CN108870407B - Method for treating sludge through chemical-looping gasification based on copper slag as oxygen carrier and device for implementing method - Google Patents
Method for treating sludge through chemical-looping gasification based on copper slag as oxygen carrier and device for implementing method Download PDFInfo
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/001—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for sludges or waste products from water treatment installations
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
- F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
- F23J15/027—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using cyclone separators
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2205/00—Waste feed arrangements
- F23G2205/12—Waste feed arrangements using conveyors
- F23G2205/121—Screw conveyor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2206/00—Waste heat recuperation
- F23G2206/20—Waste heat recuperation using the heat in association with another installation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2217/00—Intercepting solids
- F23J2217/40—Intercepting solids by cyclones
Abstract
The invention discloses a method for treating sludge by chemical refining and gasification based on copper slag as an oxygen carrier and a device for realizing the method. The method adopts a chemical chain gasification technology, takes copper slag as a precursor, is calcined and activated by high-temperature air to form an oxygen carrier, and further utilizes a double-circulating fluidized bed device to treat domestic sludge. The invention creates a utilization mechanism of solid waste, realizes the reduction, harmless and resource treatment of sludge while resource utilization of copper slag, treats waste by waste, has strong economic adaptability and meets new requirements of environmental protection.
Description
The technical field is as follows:
the invention belongs to the technical field of clean gasification of fuels, functional materials and environmental protection, and particularly relates to a method for treating sludge by chemical-looping gasification based on copper slag as an oxygen carrier and a device for realizing the method.
Background art:
the increase of population and the rapid development of global economy lead to the continuous and large increase of sludge yield in China and even all over the world, and a large amount of N, P and other organic matters, bacterial microorganisms, heavy metals, toxic pollutants and the like contained in the sludge pose serious threats to the environment if not effectively treated.
The existing sludge treatment principle is to realize reduction, resource utilization and stabilization treatment of sludge, and the treatment method mainly comprises landfill, agricultural utilization and thermochemical conversion methods. However, due to the technical and cost problems, the main sludge treatment mode in China is landfill, which has the serious defects of land resource waste, secondary pollution and the like; the thermochemical conversion method recovers energy in a part of sludge and reduces secondary pollution while effectively realizing sludge reduction treatment, and better embodies the treatment principles of sludge reduction, harmlessness and recycling.
Compared with sludge pyrolysis and combustion, the sludge gasification has the characteristics of low ash leaching toxicity, low gas pollutant discharge, wide application of generated synthesis gas and the like, but the traditional sludge gasification mode adopts air, water vapor, pure oxygen and the like as gasification agents, so that the treatment cost of sludge gasification is improved, and various gas pollutants (NOx) and sulfides are easily generated.
The copper slag is a waste material formed by mutually melting various oxides in furnace burden and fuel in the copper smelting process, and is black, compact, wear-resistant and irregular particles with metallic luster. The specific chemical composition of slag varies from furnace to furnace, from process to process, and from raw ore to raw ore, but the main component is fayalite (Fe)2SiO4) Magnetite (Fe)3O4) And copper fraction, and small amount of Ni, Co, Zn, Ag and Au. According to statistics, every ton of copper is produced, 2.2-3 tons of copper slag are probably produced; 400-ten thousand tons of copper slag are produced in copper smelting in China every year, and the accumulated amount reaches more than 5000-ten thousand tons at present, so that a large amount of accumulated copper slag not only occupies a large amount of land, but also can cause secondary pollution to atmosphere, soil and underground water.
Can realize the harmless and resource treatment of the sludge and the resource utilization of the copper slag, treats the waste by the waste, and is a new technology integrating energy conversion and environmental protection.
The invention content is as follows:
the invention aims to provide a method for treating sludge by chemical chain gasification based on copper slag as an oxygen carrier and a device for realizing the method.
