding device 7, a medium and 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; flue gas
  • the treatment system is provided with a cyclone separator 4, a gas-liquid separator 5, and a purifier 6.
  • a stirring device 13 is provided in the pyrolysis furnace.
  • the gasification furnace 1, the pyrolysis furnace 2, and the solid separator 3 are respectively connected in sequence.
  • the particle outlet 10 of the gasification furnace is connected with the low-temperature particle feeding device 11 in the pyrolysis furnace, and the particle outlet 14 of the pyrolysis furnace is connected with the solid separator 3.
  • the flue outlets of the gasification furnace 1 and the pyrolysis furnace 2 merge and are connected to 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 pulverized coal type in the fluidized bed 1 is anthracite; the pyrolysis furnace 2 is a fixed bed, and the pyrolysis furnace 2 is lignite.
  • the coal powder in the two devices needs to be dried and pulverized to below 100 mesh before entering.
  • the incompletely combusted solid is obtained, and the incompletely combusted solid is collected by the silo.
  • the silo is collected in a funnel shape and transported to the gasification furnace through a transportation device, and enters the gasification furnace from the fuel nozzle of the gasification furnace.
  • the gasification agent mentioned in gasifier 1 is a lime kiln rich in CO 2 waste gas, the composition and content are CO 2 32.2%, N 2 59.6, O 2 1.8%, CO 2.6%, H 2 O 3%, and others 2.6% .
  • the process flow chart of the method for cascade waste heat recovery using the above-mentioned device is shown in Figure 1.
  • the process is mainly composed of three parts: gasification, pyrolysis and separation.
  • the main raw materials of the gasifier are pulverized coal and 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 flow through the gasification furnace and the pyrolysis furnace respectively, and are cooled in two steps through the two chemical reactions of the gasification reaction and the pyrolysis reaction.
  • the specific steps are as follows:
  • 1100°C high-temperature particles enter the gasification furnace 1 through the high-temperature particle feeding device 7.
  • the pulverized coal After the pulverized coal is dried, it enters the gasification furnace through the gasification furnace fuel nozzle 9 with the gasification agent.
  • the furnace 1 is cooled by water cooling in the high-temperature pellet feeding device 7.
  • 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 temperature of the high-temperature particles is rapidly reduced to 700°C.
  • the particles and the generated coal slag after the primary cooling enter the medium and low temperature particle feeding device 11 of the pyrolysis furnace 2 through the particle outlet 10 of the gasifier.
  • the molar ratio of CO 2 in coal gasification agent in the elements of C CO 2 / C is 1: 1.
  • the ratio of the mass of high-temperature particles to the mass of C in the coal powder is 1:0.02.
  • the 700°C particles and coal powder enter the pyrolysis furnace 2 through the medium and low temperature particle feeding device 11 and the pyrolysis furnace fuel nozzle 12 respectively.
  • the mass ratio of pulverized coal: particles after one cooling 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 pulverized coal and the particles inside.
  • the pulverized coal quickly absorbs the heat of the particles through the pyrolysis reaction to generate solid semi-coke and pyrolysis gas.
  • the temperature of the pellets was further cooled, and the temperature was reduced to 120°C.
  • the cooled particles and the semi-coke produced after pyrolysis enter the solid separator 3 through the particle outlet.
  • the gas produced in the pyrolysis and gasification process is mixed and passed through the cyclone 4 to separate the semi-coke and ash carried by the coal gas.
  • the gas-liquid separator 5 separates the condensable tar in the coal gas by cooling and reducing the temperature, and the gas is purified.
  • the device 6 further purifies the gas into clean gas.
  • the clean gas yield is 32%, and the heating value of the clean gas is about 7000kJ/m 3 .
  • the cooled particle and semi-coke mixture is sieved and separated in the solid separator 3 according to the size of the particle size.
  • the solid semi-coke yield is 21%, the semi-coke component and mass percentage are 0.79% moisture, 12.2% volatile, 78.2% fixed carbon, and 8.8% ash.
  • the thermal efficiency is 84%, The efficiency is 77%.
  • FIG. 4 The schematic diagram of the structure of the cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification is shown in FIG. 4, and the process flow chart of the method for cascade waste heat recovery using the above device is shown in FIG.
  • the fuel in the gasification furnace 1 in Example 2 is semi-coke produced in the pyrolysis furnace 2.
  • the outlet material of the solid separator 3 enters the gasification furnace fuel nozzle 9 through a lifting device.
  • the products in the gasifier 1 in Example 2 are combustible gas and porous coke, and the specific surface area of the porous coke is above 1100 m 2 /g.
  • the combustible gas passes through the cyclone separator, gas-liquid separator and purifier to remove volatiles and condensable tar to obtain clean gas.
  • the yield of clean gas is 30%, and the calorific value of clean gas is 5000kJ/m 3 .
  • the gasification agent in Example 2 is a certain boiler flue gas, and its composition and content are CO 2 12.8%, N 2 77.1%, O 2 6.1%, CO 0.06%, H 2 O 3%, and others 0.04%.
  • the ratio of the mass of high-temperature particles in the gasifier to the mass of pulverized coal C element is 1:0.05.
  • the temperature of the particles after the first cooling is 600°C.
  • the ratio of the particle mass to the C element mass in the coal powder after the first cooling is 0.5:1.
  • the cooled particles and semi-coke mixture are sieved and separated in the solid separator 3 according to the different particle sizes.
  • the temperature of the particles after cooling is 100°C
  • the solid semi-coke yield is 23%
  • the semi-coke component and quality are 100%.
  • the component content is 0.82% moisture, 11.7% volatile, 77.1% fixed carbon, and 10.3% ash.
  • the thermal efficiency is 80%, The efficiency is 70%.
  • Example 3 the high-temperature particles are steel slag, the temperature of the steel slag is 1200°C, and the main components are shown in Table 6.
  • Example 3 the clean gas production rate is 33%, and the clean gas heating value is about 6000 kJ/m 3 ;
  • the gasification agent is a certain furnace flue gas
  • the composition and content are CO 2 30.8%, N 2 60.1%, O 2 0.6%, CO 3.2%, H 2 O 5%, SO 2 0.26 %, other 0.04%.
  • the ratio of the particle mass to the C element mass in the pulverized coal after cooling once is 0.8:1;
  • the obtained cooled particle and semi-coke mixture is sieved and separated in the solid separator 3 according to the difference in particle size.
  • the pellet temperature is 150°C
  • the solid semi-coke yield is 20%
  • the semi-coke component and mass percentage are 0.69% moisture, 12.5% volatile, 79.1% fixed carbon, and 7.8% ash.
  • the thermal efficiency is 82%, The efficiency is 74%.

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Abstract

The present invention relates to a cascade waste heat recovery apparatus and method for pyrolysis and gasification using a solid particle heat carrier. The apparatus comprises a gasifier, a pyrolysis furnace, a solid separator, and a flue gas treatment system. The gasifier, the pyrolysis furnace, and the solid separator are sequentially connected. The gasifier and a flue outlet of the pyrolysis furnace are converged and connected to the flue gas treatment system. The method comprises: high-temperature particles enter the gasifier, and a carbon-containing solid waste material A enters the gasifier by being carried in a gasification agent, and undergoes a gasification reaction with the gasification agent to generate combustible coal gas and primary cooled particles; the cooled particles and a carbon-containing solid waste material B enter the pyrolysis furnace for a pyrolysis reaction to generate pyrolysis gas and solid semicoke; after sieving, the yield of the solid semicoke is 20-23%, the fixed-carbon content thereof is increased to 77-79.1%, and the solid semicoke serves as a gasifier fuel. According to the present invention, the waste heat recovery efficiency of solid particles is increased to 80-84%, the efficiency is increased to 70-77%, combustible clean coal gas having a calorific value of 5,000-7,000 kJ/m3 can be obtained, and CO2 emissions are decreased.

Description

利用固体颗粒热载体热解气化的梯级余热回收装置及方法Cascade waste heat recovery device and method using solid particle heat carrier pyrolysis and gasification 技术领域：Technical field:
本发明属于余热回收及节能技技术领域，具体涉及利用固体颗粒热载体热解气化的梯级余热回收装置及方法。The invention belongs to the technical field of waste heat recovery and energy saving technology, and specifically relates to a stepped waste heat recovery device and method that utilizes solid particle heat carrier pyrolysis and gasification.
背景技术：Background technique:
冶金、建材、化工等行业的生产工艺具有大量高温固体散装料及固体颗粒物，如，烧结矿、球团矿及直接还原铁等。此外，冶金渣(如，高炉渣、钢渣、铜渣、镍渣等)等是金冶炼过程排出的副产品，其排出温度高(>1200℃)，蕴含有大量的显热。目前对于冶金渣传统的处理方式为水淬法，该种处理方式消耗了大量水资源，而且冲渣水所引起的环境污染也比较严重。仅以高炉渣为例，高炉渣出炉温度为1500℃左右，吨渣显热约合60kg标煤。我国高炉渣2018年产量可达2.5亿吨，约合1500万吨标准煤。因此，实现冶金工业固废的高效清洁余热回收是我国工业节能减排的关键。The production process of metallurgy, building materials, chemical industry and other industries has a large number of high-temperature solid bulk materials and solid particles, such as sintered ore, pellets and direct reduced iron. In addition, metallurgical slag (such as blast furnace slag, steel slag, copper slag, nickel slag, etc.) is a by-product discharged from the gold smelting process. Its discharge temperature is high (>1200°C) and contains a lot of sensible heat. At present, the traditional treatment method for metallurgical slag is the water quenching method, which consumes a lot of water resources, and the environmental pollution caused by the slag flushing water is also serious. Taking blast furnace slag as an example, the blast furnace slag discharge temperature is about 1500°C, and the sensible heat per ton of slag is about 60kg standard coal. The output of blast furnace slag in my country in 2018 can reach 250 million tons, which is about 15 million tons of standard coal. Therefore, the realization of high-efficiency and clean waste heat recovery from solid waste in the metallurgical industry is the key to my country's industrial energy conservation and emission reduction.