The invention aims to provide a method for treating sludge by chemical looping gasification based on copper slag as an oxygen carrier, which comprises the following steps:
(1) calcining, activating, crushing and screening the copper slag to serve as an oxygen carrier for later use;
(2) reacting the oxygen carrier obtained in the step (1) with sludge in a fuel reactor, wherein the mass ratio of the oxygen carrier to the sludge is 3-5: 1, so as to obtain reacted sludge, reduced oxygen carrier and synthesis gas, a mixture of a part of the reacted sludge and a part of the reduced oxygen carrier enters an air reactor through a material returning device, the reduced oxygen carrier reacts with air in the air reactor under the action of the air reactor to realize the regeneration of the oxygen carrier, the regenerated oxygen carrier reflows to the fuel reactor through a solid outlet pipeline of an air primary cyclone separator, and continuously reacts with the sludge in the fuel reactor to form a cycle, after the gas-solid separation of the other part of the reacted sludge, the other part of the reduced oxygen carrier and the synthesis gas, the other part of the reacted sludge and the other part of the reduced oxygen carrier are discharged through a synthesis gas ash discharge port, the synthesis gas enters the integrated heat exchanger after gas-solid separation, waste heat in the synthesis gas is recycled through the integrated heat exchanger and then is divided, one part of the synthesis gas and steam are mixed to serve as carrier gas of the fuel reactor, the volume ratio of the synthesis gas to the steam in the fuel reactor is 2-3: 6, the other part of the synthesis gas is collected for later use, and air in the air reactor is used as carrier gas of the air reactor after absorbing heat through the integrated heat exchanger. The reaction temperature of the air reactor is 850-1000 ℃, and the reaction temperature of the fuel reactor is 700-900 ℃.
The invention provides a method for treating sludge by chemical chain gasification based on copper slag as an oxygen carrier, which comprises the following steps: the method comprises the following steps of (1) alternately carrying out reduction-oxidation reaction in a fuel reactor and an air reactor by using calcined copper slag as an oxygen carrier to realize the gasification process of sludge, specifically, feeding the oxygen carrier and the sludge into the fuel reactor according to a certain feeding proportion, reacting with the sludge under a fluidization environment provided by mixed gas consisting of water vapor and synthetic gas, generating the synthetic gas by the sludge through a series of pyrolysis, gasification, water vapor conversion and oxidation reaction, and reducing the oxygen carrier to lose lattice oxygen; the reduced oxygen carrier (mixed with sludge ash) flows out of the fuel reactor along a material returning device under the action of a flow field, the generated synthesis gas (mixed with sludge ash) enters a synthesis gas cyclone separator, the synthesis gas enters a synthesis gas bag-type dust remover to remove the sludge ash after a part of ash is discharged from a synthesis gas ash discharging port in gas-solid separation, then enters an integrated heat exchanger along a pipeline, the waste heat of the synthesis gas is recovered and then is divided, a part of the synthesis gas is mixed with water vapor to be used as the carrier gas of the fuel reactor, and the other part of the synthesis gas is collected and stored; oxygen carriers (mixed with sludge ash) flow back to the air reactor together through a material returning device; the reduced oxygen carrier reacts with air in an air reactor to release a large amount of heat, and meanwhile, the oxygen carrier is oxidized by the air to recover lattice oxygen, so that regeneration is realized; the regenerated oxygen carrier (mixed with sludge ash) enters a primary air cyclone separator under the action of a flow field, the oxygen carrier and the sludge ash are separated according to the difference of mass density of the oxygen carrier and the sludge ash, and most of the oxygen carrier flows back to a fuel reactor from a solid outlet pipeline of the primary air cyclone separator to complete circulation; the sludge ash and the flue gas (a small part of oxygen carriers and sludge ash) enter a secondary air cyclone separator, gas-solid separation is carried out under the action of centrifugal force, a certain amount of sludge ash and all copper slag are separated out of a circulating system from a flue gas ash discharging port, the flue gas (sludge ash) is dedusted by a bag-type dust remover and then enters an integrated heat exchanger along a pipeline, and the flue gas (sludge ash) is discharged out of the system from a flue gas outlet after waste heat recovery; the oxygen carrier lost by ash discharge is supplemented into the system through the oxygen carrier feeder, so that the stability of the system operation is realized; wherein, air is directly extracted from the environment and enters the integrated heat exchanger, and then enters the air reactor through the air compressor after countercurrent heat exchange; the gasified water also passes through the integrated heat exchanger, is changed into steam after countercurrent heat exchange to be mixed with part of synthesis gas, and enters the fuel reactor after passing through a steam compressor.
The ash discharged from the synthesis gas ash discharge port and the flue gas ash discharge port can be collected for further utilization. Because the ash content of the sludge is high, the process of discharging a large amount of ash can cause a large amount of loss of the oxygen carrier, a large amount of high-temperature ash slag is continuously generated, at the moment, germs contained in the sludge are killed, and the sludge can be directly taken to make bricks, so that the development of a braking byproduct can be realized while not consuming too much heat energy.
Preferably, the step (1) comprises the following specific steps: heating copper slag to 1100 deg.C at 15 deg.C/min, calcining at constant temperature for 2 hr, naturally cooling to room temperature, crushing and sieving to obtain powder of less than 100 meshesThe particles are used as oxygen carriers for standby. On one hand, the high-temperature calcination decomposes the ferric silicate in the original copper slag into active component Fe2O3Or Fe3O4So that the material has the property of an oxygen carrier and has good mechanical wear resistance.
The second purpose of the invention is to provide a device for realizing the method for treating sludge by chemical chain gasification based on copper slag as an oxygen carrier, which comprises a fuel reactor, an air reactor and an integrated heat exchanger, wherein the fuel reactor is provided with a sludge feeder feed inlet and an oxygen carrier feeder feed inlet; the fuel gas recycling device comprises a fuel gas reactor, a first-stage air cyclone separator, a second-stage air cyclone separator, an integrated heat exchanger and a gas-liquid separator, wherein a gas outlet of the air reactor is communicated with the first-stage air cyclone separator through a first gas pipe, a solid outlet of the first-stage air cyclone separator is arranged inside the fuel reactor, a gas outlet of the first-stage air cyclone separator is communicated with the second-stage air cyclone separator through a second gas pipe, the second-stage air cyclone separator is communicated with a gas bag-type dust collector through a third gas pipe, an outlet of the gas bag-type dust collector is connected with a fourth; the sludge feeder is a two-stage sludge screw feeder which is formed by matching two screw feeders and a hopper bin up and down and back and forth. The invention uses the two-stage spiral sludge feeder, can reduce the condition of uneven feeding amount of sludge in a short time due to local moisture and insufficient friction force, can ensure the constant feeding amount of sludge, and is beneficial to the stable operation of a system. During the operation of the device, a large amount of ash slag is generated at an ash discharge port due to the discharge of the ash content of the sludge and the loss of the copper slag oxygen carrier, and the ash slag has good brick making potential and can better realize the resource utilization of wastes.
Preferably, a plurality of flow guide baffles are arranged in the fuel reactor. The arrangement of the drainage baffle plate enables the oxygen carrier and the sludge to fully react.
Preferably, an air pipeline is arranged on the integrated heat exchanger, the air pipeline which exchanges heat through the integrated heat exchanger is connected with the air reactor, and air in the air pipeline is used as carrier gas of the air reactor.
Preferably, the fourth syngas line is combined with a water vapor line into the fuel reactor, and syngas and water vapor are used as carrier gas for the fuel reactor.
Preferably, the bottom of the fuel reactor is provided with a fuel reactor air distribution plate, and the bottom of the air reactor is provided with an air reactor air distribution plate. The air distribution plate of the fuel reactor and the air distribution plate of the air reactor are used for supporting bed charge at the bottom of the reactor, uniformly distributing air and ensuring a normal fluidization state.
The device provided by the invention has the advantages of convenience in operation, easiness in large-scale production and good economic benefit.