为了实现冶金渣余热高效回收，改变传统方法导致的耗水、污染严重的现状，实现工艺流程末端的节能减排改造，冶金渣干法粒化及余热回收工艺是不消耗新水的前提下，通过粒化装置(如转杯、转筒、转鼓、转盘等)将液态高温炉渣转变为固体高温(1100℃左右)颗粒，继而通过与传热介质直接或者间接接触回收其颗粒的高温显热。随着粒化技术和工艺的发展成熟，干法粒化得到的渣粒球形度好，玻璃体含量高，便于后续余热回收和资源化利用。In order to achieve efficient recovery of metallurgical slag waste heat, change the current situation of serious water consumption and pollution caused by traditional methods, and realize energy-saving and emission reduction transformation at the end of the process, the metallurgical slag dry granulation and waste heat recovery process do not consume new water. The liquid high-temperature slag is converted into solid high-temperature (about 1100°C) particles through a granulation device (such as a rotating cup, a rotating drum, a rotating drum, a turntable, etc.), and then the high-temperature sensible heat of the particles is recovered through direct or indirect contact with the heat transfer medium . With the development and maturity of granulation technology and process, the slag particles obtained by dry granulation have good sphericity and high glass content, which is convenient for subsequent waste heat recovery and resource utilization.
目前的高温固体颗粒的余热回收工艺主要是物理法。该方法以水、空气等为换热介质，具有能源转换次数多、余热回收效率低的特点，回收后可产生热水或蒸汽或热空气等，其品质难以从本质上提高。采用物理法回收余热产生热水或热蒸汽，热效率为76％，
Figure PCTCN2020128913-appb-000001
效率为14.4％，34.2％。化学法主要是通过典型的吸热化学反应吸收颗粒的高温显热，产生具有较高产品附加值的化工产品。该方法将颗粒的热能转变为化学能，提高了回收过程
Figure PCTCN2020128913-appb-000002
效率。在现已公开的专利中，专利CN20190236543.6、CN201910305887.8、CN200910012471.3、CN201510283249.2等均是以熔渣为热载体，驱动煤气化反应制备合成气。 The current waste heat recovery process of high-temperature solid particles is mainly a physical method. The method uses water, air, etc. as the heat exchange medium, and has the characteristics of a large number of energy conversion times and low waste heat recovery efficiency. After recovery, hot water, steam or hot air can be generated, and its quality is difficult to be substantially improved. Using physical method to recover waste heat to produce hot water or hot steam, the thermal efficiency is 76%,
Figure PCTCN2020128913-appb-000001
The efficiency is 14.4% and 34.2%. The chemical method mainly absorbs the high temperature sensible heat of the particles through a typical endothermic chemical reaction, and produces chemical products with higher product added value. This method converts the thermal energy of the particles into chemical energy and improves the recovery process
Figure PCTCN2020128913-appb-000002
effectiveness. Among the published patents, the patents CN20190236543.6, CN201910305887.8, CN200910012471.3, CN201510283249.2, etc. all use molten slag as a heat carrier to drive the coal gasification reaction to prepare synthesis gas.
因此，如何高效回收工业生产中高温颗粒显热，降低生产过程的能耗，开发一种高效回收高温固体颗粒的余热回收方法是我国急需解决的问题。这也引起了国内外高校、研究所、企业的高度关注，但是截止目前尚未有关于该领域相关技术推广应用的报道。Therefore, how to efficiently recover the sensible heat of high-temperature particles in industrial production, reduce the energy consumption of the production process, and develop a waste heat recovery method for efficiently recovering high-temperature solid particles is an urgent problem in my country. This has also attracted great attention from universities, research institutes, and enterprises at home and abroad, but so far there is no report on the promotion and application of related technologies in this field.
发明内容：Summary of the invention:
本发明的目的是克服上述现有技术存在的不足，提供一种利用固体颗粒热载体热解气化的梯级余热回收装置及方法，可以实现高温固体颗粒余热高效回收的目标，解决了高温固 体颗粒余热回收难及回收效率低的技术问题。The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art, and provide a stepped waste heat recovery device and method using solid particle heat carrier pyrolysis and gasification, which can realize the goal of high-efficiency recovery of high-temperature solid particle waste heat, and solve the problem of high-temperature solid particles. Technical problems of difficult waste heat recovery and low recovery efficiency.
为实现上述目的，本发明采用以下技术方案：In order to achieve the above objectives, the present invention adopts the following technical solutions:
利用固体颗粒热载体热解气化的梯级余热回收装置，包括气化炉，热解炉，固体分离器及烟气处理***，其中：The cascade waste heat recovery device for pyrolysis and gasification using solid particle heat carrier, including gasification furnace, pyrolysis furnace, solid separator and flue gas treatment system, including:
所述气化炉，热解炉和固体分离器依次连接，气化炉与热解炉的烟道出口汇合并与烟气处理***连接。The gasification furnace, the pyrolysis furnace and the solid separator are connected in sequence, and the gasification furnace and the flue outlet of the pyrolysis furnace are merged and connected to the flue gas treatment system.
所述烟气处理***包括旋风分离器、气液分离器及净化器，各部件顺次连接。The flue gas processing system includes a cyclone separator, a gas-liquid separator and a purifier, and each component is connected in sequence.
所述气化炉为固定床或流化床，所述气化炉设有颗粒给料装置，气化炉燃料喷嘴和颗粒出口。The gasification furnace is a fixed bed or a fluidized bed, and the gasification furnace is provided with a particle feeding device, a gasification furnace fuel nozzle and a particle outlet.
所述热解炉为固定床，所述热解炉内设置有搅拌装置。The pyrolysis furnace is a fixed bed, and a stirring device is arranged in the pyrolysis furnace.
所述气化炉的颗粒出口与热解炉颗粒给料装置连接，热解炉的颗粒出口与固体分离器相连。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.
所述固体分离器通过提升装置与气化炉燃料喷嘴连接。固体分离器分离出的半焦混合物为气化炉提供燃料。The solid separator is connected with the fuel nozzle of the gasification furnace through a lifting device. The semi-coke mixture separated by the solid separator provides fuel for the gasifier.
采用利用固体颗粒热载体热解气化的梯级余热回收装置，进行余热回收的方法，包括以下步骤：The method of using a cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification to perform waste heat recovery includes the following steps:
步骤1，高温颗粒余热回收： Step 1. Waste heat recovery of high-temperature particles:
高温颗粒进入气化炉，含碳固废材料A在气化剂携带下进入气化炉，高温颗粒在自身重力的作用下在气化炉内自上而下运动，气化剂和含碳固废材料A在炉内发生气化反应，生成可燃煤气，同时获得一次降温后颗粒，其中，所述的高温颗粒温度为900～1200℃，按摩尔比，气化剂中气化反应成分：含碳固废材料A中C元素＝(0.2～1):1，按质量比，高温颗粒质量：含碳固废材料A中C元素＝1:(0.02～0.05)；The high-temperature particles enter the gasification furnace, and the carbon-containing solid waste material A enters the gasification furnace with the gasification agent. The high-temperature particles move from top to bottom in the gasification furnace under the action of their own gravity, and the gasification agent and the carbon-containing solid The waste material A undergoes a gasification reaction in the furnace to generate combustible gas, and at the same time obtain pellets after cooling. The temperature of the high-temperature pellets is 900-1200°C, molar ratio. The gasification reaction components in the gasification agent: C element in carbon solid waste material A=(0.2～1):1, according to mass ratio, mass of high temperature particles: C element in carbon solid waste material A=1:(0.02～0.05);
步骤2，中低温颗粒余热回收：Step 2: Recovery of waste heat from medium and low temperature particles:
一次降温后颗粒与含碳固废材料B进入热解炉，按质量比，含碳固废材料B：一次降温后颗粒＝(0.5～1):1，颗粒在热解炉内自上而下运动，含碳固废材料B在炉内发生热解反应，生成热解气和固体半焦，并获得冷却后颗粒。After a cooling, the particles and the carbon-containing solid waste material B enter the pyrolysis furnace. According to the mass ratio, the carbon-containing solid waste material B: After a cooling, the particles = (0.5-1):1, and the particles are from top to bottom in the pyrolysis furnace Movement, the carbon-containing solid waste material B undergoes a pyrolysis reaction in the furnace to generate pyrolysis gas and solid semi-coke, and obtain cooled particles.
步骤3，固体分离： Step 3. Solid separation:
冷却后的颗粒与固体半焦混合物进入固体分离器中，在固体分离器中进行筛分及分离，获得冷却后颗粒与固体半焦，其中，所述固体半焦进入气化炉，作为燃料为气化炉提供热量，所述固体半焦产率为20-23％，固体半焦中固定碳含量为77-79.1％。The cooled mixture of particles and solid semi-coke enters the solid separator, where it is screened and separated to obtain cooled particles and solid semi-coke, wherein the solid semi-coke enters the gasification furnace and is used as fuel The gasifier provides heat, the yield of the solid semi-coke is 20-23%, and the fixed carbon content in the solid semi-coke is 77-79.1%.
所述步骤1中，高温颗粒为钢铁冶炼排放的高炉渣颗粒或钢渣颗粒，粒径为1～10mm， 其中：In the step 1, the high-temperature particles are blast furnace slag particles or steel slag particles discharged from iron and steel smelting, with a particle size of 1-10 mm, where:
所述高炉渣颗粒包括组分及质量百分含量为CaO 41.21％，MgO 8.22％，SiO 2 34.38％，Al 2O 3 11.05％，Fe 2O 3 2.78％，TiO 2 0.35％，余量其他； The blast furnace slag particles include components and mass percentages: CaO 41.21%, MgO 8.22%, SiO 2 34.38%, Al 2 O 3 11.05%, Fe 2 O 3 2.78%, TiO 2 0.35%, the balance is others;
所述钢渣颗粒包括组分及质量百分含量为CaO 41.1 8％，MgO 9.26％，SiO 2 20.49％，Al 2O 3 3.08％，Fe 2O 3 20.35％，余量其他。 The steel slag particles include components and mass percentages of CaO 41.1 8%, MgO 9.26%, SiO 2 20.49%, Al 2 O 3 3.08%, Fe 2 O 3 20.35%, and the balance is others.