The invention has the beneficial effects that:
1. the invention designs a sludge two-stage spiral feeder for feeding sludge, can reduce the condition of uneven feeding amount of the sludge in a short time due to local humidity and insufficient friction force, can ensure the constant feeding amount of the sludge, and is beneficial to the stable operation of a system.
2. The invention designs two cyclone separators to separate sludge ash, which can ensure the ash removal performance of the system; because the sludge contains a large amount of ash (50 percent of dry basis), a large amount of ash is generated by sludge gasification in the circulation process and is mixed with the oxygen carrier, and when the ash is discharged by using a chemical chain gasification technology, the oxygen carrier and the ash cannot be separated by using a cyclone separator as usual; the primary air cyclone separator provides a high-power centrifugal force, so that most of ash (a small amount of oxygen carriers) enters the secondary air cyclone separator along with the flue gas, the flue gas is purified under the condition of relatively low power, the oxygen carriers and part of sludge ash are separated out of the system from the flue gas ash discharge port, and the working pressure of a downstream flue gas bag-type dust collector is reduced.
3. The invention designs the integrated heat exchanger to realize the heat exchange between the high-temperature flue gas and the synthesis gas and other carrier gases and realize the waste heat recovery, thereby ensuring the maximum utilization of resources in the sludge treatment process.
4. The invention keeps the characteristics of high quality and low purification cost of the conventional chemical-looping gasification synthesis gas: conventional gasification, for example, by adding pure oxygen or air, the former would bring a lot of energy consumption in the process of preparing pure oxygen, directly reducing the energy efficiency of the whole system; the latter will reduce the concentration of the synthesis gas, resulting in an increase in the cost of gas purification; in the chemical chain gasification process of the sludge, pure oxygen or air is not needed to be used as a gasifying agent, water vapor is used as a gasification medium, and part of synthesis gas generated by sludge gasification is particularly mixed and added to be used as carrier gas, so that reactants in a fuel reactor can be in a fluidized state, and the prepared synthesis gas is not subjected to air or O2The diluted synthesis gas has high quality and low purification cost; in addition, the oxygen carrier not only has the functions of oxidizing and catalyzing sludge, but also is a carrier of system heat, a large amount of heat released by oxidation heat release of the air reactor is carried to the fuel reactor, and the heat absorbed by gasification reduction reaction is supplemented, so that the system realizes self-heating, and energy is saved.
5. Compared with other sludge thermochemical treatment modes, the invention has the advantages that the gasification temperature is relatively low, and no gas-phase oxygen exists, so that the formation of NOx and sulfur-containing pollutants is reduced; meanwhile, due to the existence of strong reducing atmosphere and steam in the reactor, most of phosphorus in the sludge ash exists as water-soluble phosphate, which is beneficial to the recovery of phosphorus, saves energy and reduces environmental pollution.
6. The invention creates a utilization mechanism of solid waste, realizes the reduction, harmless and resource treatment of sludge while resource utilization of copper slag, treats waste by waste, has strong economic adaptability and meets new requirements of environmental protection.
Description of the drawings:
FIG. 1 is a schematic structural diagram of a device for implementing a method for treating sludge by chemical looping gasification based on copper slag as an oxygen carrier, wherein arrows indicate the flow direction of flue gas, synthesis gas, air or water vapor;
description of reference numerals: 1. an air distribution plate of the air reactor; 2. a material returning device; 3. an air reactor; 4. a fuel reactor; 5. a syngas cyclone; 6. synthetic gas bag dust collector, 7, first-stage air cyclone separator; 8. a secondary air cyclone separator; 9. a flue gas bag-type dust collector; 10. an oxygen carrier feeder; 11. a sludge two-stage screw feeder; 12. a fuel reactor grid plate; 13. a water vapor compressor; 14. an air compressor; 15. a first syngas line; 16. a second syngas line; 17. a third syngas line; 18. a fourth syngas line; 19. a first flue gas pipeline; 20. a second flue gas conduit; 21. a third flue gas pipeline; 22. a fourth flue gas pipeline; 23. a water vapor line; 24. an air line; 25. a syngas ash discharge port; 26. a flue gas ash discharge port; 27. a flue gas outlet; 28. an air inlet; 29. a gasification water inlet; 30. an integrated heat exchanger.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Unless otherwise specified, the devices and materials mentioned in the present invention are commercially available.