所述步骤1中，气化剂为水蒸气，CO 2，富CO 2气体或空气，所述富CO 2气体为工业炉窑或锅炉产生的含CO 2废气，气化剂中气化反应成分为H 2O、CO 2/或O 2。 Step 1, the gasifying agent is steam, CO 2, CO 2 rich gas or air, CO 2 -containing flue gas of the CO 2 rich gas generated as boiler or industrial furnace, gasification agent in the gasification reaction components It is H 2 O, CO 2 / or O 2 .
所述步骤1中，气化剂为富CO 2烟气，烟气中CO 2含量为10-40％，N含量为60-90％。 In the step 1, the gasification agent is CO 2 rich flue gas, the CO 2 content in the flue gas is 10-40%, and the N content is 60-90%.
所述步骤1中，气化反应快速吸收颗粒的热量，并产生可燃煤气；与此同时，高温颗粒温度被快速冷却，一次降温后颗粒温度为500～800℃，一次降温后颗粒通过颗粒出口进入热解炉的颗粒给料装置。In the step 1, the gasification reaction quickly absorbs the heat of the particles and produces combustible gas; at the same time, the temperature of the high-temperature particles is rapidly cooled, and the temperature of the particles after a cooling is 500-800℃, and the particles enter through the particle outlet after a cooling. Pyrolysis furnace pellet feeding device.
所述步骤1中，可燃煤气携带有半焦及灰分。In the step 1, the combustible gas carries semi-coke and ash.
所述步骤1中，气化炉气化反应的化学反应方程式如下：In the step 1, the chemical reaction equation of the gasification reaction of the gasifier is as follows:
C+CO 2(g)＝2CO(g)173.4kJ/mol(1) C+CO 2 (g)=2CO(g)173.4kJ/mol(1)
C+H 2O(g)＝CO(g)+H 2(g)135.6kJ/mol(2) C+H 2 O(g)=CO(g)+H 2 (g)135.6kJ/mol(2)
所述步骤1和2中，含碳固废材料A或B为煤粉或生物质或污泥或塑料或橡胶等工业、农业及生物含碳废弃材料，其碳元素含量在20-70％。In the steps 1 and 2, the carbon-containing solid waste material A or B is industrial, agricultural and biological carbon-containing waste materials such as coal powder or biomass or sludge or plastic or rubber, and its carbon content is 20-70%.
所述步骤1和2中，含碳固废材料A或B在进入热解炉或气化炉前需要进行干燥处理。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 gasification furnace.
所述步骤1和2中，含碳固废材料为煤粉。In the steps 1 and 2, the carbon-containing solid waste material is pulverized coal.
所述步骤2中，热解反应快速吸收一次降温后颗粒的热量，一次降温后颗粒温度被进一步冷却，冷却后颗粒温度≤200℃。冷却后的颗粒与热解后产生的固体半焦通过颗粒出口进入固体分离器。In the step 2, the pyrolysis reaction quickly absorbs the heat of the particles after a cooling, and the temperature of the particles is further cooled after the cooling, and the temperature of the particles after cooling is less than or equal to 200°C. The cooled particles and the solid semi-coke produced after pyrolysis enter the solid separator through the particle outlet.
所述步骤2中，热解气中包括煤气，热解气与步骤1获得的可燃煤气汇合，经气液分离器分离出热解气中的凝结性焦油和可燃煤气中的半焦与灰分，经净化器分离烟尘，获得洁净煤气。洁净煤气的热值在5000-7000kJ/m 3。 In the step 2, the pyrolysis gas includes coal gas, the pyrolysis gas is combined with the combustible gas obtained in step 1, and the condensable tar in the pyrolysis gas and the semi-coke and ash in the combustible gas are separated by a gas-liquid separator. The smoke and dust are separated by the purifier to obtain clean gas. The calorific value of clean gas is 5000-7000kJ/m 3 .
所述利用固体颗粒热载体进行热解气化的梯级余热回收方法，经过梯级余热回收后，热效率达80-84％，
Figure PCTCN2020128913-appb-000003
效率为70-77％。 In the cascade waste heat recovery method using solid particulate heat carrier for pyrolysis and gasification, after the cascade waste heat recovery, the thermal efficiency reaches 80-84%,
Figure PCTCN2020128913-appb-000003
The efficiency is 70-77%.
本发明的有益效果：The beneficial effects of the present invention:
(1)利用所述工艺***及方法可高效回收固体颗粒余热，将固体颗粒余热回收效率提高至80-84％，效率提高至70-77％；(1) The use of the process system and method can efficiently recover the waste heat of solid particles, and increase the waste heat recovery efficiency of solid particles to 80-84%, and the efficiency to 70-77%;
(2)该方法可将固体颗粒余热转换为热值为5000-7000kJ/ 3的可燃性洁净煤气、固定碳含量 在77-79.1％的固体半焦等具有高附加值产品； (2) This method can convert the waste heat of solid particles into flammable clean gas with a calorific value of 5000-7000kJ/3 , solid semi-coke with a fixed carbon content of 77-79.1% and other high value-added products;
(3)在保护环境、节约资源的同时，该***及方法采用富CO 2烟气为气化剂时，回收每kg炉渣颗粒余热，可减少温室气体CO 2 30L以上。 (3) While protecting the environment and saving resources, when the system and method use CO 2 rich flue gas as the gasification agent, the waste heat of each kg of slag particles can be recovered, and the greenhouse gas CO 2 can be reduced by more than 30L.
附图说明：Description of the drawings:
图1为本发明实施例1的利用固体颗粒热载体热解气化的梯级余热回收方法工艺流程图；FIG. 1 is a process flow diagram of a stepped waste heat recovery method using solid particle heat carrier pyrolysis and gasification according to Embodiment 1 of the present invention;
图2为本发明实施例1的利用固体颗粒热载体热解气化的梯级余热回收装置结构示意图；2 is a schematic structural diagram of a cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification according to Embodiment 1 of the present invention;
图3为本发明实施例2的利用固体颗粒热载体热解气化的梯级余热回收方法工艺流程图；3 is a process flow diagram of a stepped waste heat recovery method using solid particle heat carrier pyrolysis and gasification according to Embodiment 2 of the present invention;
图4为本发明实施例2的利用固体颗粒热载体热解气化的梯级余热回收装置结构示意图；其中：4 is a schematic structural diagram of a stepped waste heat recovery device using solid particle heat carrier pyrolysis and gasification according to Embodiment 2 of the present invention; among them:
1-气化炉，2-热解炉，3-固体分离器，4-旋风分离器，5-气液分离器，6-净化器，7-高温颗粒给料装置，8-料仓，9-气化炉燃料喷嘴，10-气化炉颗粒出口，11-中低温颗粒给料装置，12-热解炉燃料喷嘴，13-搅拌装置，14-热解炉颗粒出口。1-gasification furnace, 2-pyrolysis furnace, 3-solid separator, 4-cyclone separator, 5-gas-liquid separator, 6-purifier, 7-high temperature particle feeding device, 8-silo, 9 -Gasifier fuel nozzle, 10-gasifier particle outlet, 11-medium and low temperature particle feeding device, 12-pyrolysis furnace fuel nozzle, 13-stirring device, 14-pyrolysis furnace particle outlet.
具体实施方式：Detailed ways:
下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail below in conjunction with the embodiments.
下面以1kg炉渣颗粒为例，按照质量守恒及能量守恒定律对气化及热解过程中所需物料及生成的产物进行计算。The following takes 1kg slag particles as an example, and calculates the required materials and products in the process of gasification and pyrolysis according to the law of conservation of mass and energy.
计算条件如下：The calculation conditions are as follows:
气化炉内高温炉渣颗粒入口温度为1100℃，出口温度为700℃；热解炉内中低温炉渣颗粒入口温度为700℃，出口温度为100℃，炉渣比热容为C m1＝1.2kJ/(kg·℃)，炉渣颗粒质量用m1。 The inlet temperature of the high-temperature slag particles in the gasifier is 1100°C and the outlet temperature is 700°C; the inlet temperature of the medium and low temperature slag particles in the pyrolysis furnace is 700°C, the outlet temperature is 100°C, and the slag specific heat capacity is C m1 =1.2kJ/(kg ·℃), the mass of slag particles uses m1.
气化及热解炉内燃料均为煤粉，煤粉中C＝64.4％，H＝4.2％，O＝8.8％，灰分含量＝20％，固定碳含量为44.8％，挥发分含量为32.8％，煤粉比热容C m2为1.1kJ/(kg·℃)，煤粉质量用m 2表示。 The fuel in the gasification and pyrolysis furnace is pulverized coal. The pulverized coal contains C=64.4%, H=4.2%, O=8.8%, ash content=20%, fixed carbon content 44.8%, volatile content 32.8% , The specific heat capacity C m2 of pulverized coal is 1.1kJ/(kg·℃), and the mass of pulverized coal is expressed in m 2 .
气化剂为富CO 2烟气，烟气成分为(CO 2＝40％，N 2＝60％)，比热容用C m3表示，N 2比热容1.03kJ/(kg·℃)，CO 2比热容0.84kJ/(kg·℃)，气化剂质量用m 3表示。 The gasification agent is CO 2 rich flue gas, the flue gas composition is (CO 2 ＝40%, N 2 ＝60%), the specific heat capacity is expressed by C m3 , the specific heat capacity of N 2 is 1.03kJ/(kg·℃), and the specific heat capacity of CO 2 is 0.84 kJ/(kg·℃), the mass of gasification agent is expressed in m 3 .