Example 1:
1) preparation of oxygen carrier and sludge:
the method comprises the following steps of (1) crushing original copper slag provided by Nanjing iron and steel works as a matrix, wherein the average particle size is about 1 mm; uniformly placing the mixture in a high-temperature muffle furnace, keeping the stacking thickness at 15mm, heating the mixture from room temperature to 1100 ℃ at a speed of 15 ℃/min, keeping the temperature for 2 hours, continuously introducing fresh air into the furnace in the calcining process to realize air calcination, and naturally cooling the air to the room temperature; the target oxygen carrier is obtained after taking out, crushing, screening (100 meshes) and storing, the element analysis of the original copper slag and the copper slag calcined at 1100 ℃ is shown in Table 1, and the calcination causes the increase of the oxygen element content in the oxygen carrier because of the decomposition reaction (Eq.1) of the ferric silicate. 2Fe2SiO4+ (sufficient) O2→2Fe2O3+2SiO2(Eq.1)
TABLE 1 elemental analysis of the original copper slag
The adopted sludge raw material is domestic sludge from Guangzhou cis-Ded sewage treatment plants. Dried at 105 ℃ for 48 hours and then sieved through an 80 mesh screen for commercial and elemental analyses as shown in table 2:
TABLE 2 elemental and Industrial analysis of sludge
2) The device operation scheme is as follows:
the structure of the device shown in fig. 1 is schematically illustrated, and mainly comprises an air reactor 3, a fuel reactor 4, a synthesis gas cyclone separator 5, a primary air cyclone separator 7, a secondary air cyclone separator 8, a material returning device 2, an oxygen carrier feeder 10, a sludge two-stage screw feeder 11, an air compressor 14, a water vapor compressor 13 and an integrated heat exchanger 30, and a circulating system is formed by pipelines with corresponding sizes.
The fuel reactor 4 is connected with the air reactor 3 through the return feeder 2, a synthesis gas outlet of the fuel reactor 4 is communicated with the synthesis gas cyclone separator 5 through a first synthesis gas pipeline 15, the synthesis gas cyclone separator 5 is communicated with the synthesis gas bag-type dust remover 6 through a second synthesis gas pipeline 16, and a third synthesis gas pipeline 17 connected with the synthesis gas bag-type dust remover outlet is divided into a fourth synthesis gas pipeline 18 and a synthesis gas collecting pipeline after passing through the integrated heat exchanger 30; the gas outlet of air reactor 3 and one-level air cyclone 7 are communicated through a first gas pipeline 19, the solid outlet of one-level air cyclone 7 is arranged in the inside of fuel reactor 4, the gas outlet of one-level air cyclone 7 and second-level air cyclone 8 are communicated through a second gas pipeline 20, second-level air cyclone 8 and gas bag-type dust collector 9 are communicated through a third gas pipeline 21, the outlet of gas bag-type dust collector 9 is connected with a fourth gas pipeline 22, the fourth gas pipeline 22 passes through an integrated heat exchanger 30 to extend, and the end of the fourth gas pipeline 22 is provided with a gas outlet 27.