气化炉产生的煤气出口温度为800℃；热解炉产生的热解气出口温度为300℃。The outlet temperature of the coal gas produced by the gasifier is 800°C; the outlet temperature of the pyrolysis gas produced by the pyrolysis furnace is 300°C.
气化过程碳转化率、热解转化率均按照100％计算。The carbon conversion rate and pyrolysis conversion rate in the gasification process are calculated as 100%.
(1)气化炉(1) Gasifier
根据能量守恒定律：炉渣释放的热量＝气化反应吸收的热量，煤气化反应所需煤粉的物质的量为：According to the law of conservation of energy: the heat released by the slag = the heat absorbed by the gasification reaction, and the amount of pulverized coal required for the coal gasification reaction is:
热量收入项如下：The calorie income items are as follows:
1)炉渣代入的物理热1) Physical heat substituted by slag
Qi n-1＝C m1×1×t 1＝1.2×1×(1100)kJ＝1320.0kJ(3) Qi n-1 ＝C m1 ×1×t 1 ＝1.2×1×(1100)kJ＝1320.0kJ(3)
2)煤粉带入的物理热2) Physical heat brought by pulverized coal
Qi n-2＝C m2×m 2×t 2＝1.1×m 2×(20)(4) Qi n-2 ＝C m2 ×m 2 ×t 2 ＝1.1×m 2 ×(20)(4)
3)气化剂带入的物理热3) Physical heat brought by the gasification agent
Qi n-3＝C m3×m 3×t 3＝0.954×m 3×(20)(5) Qi n-3 = C m3 ×m 3 ×t 3 =0.954×m 3 ×(20)(5)
热量支出项如下：The calorie expenditure items are as follows:
4)气化反应吸收的热量4) Heat absorbed by gasification reaction
Figure PCTCN2020128913-appb-000004
Figure PCTCN2020128913-appb-000004
5)颗粒带走物理热量5) The particles take away physical heat
Q out-2＝C m1×1×t 1'＝1.2×1×(700)kJ＝840.0kJ(7) Q out-2 = C m1 ×1×t 1 '=1.2×1×(700)kJ=840.0kJ(7)
6)煤渣带出的物理热6) Physical heat brought by cinder
Q out-3＝C m2×m 2×0.2×t 2'＝1.1×m 2×0.2×900＝198×m 2kJ(8) Q out-3 = C m2 ×m 2 ×0.2×t 2 '=1.1×m 2 ×0.2×900=198×m 2 kJ(8)
7)烟气带出的物理热7) Physical heat brought by the flue gas
Figure PCTCN2020128913-appb-000005
Figure PCTCN2020128913-appb-000005
根据煤粉与CO 2气化反应质量关系可得： According to the relationship between coal powder and CO 2 gasification reaction quality:
Figure PCTCN2020128913-appb-000006
Figure PCTCN2020128913-appb-000006
根据能量守恒定律，Q in＝Q out，联立方程，根据设定条件可计算出在气化炉中每处理1kg炉渣颗粒，需要消耗煤粉0.0296kg，产生CO 0.089kg(约合71L)，气化炉热效率为57.4％。若考虑烟气在冷却器余热回收，当烟气余热回收率为60％，则气化炉热效率可达82％。气化过程采用的富CO 2气化剂为工业炉窑或锅炉产生的含CO 2废气，即利用本发明的方法每处理1kg炉渣，就可以吸收0.07kg的CO 2废气，那么按照每年我国产生的2.5亿吨炉渣计算，用此方法每年就可以吸收CO 2高达1750万吨。气化炉物料投入量及产物产出量计算结果如表1所 示。 According to the law of conservation of energy, Q in ＝Q out , the simultaneous equation, according to the set conditions, can calculate that for every 1kg of slag particles processed in the gasifier, it needs to consume 0.0296kg of pulverized coal and produce 0.089kg of CO (about 71L). The thermal efficiency of the gasifier is 57.4%. If considering the waste heat recovery of the flue gas in the cooler, when the flue gas waste heat recovery rate is 60%, the thermal efficiency of the gasifier can reach 82%. CO 2 -containing waste gas CO 2 rich gasification gasification agent is produced using industrial boilers or furnaces, i.e. using a method of the present invention per 1kg of slag handling, can 0.07kg CO 2 absorption in the exhaust gas, so that the annual generation of Based on the calculation of 250 million tons of slag, this method can absorb up to 17.5 million tons of CO 2 each year. The calculation results of gasifier material input and product output are shown in Table 1.
表1气化炉中物料投入量及产物产出量计算结果Table 1 Calculation results of material input and product output in the gasifier
Figure PCTCN2020128913-appb-000007
Figure PCTCN2020128913-appb-000007
表2气化炉热收支平衡表Table 2 Gasifier heat balance sheet
Figure PCTCN2020128913-appb-000008
Figure PCTCN2020128913-appb-000008
(2)热解过程(2) Pyrolysis process
煤分解热按照448kJ/(kg)计算，煤热分解产物按照CO和H 2计算，煤粉中C元素转变为固定碳及CO，H元素完全转变为H 2。 The decomposition heat of coal is calculated according to 448kJ/(kg), and the thermal decomposition products of coal are calculated according to CO and H 2. The C element in the pulverized coal is transformed into fixed carbon and CO, and the H element is completely transformed into H 2 .
同理，按照上述计算方式，可得热解炉内物料投入量及产物产出量计算结果如表3所示。Similarly, according to the above calculation method, the calculation results of the material input and product output in the pyrolysis furnace are shown in Table 3.
表3热解炉中物料投入量及产物产出量计算结果Table 3 Calculation results of material input and product output in the pyrolysis furnace
Figure PCTCN2020128913-appb-000009
Figure PCTCN2020128913-appb-000009
表4热解炉热收支平衡表Table 4 Pyrolysis furnace heat balance sheet
Figure PCTCN2020128913-appb-000010
Figure PCTCN2020128913-appb-000010
根据设定条件可计算出在热解炉中每处理1kg炉渣颗粒，需要消耗煤粉1.263kg，产生CO 0.195kg(约合155L)，H 2 0.053kg(约合590L)，产生半焦0.818kg，热解炉的理论热效率为82.3％。
Figure PCTCN2020128913-appb-000011
效率的计算式如下。 According to the set conditions, it can be calculated that every 1kg of slag particles processed in the pyrolysis furnace needs to consume 1.263kg of coal powder, produce 0.195kg of CO (approximately 155L), H 2 0.053kg (approximately 590L), and produce 0.818kg of semi-coke , The theoretical thermal efficiency of the pyrolysis furnace is 82.3%.
Figure PCTCN2020128913-appb-000011
The calculation formula of efficiency is as follows.
Figure PCTCN2020128913-appb-000012
Figure PCTCN2020128913-appb-000012
通过整体计算，气化炉及热解炉组成的工艺***，整体热效率可达84.7％，
Figure PCTCN2020128913-appb-000013
效率可达77.4％。 Through overall calculation, the overall thermal efficiency of the process system composed of gasifier and pyrolysis furnace can reach 84.7%.
Figure PCTCN2020128913-appb-000013
The efficiency can reach 77.4%.
通过对利用固体颗粒热载体热解气化的梯级余热回收装置及方法中气化及热解部分的理论分析及计算可知，本发明为高温颗粒的梯级余热回收提供了崭新思路。The theoretical analysis and calculation of the gasification and pyrolysis parts of the cascade waste heat recovery device and method using solid particle heat carrier pyrolysis and gasification show that the present invention provides a new idea for the cascade waste heat recovery of high-temperature particles.
利用固体颗粒热载体热解气化的梯级余热回收装置，包括气化炉，热解炉，固体分离器及烟气处理***，其中：The cascade waste heat recovery device for pyrolysis and gasification using solid particle heat carrier, including gasification furnace, pyrolysis furnace, solid separator and flue gas treatment system, including:
所述气化炉，热解炉和固体分离器依次连接，气化炉与热解炉的烟道出口汇合并与烟气处理***连接。The gasification furnace, the pyrolysis furnace and the solid separator are connected in sequence, and the gasification furnace and the flue outlet of the pyrolysis furnace are merged and connected to the flue gas treatment system.
所述烟气处理***包括旋风分离器、气液分离器及净化器，各部件顺次连接。The flue gas processing system includes a cyclone separator, a gas-liquid separator and a purifier, and each component is connected in sequence.
所述气化炉为固定床或流化床，所述气化炉设有颗粒给料装置，气化炉燃料喷嘴和颗粒出口。The gasification furnace is a fixed bed or a fluidized bed, and the gasification furnace is provided with a particle feeding device, a gasification furnace fuel nozzle and a particle outlet.
所述热解炉为固定床，所述热解炉内设置有搅拌装置。The pyrolysis furnace is a fixed bed, and a stirring device is arranged in the pyrolysis furnace.
所述气化炉的颗粒出口与热解炉颗粒给料装置连接，热解炉的颗粒出口与固体分离器相连。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.
所述固体分离器通过提升装置与气化炉燃料喷嘴连接。固体分离器分离出的半焦混合物为气化炉提供燃料。The solid separator is connected with the fuel nozzle of the gasification furnace through a lifting device. The semi-coke mixture separated by the solid separator provides fuel for the gasifier.