The sludge two-stage screw feeder 11 is formed by matching two screw feeders with a hopper bin up and down and back and forth; a pipeline is arranged at the right side of the top of the air reactor 3 and is connected with a primary air cyclone separator 7; the gas outlet of the primary air cyclone separator 7 is connected with a secondary air cyclone separator 8; a solid outlet at the lower part of the secondary air cyclone separator 8 is a flue gas ash discharging port 26, a flue gas outlet at the upper part is connected with a flue gas bag-type dust collector 9, and then enters the integrated heat exchanger 30 along with a fourth flue gas pipeline 22 to recover heat, and finally is discharged from a flue gas outlet 27; a solid outlet pipeline at the lower part of the secondary air cyclone separator 8 extends into the fuel reactor 4 and is close to the right side of the sludge two-stage spiral feeder 11; two drainage baffles are designed in the fuel reactor 4, and a synthesis gas outlet is designed on the fuel reactor and connected with a synthesis gas cyclone separator 5; the synthesis gas is led into a synthesis gas bag-type dust collector 6 through a gas outlet at the upper part of a synthesis gas cyclone separator 5, and then led into an integrated heat exchanger 30, then the synthesis gas is shunted at the outlet of the integrated heat exchanger 30, one part of the synthesis gas is mixed with a water vapor pipeline 23 at the outlet of the integrated heat exchanger 30 to be used as a carrier gas of a fuel reactor 4, the other part of the synthesis gas is utilized through a synthesis gas collecting port, and the synthesis gas ash discharging port 25 is arranged at the lower part of the synthesis gas cyclone separator 5; the fuel reactor 4 and the air reactor 3 are connected by a return feeder 2; the gasification water flows through the integrated heat exchanger 30 in a countercurrent way from the gasification water inlet 29, is mixed with the shunted synthesis gas, directly enters the bottom of the fuel reactor 4 after passing through the vapor compressor 13, and enters the fuel reactor 4 through the air distribution plate 12 of the fuel reactor; after passing through the integrated heat exchanger 30 in a counter-current manner through the air inlet 28, the fresh air passes through the air line 24 provided with the air compressor 14 and directly enters the bottom of the air reactor 3, passes through the air distribution plate 1 of the air reactor and enters the air reactor 3.
When the system starts to operate, the prepared oxygen carrier and sludge enter a fuel reactor 8 according to the mass ratio of 5:1, react with the sludge under the fluidization environment provided by the mixed gas consisting of water vapor and synthesis gas, the sludge generates synthesis gas (R (2) -R (8)) through a series of pyrolysis, gasification, water vapor conversion and oxidation reactions, and meanwhile, the oxygen carrier is reduced to lose lattice oxygen; the reduced oxygen carrier (mixed with sludge ash) flows out of the fuel reactor 4 along the return feeder 2 under the action of a flow field, a small part of the oxygen carrier and the sludge ash are carried by the synthesis gas and enter the synthesis gas cyclone separator 5, a small part of the oxygen carrier and the sludge ash are discharged from a synthesis gas ash discharge port 25 after the gas-solid separation of the synthesis gas cyclone separator 5, the synthesis gas enters the synthesis gas bag-type dust remover 6 along a second synthesis gas pipeline 16 after the gas-solid separation of the synthesis gas cyclone separator 5, the synthesis gas enters the integrated heat exchanger 30 through a third synthesis gas pipeline 17, the synthesis gas after waste heat recovery is divided into two parts, one part of the synthesis gas is mixed with a water vapor pipeline 23 through a fourth synthesis gas pipeline 18 to serve as the carrier gas of the fuel reactor 4, and the volume ratio of the synthesis gas and the water vapor entering the fuel reactor is 3: 6; the other part of the synthesis gas is reserved and collected by a synthesis gas collecting pipeline; the oxygen carrier (mixed with sludge ash) flows back to the air reactor 3 through the material returning device 2; the reduced oxygen carrier reacts with air in the air reactor 3 to release a large amount of heat, and meanwhile, the oxygen carrier is oxidized by the air to recover lattice oxygen, so that regeneration is realized; the regenerated oxygen carrier (mixed with the sludge ash) enters the primary air cyclone separator 7 under the action of a flow field, the oxygen carrier and the sludge ash are separated according to the difference of mass density of the oxygen carrier and the sludge ash, and most of the oxygen carrier flows back to the fuel reactor 4 from a solid outlet pipeline of the primary air cyclone separator 7 to complete circulation; the sludge ash and the flue gas (a small part of oxygen carriers) enter a secondary air cyclone separator 8, gas-solid separation is carried out under the action of centrifugal force, part of the sludge ash (residual oxygen carriers) is separated out of a circulating system from a flue gas ash discharging port 26, the flue gas enters a flue gas bag-type dust remover 9 along a fourth flue gas pipeline 22 and then enters an integrated heat exchanger 30, and the flue gas is discharged out of the system from a flue gas outlet 27 after waste heat recovery; the oxygen carrier lost by ash discharge is supplemented to enter the system through the oxygen carrier feeder 6, so that the feeding mass ratio of the oxygen carrier to the sludge is ensured to be 5 in the operation process, and the stability of the system operation is realized; wherein fresh air is directly extracted from the environment, enters the integrated heat exchanger 30 through the air inlet 28, performs counter-current heat exchange, and then enters the air reactor 3 through the air compressor 14; the gasified water is introduced from a gasification water inlet 29, passes through an integrated heat exchanger 30, is changed into steam after countercurrent heat exchange to be mixed with part of synthesis gas, passes through a steam compressor 13 and then enters the fuel reactor 4; throughout the reaction, the air reactor 3 was maintained at a high temperature of 900 ℃ while the fuel reactor 4 was maintained at a temperature of 900 ℃.