采用利用固体颗粒热载体热解气化的梯级余热回收装置，进行余热回收的方法，包括以下步骤：The method of using a cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification to perform waste heat recovery includes the following steps:
步骤1，高温颗粒余热回收： Step 1. Waste heat recovery of high-temperature particles:
高温颗粒进入气化炉，含碳固废材料A在气化剂携带下进入气化炉，高温颗粒在自身重力的作用下在气化炉内自上而下运动，气化剂和含碳固废材料A在炉内发生气化反应，生成可燃煤气，同时获得一次降温后颗粒，其中，所述的高温颗粒温度为900～1200℃，按摩尔比，气化剂中气化反应成分：含碳固废材料A中C元素＝(0.2～1):1，按质量比，高温颗粒质量：含碳固废材料A中C元素＝1:(0.02～0.05)；The high-temperature particles enter the gasification furnace, and the carbon-containing solid waste material A enters the gasification furnace with the gasification agent. The high-temperature particles move from top to bottom in the gasification furnace under the action of their own gravity, and the gasification agent and the carbon-containing solid The waste material A undergoes a gasification reaction in the furnace to generate combustible gas, and at the same time obtain pellets after cooling. The temperature of the high-temperature pellets is 900-1200°C, molar ratio. The gasification reaction components in the gasification agent: C element in carbon solid waste material A=(0.2～1):1, according to mass ratio, mass of high temperature particles: C element in carbon solid waste material A=1:(0.02～0.05);
步骤2，中低温颗粒余热回收：Step 2: Recovery of waste heat from medium and low temperature particles:
一次降温后颗粒与含碳固废材料B进入热解炉，按质量比，含碳固废材料B：一次降温后颗粒＝(0.5～1):1，颗粒在热解炉内自上而下运动，含碳固废材料B在炉内发生热解反应，生成热解气和固体半焦，并获得冷却后颗粒。After a cooling, the particles and the carbon-containing solid waste material B enter the pyrolysis furnace. According to the mass ratio, the carbon-containing solid waste material B: After a cooling, the particles = (0.5-1):1, and the particles are from top to bottom in the pyrolysis furnace Movement, the carbon-containing solid waste material B undergoes a pyrolysis reaction in the furnace to generate pyrolysis gas and solid semi-coke, and obtain cooled particles.
步骤3，固体分离： Step 3. Solid separation:
冷却后的颗粒与固体半焦混合物进入固体分离器中，在固体分离器中进行筛分及分离，获得冷却后颗粒与固体半焦，其中，所述固体半焦进入气化炉，作为燃料为气化炉提供热量，所述固体半焦产率为20-23％，固体半焦中固定碳含量为77-79.1％。The cooled mixture of particles and solid semi-coke enters the solid separator, where it is screened and separated to obtain cooled particles and solid semi-coke, wherein the solid semi-coke enters the gasification furnace and is used as fuel The gasifier provides heat, the yield of the solid semi-coke is 20-23%, and the fixed carbon content in the solid semi-coke is 77-79.1%.
所述步骤1中，高温颗粒为钢铁冶炼排放的高炉渣颗粒或钢渣颗粒，粒径为1～10mm，其中：In the step 1, the high-temperature particles are blast furnace slag particles or steel slag particles discharged from iron and steel smelting, with a particle size of 1-10 mm, where:
所述高炉渣颗粒包括组分及质量百分含量为CaO 41.21％，MgO 8.22％，SiO 234.38％，Al 2O 3 11.05％，Fe 2O 3 2.78％，TiO 2 0.35％，余量其他； The blast furnace slag particles include components and mass percentages: CaO 41.21%, MgO 8.22%, SiO 2 34.38%, Al 2 O 3 11.05%, Fe 2 O 3 2.78%, TiO 2 0.35%, the balance is others;
所述钢渣颗粒包括组分及质量百分含量为CaO 41.1 8％，MgO 9.26％，SiO 2 20.49％，Al 2O 3 3.08％，Fe 2O 3 20.35％，余量其他。 The steel slag particles include components and mass percentages of CaO 41.1 8%, MgO 9.26%, SiO 2 20.49%, Al 2 O 3 3.08%, Fe 2 O 3 20.35%, and the balance is others.
所述步骤1中，气化剂为水蒸气，CO 2，富CO 2气体或空气，所述富CO 2气体为工业炉窑或锅炉产生的含CO 2废气，气化剂中气化反应成分为H 2O、CO 2/或O 2。 Step 1, the gasifying agent is steam, CO 2, CO 2 rich gas or air, CO 2 -containing flue gas of the CO 2 rich gas generated as boiler or industrial furnace, gasification agent in the gasification reaction components It is H 2 O, CO 2 / or O 2 .
所述步骤1中，气化剂为富CO 2烟气，烟气中CO 2含量为10-40％，N含量为60-90％。 In the step 1, the gasification agent is CO 2 rich flue gas, the CO 2 content in the flue gas is 10-40%, and the N content is 60-90%.
所述步骤1中，气化反应快速吸收颗粒的热量，并产生可燃煤气；与此同时，高温颗 粒温度被快速冷却，一次降温后颗粒温度为500～800℃，一次降温后颗粒通过颗粒出口进入热解炉的颗粒给料装置。In the step 1, the gasification reaction quickly absorbs the heat of the particles and produces combustible gas; at the same time, the temperature of the high-temperature particles is rapidly cooled, and the temperature of the particles after a cooling is 500-800℃, and the particles enter through the particle outlet after a cooling. Pyrolysis furnace pellet feeding device.
所述步骤1中，可燃煤气携带有半焦及灰分。In the step 1, the combustible gas carries semi-coke and ash.
所述步骤1中，气化炉气化反应的化学反应方程式如下：In the step 1, the chemical reaction equation of the gasification reaction of the gasifier is as follows:
C+CO 2(g)＝2CO(g)173.4kJ/mol(1) C+CO 2 (g)=2CO(g)173.4kJ/mol(1)
C+H 2O(g)＝CO(g)+H 2(g)135.6kJ/mol(2) C+H 2 O(g)=CO(g)+H 2 (g)135.6kJ/mol(2)
所述步骤1和2中，含碳固废材料A或B为煤粉或生物质或污泥或塑料或橡胶等工业、农业及生物含碳废弃材料，其碳元素含量在20-70％。In the steps 1 and 2, the carbon-containing solid waste material A or B is industrial, agricultural and biological carbon-containing waste materials such as coal powder or biomass or sludge or plastic or rubber, and its carbon content is 20-70%.
所述步骤1和2中，含碳固废材料A或B在进入热解炉或气化炉前需要进行干燥处理。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 gasification furnace.
所述步骤1和2中，含碳固废材料为煤粉。In the steps 1 and 2, the carbon-containing solid waste material is pulverized coal.
所述步骤2中，热解反应快速吸收一次降温后颗粒的热量，一次降温后颗粒温度被进一步冷却，冷却后颗粒温度≤200℃。冷却后的颗粒与热解后产生的固体半焦通过颗粒出口进入固体分离器。In the step 2, the pyrolysis reaction quickly absorbs the heat of the particles after a cooling, and the temperature of the particles is further cooled after the cooling, and the temperature of the particles after cooling is less than or equal to 200°C. The cooled particles and the solid semi-coke produced after pyrolysis enter the solid separator through the particle outlet.
所述步骤2中，热解气中包括煤气，热解气与步骤1获得的可燃煤气汇合，经气液分离器分离出热解气中的凝结性焦油和可燃煤气中的半焦与灰分，经净化器分离烟尘，获得洁净煤气。洁净煤气的热值在5000-7000kJ/m 3。 In the step 2, the pyrolysis gas includes coal gas, the pyrolysis gas is combined with the combustible gas obtained in step 1, and the condensable tar in the pyrolysis gas and the semi-coke and ash in the combustible gas are separated by a gas-liquid separator. The dust is separated by the purifier to obtain clean gas. The calorific value of clean gas is 5000-7000kJ/m 3 .
所述利用固体颗粒热载体进行热解气化的梯级余热回收方法，经过梯级余热回收后，热效率达80-84％，
Figure PCTCN2020128913-appb-000014
效率为70-77％。 In the cascade waste heat recovery method using solid particulate heat carrier for pyrolysis and gasification, after the cascade waste heat recovery, the thermal efficiency reaches 80-84%,
Figure PCTCN2020128913-appb-000014
The efficiency is 70-77%.
以下实例中，采用的煤粉中C＝64.4％，H＝4.2％，O＝8.8％，灰分含量＝20％，固定碳含量为44.8％，挥发分含量为32.8％，煤粉比热容C m2为1.1kJ/(kg·℃)。 In the following example, C=64.4%, H=4.2%, O=8.8%, ash content=20%, fixed carbon content of 44.8%, volatile content of 32.8%, and specific heat capacity of pulverized coal C m2 1.1kJ/(kg·℃).
实施例1Example 1
本发明实施采用的炉渣来源于国内某钢铁企业高炉的排渣，主要成分如表5所示。The slag used in the implementation of the present invention comes from the slag discharge of a domestic iron and steel enterprise blast furnace, and the main components are shown in Table 5.
表5炉渣颗粒化学成分％Table 5 Chemical composition of slag particles%
Figure PCTCN2020128913-appb-000015
Figure PCTCN2020128913-appb-000015
利用固体颗粒热载体热解气化的梯级余热回收装置结构示意图如图2所示，包括气化炉1，热解炉2，固体分离器3及其附属设备，热解炉2、气化炉1主要由炉体，送料装置***及烟气处理装置***组成。送料装置***设有高颗粒给料装置7，中低温颗粒给料装置11，气化炉燃料喷嘴9，热解炉燃料喷嘴12，气化炉颗粒出口10，热解炉颗粒出口14；烟气处理***设有 旋风分离器4，气液分离器5，净化器6。此外，热解炉内设置有搅拌装置13。气化炉1，热解炉2，固体分离器3分别顺次连接。气化炉颗粒出口10与热解炉中低温颗粒给料装置11连接，热解炉颗粒出口14与固体分离器3相连。气化炉1与热解炉2的烟道出口汇合并与旋风分离器4、气液分离器5及净化器6顺次连接。The schematic diagram of the cascade waste heat recovery device using solid particle heat carrier pyrolysis gasification is shown in Figure 2, including gasification furnace 1, pyrolysis furnace 2, solid separator 3 and its auxiliary equipment, pyrolysis furnace 2, gasification furnace 1 Mainly composed of furnace body, feeding device system and flue gas processing device system. The feeding device system is provided with a high particle feeding device 7, a medium and 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; flue gas The treatment system is provided with a cyclone separator 4, a gas-liquid separator 5, and a purifier 6. In addition, a stirring device 13 is provided in the pyrolysis furnace. The gasification furnace 1, the pyrolysis furnace 2, and the solid separator 3 are respectively connected in sequence. The particle outlet 10 of the gasification furnace is connected with the low-temperature particle feeding device 11 in the pyrolysis furnace, and the particle outlet 14 of the pyrolysis furnace is connected with the solid separator 3. The flue outlets of the gasification furnace 1 and the pyrolysis furnace 2 merge and are connected to the cyclone separator 4, the gas-liquid separator 5 and the purifier 6 in sequence.