C/H+[O]→H2/CH4/CO/CnHm/CO2/H2O R(2)
CO+H2O→CO2+H2R(3)
C+H2O→CO+H2R(4)
CH4+H2O→CO+3H2R(5)
CO+3Fe2O3→CO2+2Fe3O4R(6)
C+2H2→CH4R(7)
C+CO2→2CO R(8)
The operating parameters and results in this example are shown in table 3. Table 3 shows the conditions for treating the 1100 ℃ calcined copper slag in examples 1 to 4 and the gas contents of carbon dioxide, hydrogen, carbon monoxide and methane in the syngas obtained by the treatment with the apparatus of the present invention.
Examples 2 to 4 are substantially the same as example 1 except for the differences shown in Table 3.
TABLE 3
The method for treating sludge by chemical looping gasification based on copper slag as an oxygen carrier and the device for realizing the method provided by the invention are described in detail above, the description of the above embodiments is only used for helping understanding the technical scheme of the invention and the core idea thereof, and it should be noted that, for those skilled in the art, the invention can be modified and modified in several ways without departing from the principle of the invention, and the modified and modified are also within the protection scope of the claims of the invention.
Claims (1)
1. A method for treating sludge by chemical chain gasification based on copper slag as an oxygen carrier is characterized by comprising the following steps:
(1) heating the copper slag to 1100 ℃ at a speed of 15 ℃/min, calcining at a constant temperature, naturally cooling to room temperature, crushing and screening particles smaller than 100 meshes to serve as oxygen carriers for later use;
(2) reacting the oxygen carrier obtained in the step (1) with sludge in a fuel reactor, wherein the mass ratio of the oxygen carrier to the sludge is 3-5: 1, so as to obtain reacted sludge, reduced oxygen carrier and synthesis gas, a mixture of a part of the reacted sludge and a part of the reduced oxygen carrier enters an air reactor through a material returning device, the reduced oxygen carrier reacts with air in the air reactor under the action of the air reactor to realize the regeneration of the oxygen carrier, the regenerated oxygen carrier reflows to the fuel reactor through a solid outlet pipeline of an air primary cyclone separator, and continuously reacts with the sludge in the fuel reactor to form a cycle, after the gas-solid separation of the other part of the reacted sludge, the other part of the reduced oxygen carrier and the synthesis gas, the other part of the reacted sludge and the other part of the reduced oxygen carrier are discharged through a synthesis gas ash discharge port, the synthesis gas enters an integrated heat exchanger after gas-solid separation of a synthesis gas cyclone separator, waste heat in the synthesis gas is recovered through the integrated heat exchanger and then is divided, one part of the synthesis gas is mixed with water vapor to be used as carrier gas of a fuel reactor, the volume ratio of the synthesis gas to the water vapor in the fuel reactor is 2-3: 6, the other part of the synthesis gas is collected for later use, and fresh air is used as the carrier gas of an air reactor after heat absorption through the integrated heat exchanger;