气化炉1为流化床，流化床1中煤粉类型为无烟煤；热解炉2为固定床，热解炉2中煤粉为褐煤。两个装置中煤粉在进入前需要经过干燥并磨碎至为100目以下。The gasification furnace 1 is a fluidized bed, and the pulverized coal type in the fluidized bed 1 is anthracite; the pyrolysis furnace 2 is a fixed bed, and the pyrolysis furnace 2 is lignite. The coal powder in the two devices needs to be dried and pulverized to below 100 mesh before entering.
可燃煤气经旋风分离器后，获得未能完全燃烧的固体，未完全燃烧固体经料仓收集。料仓呈漏斗状收集后并通过输运装置运送至气化炉，由气化炉燃料喷嘴进入气化炉。After the combustible gas passes through the cyclone separator, the incompletely combusted solid is obtained, and the incompletely combusted solid is collected by the silo. The silo is collected in a funnel shape and transported to the gasification furnace through a transportation device, and enters the gasification furnace from the fuel nozzle of the gasification furnace.
气化炉1中所述气化剂为某石灰窑富CO 2废气，成分及含量为CO 2 32.2％，N 2 59.6，O 21.8％，CO 2.6％，H 2O 3％，其他2.6％。 The gasification agent mentioned in gasifier 1 is a lime kiln rich in CO 2 waste gas, the composition and content are CO 2 32.2%, N 2 59.6, O 2 1.8%, CO 2.6%, H 2 O 3%, and others 2.6% .
采用上述装置进行梯级余热回收的方法，工艺流程图如图1所示。该工艺主要由气化、热解及分离三部分组成。气化炉的主要原料为煤粉、气化剂，产品为合成气。热解炉主要原料为煤粉，产品为热解气。高温颗粒分别流经气化炉及热解炉，并通过气化反应及热解反应两种化学反应分两步降温，具体步骤如下：The process flow chart of the method for cascade waste heat recovery using the above-mentioned device is shown in Figure 1. The process is mainly composed of three parts: gasification, pyrolysis and separation. The main raw materials of the gasifier are pulverized coal and 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 flow through the gasification furnace and the pyrolysis furnace respectively, and are cooled in two steps through the two chemical reactions of the gasification reaction and the pyrolysis reaction. The specific steps are as follows:
(1)高温颗粒余热回收(1) Waste heat recovery of high-temperature particles
1100℃的高温颗粒(粒径为1mm～10mm)通过高温颗粒给料装置7进入气化炉1，煤粉经干燥处理后，在气化剂的携带下通过气化炉燃料喷嘴9进入气化炉1，在高温颗粒给料装置7中内部通过水冷进行冷却。高温颗粒在气化炉1内自上而下运动，气化反应快速吸收颗粒的热量，并产生煤气；高温颗粒温度迅速降低至700℃。随后，一次降温后颗粒及产生的煤渣通过气化炉颗粒出口10进入热解炉2的中低温颗粒给料装置11。1100℃ high-temperature particles (with a particle size of 1mm～10mm) enter the gasification furnace 1 through the high-temperature particle feeding device 7. After the pulverized coal is dried, it enters the gasification furnace through the gasification furnace fuel nozzle 9 with the gasification agent. The furnace 1 is cooled by water cooling in the high-temperature pellet feeding device 7. 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 temperature of the high-temperature particles is rapidly reduced to 700°C. Subsequently, the particles and the generated coal slag after the primary cooling enter the medium and low temperature particle feeding device 11 of the pyrolysis furnace 2 through the particle outlet 10 of the gasifier.
气化剂中CO 2与煤粉中C元素的摩尔比为CO 2/C为1:1。高温颗粒质量与煤粉中C元素质量比为1:0.02。 The molar ratio of CO 2 in coal gasification agent in the elements of C CO 2 / C is 1: 1. The ratio of the mass of high-temperature particles to the mass of C in the coal powder is 1:0.02.
(2)中低温颗粒余热回收(2) Waste heat recovery of medium and low temperature particles
一次降温后700℃的颗粒以及煤粉分别通过中低温颗粒给料装置11、热解炉燃料喷嘴12进入热解炉2。热解炉中，煤粉：一次降温后颗粒的质量比为0.8:1。颗粒在热解炉内自上而下运动，搅拌装置13在内部将煤粉与颗粒进行充分搅拌混合。煤粉通过热解反应快速吸收颗粒的热量生成固体半焦及热解气。与此同时，颗粒温度被进一步冷却，温度降低至120℃。冷却后的颗粒与热解后产生的半焦通过颗粒出口进入固体分离器3。After the first cooling, the 700°C particles and coal powder enter the pyrolysis furnace 2 through the medium and low temperature particle feeding device 11 and the pyrolysis furnace fuel nozzle 12 respectively. In the pyrolysis furnace, the mass ratio of pulverized coal: particles after one cooling 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 pulverized coal and the particles inside. The pulverized coal quickly absorbs the heat of the particles through the pyrolysis reaction to generate solid semi-coke and pyrolysis gas. At the same time, the temperature of the pellets was further cooled, and the temperature was reduced to 120°C. The cooled particles and the semi-coke produced after pyrolysis enter the solid separator 3 through the particle outlet.
热解及气化过程的产气混合后经过旋风分离器4将煤气携带出的半焦及灰分进行分离，气液分离器5通过冷却降温将煤气中的具有凝结性的焦油进行分离，煤气净化器6将煤气进一步净化成洁净煤气，洁净煤气产率为32％，洁净煤气热值约为7000kJ/m 3。 The gas produced in the pyrolysis and gasification process is mixed and passed through the cyclone 4 to separate the semi-coke and ash carried by the coal gas. The gas-liquid separator 5 separates the condensable tar in the coal gas by cooling and reducing the temperature, and the gas is purified. The device 6 further purifies the gas into clean gas. The clean gas yield is 32%, and the heating value of the clean gas is about 7000kJ/m 3 .
(3)固体分离(3) Solid separation
冷却后的颗粒与半焦混合物在固体分离器3中根据粒径大小的不同完成筛分及分离。固体半焦产率为21％，半焦组分及质量百分含量为水分0.79％，挥发分12.2％，固定碳78.2％，灰分8.8％。The cooled particle and semi-coke mixture is sieved and separated in the solid separator 3 according to the size of the particle size. The solid semi-coke yield is 21%, the semi-coke component and mass percentage are 0.79% moisture, 12.2% volatile, 78.2% fixed carbon, and 8.8% ash.
本实施例中，热效率为84％，
Figure PCTCN2020128913-appb-000016
效率为77％。 In this embodiment, the thermal efficiency is 84%,
Figure PCTCN2020128913-appb-000016
The efficiency is 77%.
实施例2Example 2
利用固体颗粒热载体热解气化的梯级余热回收装置结构示意图如图4所示，采用上述装置进行梯级余热回收的方法，工艺流程图如图3所示。The schematic diagram of the structure of the cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification is shown in FIG. 4, and the process flow chart of the method for cascade waste heat recovery using the above device is shown in FIG.
与实施例1相比，其不同点在于：Compared with Example 1, the difference lies in:
(1)工艺方法上，实施例2中气化炉1中燃料为热解炉2中产生的半焦，装置结构上，固体分离器3的出口物料通过提升装置进入气化炉燃料喷嘴9。(1) In terms of process method, the fuel in the gasification furnace 1 in Example 2 is semi-coke produced in the pyrolysis furnace 2. In terms of the device structure, the outlet material of the solid separator 3 enters the gasification furnace fuel nozzle 9 through a lifting device.
(2)实施例2中气化炉1中产品为可燃煤气及多孔性焦炭，多孔性焦炭比表面积在1100m 2/g以上。可燃煤气经旋风分离器，气液分离器和净化器，去除挥发分和凝结性焦油，获得洁净煤气，洁净煤气产率为30％，洁净煤气热值为5000kJ/m 3。 (2) The products in the gasifier 1 in Example 2 are combustible gas and porous coke, and the specific surface area of the porous coke is above 1100 m 2 /g. The combustible gas passes through the cyclone separator, gas-liquid separator and purifier to remove volatiles and condensable tar to obtain clean gas. The yield of clean gas is 30%, and the calorific value of clean gas is 5000kJ/m 3 .
(3)实施例2中气化剂为某锅炉烟气，成分及含量为CO 2 12.8％，N 2 77.1％，O 2 6.1％，CO 0.06％，H 2O 3％，其他0.04％。 (3) The gasification agent in Example 2 is a certain boiler flue gas, and its composition and content are CO 2 12.8%, N 2 77.1%, O 2 6.1%, CO 0.06%, H 2 O 3%, and others 0.04%.
(4)实施例2中气化炉1中烟气中CO 2与煤粉中C元素的摩尔比为CO 2/C 0.2:1。气化炉中高温颗粒质量与煤粉C元素质量比为1:0.05。 Molar ratio (4) Example gasifier 21 CO 2 in the flue gas in the pulverized coal and of the element C CO 2 / C 0.2: 1. The ratio of the mass of high-temperature particles in the gasifier to the mass of pulverized coal C element is 1:0.05.