the device for realizing the method for treating the sludge through chemical chain gasification based on the copper slag as the oxygen carrier comprises a fuel reactor, an air reactor and an integrated heat exchanger, wherein a sludge feeder feeding port and an oxygen carrier feeder feeding port are arranged on the fuel reactor, the fuel reactor is connected with the air reactor through a material returning device, a synthetic gas outlet of the fuel reactor is communicated with a synthetic gas cyclone separator through a first synthetic gas pipeline, the synthetic gas cyclone separator is communicated with a synthetic gas bag-type dust collector through a second synthetic gas pipeline, and a third synthetic gas pipeline connected with the outlet of the synthetic gas bag-type dust collector is divided into a fourth synthetic gas pipeline and a synthetic gas collecting pipeline after passing through the integrated heat exchanger; the fuel gas recycling device comprises a fuel gas reactor, a first-stage air cyclone separator, a second-stage air cyclone separator, a sludge feeder, a first-stage air cyclone separator, a second-stage air cyclone separator, a third-stage spiral feeder and a second-stage spiral feeder, wherein a flue gas outlet of the air reactor is communicated with the first-stage air cyclone separator through a first flue gas pipeline; a plurality of drainage baffles are arranged in the fuel reactor; an air pipeline is arranged on the integrated heat exchanger, the air pipeline which exchanges heat through the integrated heat exchanger is connected with the air reactor, and air in the air pipeline is used as carrier gas of the air reactor; the fourth synthesis gas pipeline and the water vapor pipeline are merged and enter the fuel reactor, and the synthesis gas and the water vapor are used as carrier gas of the fuel reactor; the bottom of the fuel reactor is provided with a fuel reactor air distribution plate, and the bottom of the air reactor is provided with an air reactor air distribution plate.
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| CN201810458112.XA CN108870407B (en) | 2018-05-14 | 2018-05-14 | Method for treating sludge through chemical-looping gasification based on copper slag as oxygen carrier and device for implementing method |
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| CN110342770A (en) * | 2019-07-15 | 2019-10-18 | 河南城建学院 | Sludge chemical chain gasification system and technique based on steel slag oxygen carrier |
| CN111534332B (en) * | 2020-04-28 | 2021-06-11 | 东南大学 | Microwave-assisted chemical-looping gasification soil heavy metal restoration plant heat treatment method |
| CN111732990B (en) * | 2020-06-22 | 2023-04-07 | 青岛理工大学 | Preparation process and method of oxygen carrier for chemical chain gasification of carbon-containing solid waste |
| CN111911934B (en) * | 2020-07-28 | 2022-05-27 | 东南大学 | Method for treating hazardous waste by using oxygen carrier to assist combustion of rotary kiln |
| CN113188129B (en) * | 2020-12-25 | 2022-08-05 | 中国科学院广州能源研究所 | Method and device for removing pollutants by organic solid waste pyrolysis coupling chemical chain combustion |
| CN115069256A (en) * | 2022-07-27 | 2022-09-20 | 中国科学院广州能源研究所 | Oxygen carrier and application thereof in chemical-looping gasification of cellulose solid wastes |
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| CN102410530A (en) * | 2011-10-26 | 2012-04-11 | 昆明理工大学 | Method for preparing oxygen carrier for chemical-looping combustion by utilizing copper residues |
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| CN1795257A (en) * | 2003-05-29 | 2006-06-28 | 阿尔斯托姆科技有限公司 | Hot solids gasifier with co sb 2 /sb removal and hydrogen production |
| CN102410530A (en) * | 2011-10-26 | 2012-04-11 | 昆明理工大学 | Method for preparing oxygen carrier for chemical-looping combustion by utilizing copper residues |
| CN107142125A (en) * | 2017-06-07 | 2017-09-08 | 中国科学院广州能源研究所 | A kind of sludge chemical chain gasification orientation produces synthetic gas method and realizes the device of this method |
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