(6)一次降温后颗粒温度为600℃，热解炉中，一次降温后颗粒质量与煤粉中C元素质量比为0.5：1。(6) The temperature of the particles after the first cooling is 600°C. In the pyrolysis furnace, the ratio of the particle mass to the C element mass in the coal powder after the first cooling is 0.5:1.
冷却后的颗粒与半焦混合物在固体分离器3中根据粒径大小的不同完成筛分及分离，冷却后颗粒温度为100℃，固体半焦产率为23％，半焦组分及质量百分含量为水分0.82％，挥发分11.7％，固定碳77.1％，灰分10.3％。The cooled particles and semi-coke mixture are sieved and separated in the solid separator 3 according to the different particle sizes. The temperature of the particles after cooling is 100°C, the solid semi-coke yield is 23%, and the semi-coke component and quality are 100%. The component content is 0.82% moisture, 11.7% volatile, 77.1% fixed carbon, and 10.3% ash.
本实施例中，热效率为80％，
Figure PCTCN2020128913-appb-000017
效率为70％。 In this embodiment, the thermal efficiency is 80%,
Figure PCTCN2020128913-appb-000017
The efficiency is 70%.
实施例3Example 3
同实施例1，其不同点在于：Same as Example 1, the difference lies in:
(1)实施例3中高温颗粒为钢渣，钢渣温度为1200℃，主要成分如表6所示。(1) In Example 3, the high-temperature particles are steel slag, the temperature of the steel slag is 1200°C, and the main components are shown in Table 6.
表6钢渣颗粒化学成分％Table 6 Chemical composition of steel slag particles%
Figure PCTCN2020128913-appb-000018
Figure PCTCN2020128913-appb-000018
(2)实施例3中，洁净煤气产率为33％，洁净煤气热值约为6000kJ/m 3； (2) In Example 3, the clean gas production rate is 33%, and the clean gas heating value is about 6000 kJ/m 3 ;
(4)实施例3中，气化剂为某炉窑烟气，成分及含量为CO 2 30.8％，N 2 60.1％，O 2 0.6％，CO 3.2％，H 2O 5％，SO 2 0.26％，其他0.04％。 (4) In Example 3, the gasification agent is a certain furnace flue gas, the composition and content are CO 2 30.8%, N 2 60.1%, O 2 0.6%, CO 3.2%, H 2 O 5%, SO 2 0.26 %, other 0.04%.
(5)实施例3中，气化炉1中烟气中CO 2与煤粉中C元素的摩尔比为CO 2/C 1:1。高温颗粒质量与煤粉C元素质量比为1:0.05，一次降温后颗粒温度为800℃。 Molar ratio (5) in Example 3, CO 2 in the flue gas in the gasification furnace in the pulverized coal and the element C 1 is CO 2 / C 1: 1. The ratio of the mass of high-temperature particles to the mass of pulverized coal C element is 1:0.05, and the temperature of the particles after a cooling is 800°C.
热解炉中，一次降温后颗粒质量与煤粉中C元素质量比为0.8：1-；In the pyrolysis furnace, the ratio of the particle mass to the C element mass in the pulverized coal after cooling once is 0.8:1;
获得的冷却后的颗粒与半焦混合物在固体分离器3中根据粒径大小的不同完成筛分及分离。冷却后颗粒温度为150℃，固体半焦产率为20％，半焦组分及质量百分含量为水分0.69％，挥发分12.5％，固定碳79.1％，灰分7.8％。The obtained cooled particle and semi-coke mixture is sieved and separated in the solid separator 3 according to the difference in particle size. After cooling, the pellet temperature is 150°C, the solid semi-coke yield is 20%, the semi-coke component and mass percentage are 0.69% moisture, 12.5% volatile, 79.1% fixed carbon, and 7.8% ash.
本实施例中，热效率为82％，
Figure PCTCN2020128913-appb-000019
效率为74％。 In this embodiment, the thermal efficiency is 82%,
Figure PCTCN2020128913-appb-000019
The efficiency is 74%.

Claims (9)

  1. 利用固体颗粒热载体热解气化的梯级余热回收装置，其特征在于，包括气化炉，热解炉，固体分离器及烟气处理***，其中：The cascade waste heat recovery device for pyrolysis and gasification using solid particle heat carrier is characterized by comprising a gasification furnace, a pyrolysis furnace, a solid separator and a flue gas treatment system, among which:
    所述气化炉，热解炉和固体分离器依次连接，气化炉与热解炉的烟道出口汇合并与烟气处理***连接。The gasification furnace, the pyrolysis furnace and the solid separator are connected in sequence, and the gasification furnace and the flue outlet of the pyrolysis furnace are merged and connected to the flue gas treatment system.
  2. 根据权利要求1所述的利用固体颗粒热载体热解气化的梯级余热回收装置，其特征在于：The cascade waste heat recovery device using solid particle heat carrier pyrolysis and gasification according to claim 1, characterized in that:
    所述烟气处理***包括旋风分离器、气液分离器及净化器，各部件顺次连接；The flue gas treatment system includes a cyclone separator, a gas-liquid separator and a purifier, and each component is connected in sequence;
    所述气化炉为固定床或流化床，所述气化炉设有颗粒给料装置，气化炉燃料喷嘴和颗粒出口；The gasification furnace is a fixed bed or a fluidized bed, and the gasification furnace is provided with a particle feeding device, a gasification furnace fuel nozzle and a particle outlet;
    所述热解炉为固定床，所述热解炉内设置有搅拌装置；The pyrolysis furnace is a fixed bed, and a stirring device is arranged in the pyrolysis furnace;
    所述气化炉的颗粒出口与热解炉颗粒给料装置连接，热解炉的颗粒出口与固体分离器相连。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. 根据权利要求1所述的利用固体颗粒热载体热解气化的梯级余热回收装置，其特征在于，所述固体分离器通过提升装置与气化炉燃料喷嘴连接。The stepped waste heat recovery device for pyrolysis and gasification of solid particulate heat carriers according to claim 1, wherein the solid separator is connected to the fuel nozzle of the gasifier through a lifting device.
  4. 采用权利要求1所述的利用固体颗粒热载体热解气化的梯级余热回收装置，利用固体颗粒热载体热解气化的梯级余热回收的方法，其特征在于，包括以下步骤：Using the stepped waste heat recovery device using solid particle heat carrier pyrolysis and gasification according to claim 1, and the stepped waste heat recovery method using solid particle heat carrier pyrolysis and gasification, it is characterized in that it comprises the following steps:
    步骤1，高温颗粒余热回收：Step 1. Waste heat recovery of high-temperature particles:
    高温颗粒进入气化炉，含碳固废材料A在气化剂携带下进入气化炉，高温颗粒在气化炉内自上而下运动，气化剂和含碳固废材料A在炉内发生气化反应，生成可燃煤气，同时获得一次降温后颗粒，其中，所述的高温颗粒温度为900～1200℃，按摩尔比，气化剂中气化反应成分：含碳固废材料A中C元素＝(0.2～1):1，按质量比，高温颗粒质量：含碳固废材料A中C元素＝1:(0.02～0.05)，所述的气化剂为水蒸气，CO 2，富CO 2烟气或空气，所述富CO 2气体为工业炉窑或锅炉产生的含CO 2废气，气化剂中气化反应成分为H 2O、CO 2/或O 2，所述的含碳固废材料A中碳元素含量在20-70％； The high-temperature particles enter the gasification furnace, and the carbon-containing solid waste material A enters the gasification furnace with the gasification agent. The high-temperature particles move from top to bottom in the gasification furnace, and the gasification agent and carbon-containing solid waste material A are in the furnace. A gasification reaction occurs to generate combustible gas, and at the same time, particles after cooling are obtained. The temperature of the high-temperature particles is 900-1200℃, molar ratio, and the gasification reaction component in the gasification agent: carbon-containing solid waste material A C element=(0.2～1):1, according to the mass ratio, the mass of high-temperature particles: C element in carbon-containing solid waste material A=1:(0.02～0.05), the gasification agent is water vapor, CO 2 , CO 2 rich flue gas or air, the CO 2 rich gas is CO 2 containing waste gas produced by industrial furnaces or boilers, the gasification reaction component in the gasification agent is H 2 O, CO 2 / or O 2 , The carbon content in the carbon-containing solid waste material A is 20-70%;
    步骤2，中低温颗粒余热回收：Step 2: Recovery of waste heat from medium and low temperature particles:
    一次降温后颗粒与含碳固废材料B进入热解炉，按质量比，含碳固废材料B：一次降温后颗粒＝(0.5～1):1，颗粒在热解炉内自上而下运动，含碳固废材料B在炉内发生热解反应，生成热解气和固体半焦，并获得冷却后颗粒，其中，所述的含碳固废材料A中碳元素含量在20-70％；After a cooling, the particles and the carbon-containing solid waste material B enter the pyrolysis furnace. According to the mass ratio, the carbon-containing solid waste material B: After a cooling, the particles = (0.5-1):1, and the particles are from top to bottom in the pyrolysis furnace Movement, the carbon-containing solid waste material B undergoes a pyrolysis reaction in the furnace to generate pyrolysis gas and solid semi-coke, and obtain cooled particles, wherein the carbon content of the carbon-containing solid waste material A is 20-70 %;
    步骤3，固体分离：Step 3. Solid separation:
    冷却后的颗粒与固体半焦混合物进入固体分离器中，在固体分离器中进行筛分及分离，获得冷却后颗粒与固体半焦，其中，所述固体半焦进入气化炉，作为燃料为气化炉提供热量， 所述固体半焦产率为20-23％，固体半焦中固定碳含量为77-79.1％。The cooled mixture of particles and solid semi-coke enters the solid separator, where it is screened and separated to obtain cooled particles and solid semi-coke, wherein the solid semi-coke enters the gasification furnace and is used as fuel The gasifier provides heat, the yield of the solid semi-coke is 20-23%, and the fixed carbon content in the solid semi-coke is 77-79.1%.
  5. 根据权利要求4所述的利用固体颗粒热载体热解气化的梯级余热回收的方法，其特征在于，所述步骤1中，高温颗粒为钢铁冶炼排放的高炉渣颗粒或钢渣颗粒，粒径为1～10mm，其中：The method for cascade waste heat recovery using solid particle heat carrier pyrolysis and gasification according to claim 4, characterized in that, in the step 1, the high-temperature particles are blast furnace slag particles or steel slag particles discharged from iron and steel smelting, and the particle size is 1～10mm, of which:
    所述高炉渣颗粒包括组分及质量百分含量为CaO 41.21％，MgO 8.22％，SiO 234.38％，Al 2O 311.05％，Fe 2O 32.78％，TiO 20.35％，余量其他； The blast furnace slag particles include components and mass percentages: CaO 41.21%, MgO 8.22%, SiO 2 34.38%, Al 2 O 3 11.05%, Fe 2 O 3 2.78%, TiO 2 0.35%, the balance is others;
    所述钢渣颗粒包括组分及质量百分含量为CaO 41.18％，MgO 9.26％，SiO 220.49％，Al 2O 33.08％，Fe 2O 320.35％，余量其他。 The steel slag particles include components and mass percentages of CaO 41.18%, MgO 9.26%, SiO 2 20.49%, Al 2 O 3 3.08%, Fe 2 O 3 20.35%, and the balance is others.
  6. 根据权利要求4所述的利用固体颗粒热载体热解气化的梯级余热回收的方法，其特征在于，所述步骤1中，气化剂为富CO 2烟气，烟气中CO 2含量为10-40％，N含量为60-90％。 The method for cascade waste heat recovery using solid particle heat carrier pyrolysis gasification according to claim 4, characterized in that, in the step 1, the gasification agent is CO 2 rich flue gas, and the CO 2 content in the flue gas is 10-40%, N content is 60-90%.
  7. 根据权利要求4所述的利用固体颗粒热载体热解气化的梯级余热回收的方法，其特征在于，所述含碳固废材料A或B为煤粉或生物质或污泥或塑料或橡胶工业、农业及生物含碳废弃材料，所述含碳固废材料A或B在进入热解炉或气化炉前需要进行干燥处理。The method for cascade waste heat recovery using solid particle heat carrier pyrolysis and gasification according to claim 4, wherein the carbon-containing solid waste material A or B is coal powder or biomass or sludge or plastic or rubber Industrial, agricultural and biological carbon-containing waste materials, the carbon-containing solid waste materials A or B need to be dried before entering the pyrolysis furnace or gasification furnace.
  8. 根据权利要求4所述的利用固体颗粒热载体热解气化的梯级余热回收的方法，其特征在于，所述步骤2中，热解气中包括煤气，热解气与步骤1获得的可燃煤气汇合，经气液分离器分离出热解气中的凝结性焦油和可燃煤气中的半焦与灰分，经净化器分离烟尘，获得洁净煤气，洁净煤气的热值在5000-7000kJ/m 3。 The method for cascaded waste heat recovery using solid particle heat carrier pyrolysis gasification according to claim 4, characterized in that, in the step 2, the pyrolysis gas includes coal gas, and the pyrolysis gas is combined with the combustible gas obtained in step 1. Convergence, the condensable tar in the pyrolysis gas and the semi-coke and ash in the combustible gas are separated by the gas-liquid separator, and the smoke and dust are separated by the purifier to obtain clean gas. The calorific value of the clean gas is 5000-7000kJ/m 3 .
  9. 根据权利要求4所述的利用固体颗粒热载体热解气化的梯级余热回收的方法，其特征在于，所述利用固体颗粒热载体进行热解气化的梯级余热回收方法，经过梯级余热回收后，热效率达80-84％，
    Figure PCTCN2020128913-appb-100001
    效率为70-77％。     The method for cascade waste heat recovery using solid particulate heat carrier pyrolysis and gasification according to claim 4, wherein the cascade waste heat recovery method using solid particulate heat carrier for pyrolysis and gasification, after cascade waste heat recovery , The thermal efficiency reaches 80-84%,
    Figure PCTCN2020128913-appb-100001
    The efficiency is 70-77%.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113392529A (en) * 2021-06-18 2021-09-14 马鞍山钢铁股份有限公司 Blast furnace area thermal state online analysis method
CN113944925A (en) * 2021-10-14 2022-01-18 北京工商大学 Partition-type enhanced heat exchange decoupling gasification combustion system for high-moisture-content granular fuel
CN115216346A (en) * 2022-06-27 2022-10-21 上海蓝瑞环保能源科技有限公司 Method and system for preparing hydrogen-rich gas by using organic solid waste
CN115449402A (en) * 2022-09-13 2022-12-09 北京航天迈未科技有限公司 Treatment system and treatment method for solid organic matters

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110872531B (en) * 2019-12-12 2021-07-13 青岛理工大学 Step waste heat recovery device and method utilizing pyrolysis gasification of solid particle heat carrier
CN111423085A (en) * 2020-04-22 2020-07-17 青岛理工大学 Method for preparing hydrogen-rich synthesis gas by utilizing metallurgical slag waste heat to treat sludge in grading manner
CN111733322A (en) * 2020-06-22 2020-10-02 青岛理工大学 Device system and method for absorbing copper slag waste heat in stepped manner based on coal gasification reaction
CN112625709A (en) * 2020-12-09 2021-04-09 青岛理工大学 Device system and method for driving coal and sludge to be pyrolyzed together by utilizing waste heat of iron-removing tailings
CN113981248B (en) * 2021-10-09 2022-09-13 济南恒誉环保科技股份有限公司 Utilize device of solid useless pyrolysis product processing ilmenite ore
CN114369691A (en) * 2022-01-04 2022-04-19 中冶南方工程技术有限公司 Urban solid waste and iron making cooperative system and method based on blast furnace slag waste heat utilization
CN115287100B (en) * 2022-07-05 2023-06-27 西安交通大学 Underground in-situ gasification-pyrolysis-waste heat utilization integrated system for oil-rich coal

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102191088A (en) * 2011-04-12 2011-09-21 浙江大学 Solid fuel double fluidized bed thermal pyrolysis grade transformation device and method
CN110872531A (en) * 2019-12-12 2020-03-10 青岛理工大学 Step waste heat recovery device and method utilizing pyrolysis gasification of solid particle heat carrier
CN110923387A (en) * 2019-12-12 2020-03-27 青岛理工大学 Iron-containing metallurgical slag particle step waste heat recovery and direct reduction system and method

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101113341B (en) * 2007-09-11 2010-10-13 昆明理工大学 Method for preparing combustible gas by using metallurgy molten slag and solid combustible substance
CN101597658B (en) * 2009-07-10 2010-12-08 东北大学 Coal gasification system and method of blast furnace slags
RU2521638C2 (en) * 2012-09-17 2014-07-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Чувашский государственный университет имени И.Н. Ульянова" Gasification of carbon-bearing solid fuels
CN105567327B (en) * 2016-02-25 2018-01-09 青岛理工大学 A kind of method that high humidity sludge gasification based on blast furnace slag waste heat recovery produces hydrogen-rich combustion gas
CN106944458A (en) * 2017-03-15 2017-07-14 北京神雾环境能源科技集团股份有限公司 The system and method for handling house refuse
CN107325846B (en) * 2017-06-28 2019-10-11 大连理工大学 A kind of pyrolysis of coal chemical chain gasification coupling technique based on low-order coal cascade utilization
CN107760383A (en) * 2017-11-13 2018-03-06 中国矿业大学(北京) Blast furnace slag waste heat catalytic pyrolysis biomass gas technology
CN109777519B (en) * 2019-03-27 2021-02-05 东北大学 Blast furnace slag waste heat driving gasification reaction system
CN110358578A (en) * 2019-06-28 2019-10-22 华中科技大学 A kind of fire coal coupled biological matter power generating simultaneously charcoal system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102191088A (en) * 2011-04-12 2011-09-21 浙江大学 Solid fuel double fluidized bed thermal pyrolysis grade transformation device and method
CN110872531A (en) * 2019-12-12 2020-03-10 青岛理工大学 Step waste heat recovery device and method utilizing pyrolysis gasification of solid particle heat carrier
CN110923387A (en) * 2019-12-12 2020-03-27 青岛理工大学 Iron-containing metallurgical slag particle step waste heat recovery and direct reduction system and method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
1 July 2011, article DU, WENYA: "The Experimental Study of Coal Gasification in Blast Furnace Slag", pages: 1 - 140, XP055820164 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113392529A (en) * 2021-06-18 2021-09-14 马鞍山钢铁股份有限公司 Blast furnace area thermal state online analysis method
CN113944925A (en) * 2021-10-14 2022-01-18 北京工商大学 Partition-type enhanced heat exchange decoupling gasification combustion system for high-moisture-content granular fuel
CN113944925B (en) * 2021-10-14 2023-08-15 北京工商大学 Partition wall type reinforced heat exchange thermal decoupling gasification combustion system for high-water-content granular fuel
CN115216346A (en) * 2022-06-27 2022-10-21 上海蓝瑞环保能源科技有限公司 Method and system for preparing hydrogen-rich gas by using organic solid waste
CN115216346B (en) * 2022-06-27 2024-04-12 上海蓝瑞环保能源科技有限公司 Method and system for preparing hydrogen-rich fuel gas by utilizing organic solid waste
CN115449402A (en) * 2022-09-13 2022-12-09 北京航天迈未科技有限公司 Treatment system and treatment method for solid organic matters

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