CN217235616U - Waste gas and waste liquid incineration and recovery processing device containing chlorosilane - Google Patents
Waste gas and waste liquid incineration and recovery processing device containing chlorosilane Download PDFInfo
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- CN217235616U CN217235616U CN202220902531.XU CN202220902531U CN217235616U CN 217235616 U CN217235616 U CN 217235616U CN 202220902531 U CN202220902531 U CN 202220902531U CN 217235616 U CN217235616 U CN 217235616U
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The utility model provides a waste gas and waste liquid incineration and recovery processing device that contain chlorosilane, processing apparatusThe system comprises an incinerator, a waste heat boiler, a quench tower, a dust remover, a hydrochloric acid absorption tower, an alkaline washing tower, a reheater, an SCR reactor and adsorption equipment which are connected in sequence; the top of the incinerator is provided with a burner, and the outlet of the burner is connected to the top inlet of the incinerator. Processing apparatus uses burning furnace as the source, burns the processing to chlorosilane-containing's waste gas and waste liquid, turns into the material of easy processing with chlorosilane, connects gradually equipment at different levels again and separates or retrieves reaction product and the heat that carries, retrieves and obtains SiO 2 The products such as hydrochloric acid and the like solve the problems that the conventional method is not thorough in treatment of the wastes and chloride ions are difficult to remove, greatly improve the removal rate of chlorosilane-containing, and have high product and waste heat recovery rates; the treatment device has reasonable structural design, does not cause secondary pollution, and is environment-friendly and economical.
Description
Technical Field
The utility model belongs to the technical field of waste recovery processing, a waste gas and waste liquid that contain chlorosilane burn and recovery processing device is related to, especially relate to a discharged waste gas and waste liquid that contain chlorosilane burn and recovery processing device in the polycrystalline silicon production process.
Background
With the rapid development of the microelectronic industry and the photovoltaic industry, the demand for the basic raw material of polycrystalline silicon is increasing day by day, and the polycrystalline silicon is widely applied to various subjects and fields such as chemical industry, metallurgy, machinery, electronics and the like. With the continuous expansion of the yield and scale of polysilicon, a large amount of waste gas and waste liquid containing chlorosilane and other pollutants is discharged during the production process, and environmental protection and safety problems are caused if the pollutants are not treated in time, which is one of the bottlenecks to be solved urgently in the whole polysilicon industry chain.
According to the raw materials used in the production of polysilicon, the generated waste gas and waste liquid contain chlorosilane such as trichlorosilane, silicon tetrachloride and dichlorosilane and a small amount of metal impurity chloride, and for the treatment of the waste gas and the waste liquid, a hydrolysis alkali absorption method, a lime milk neutralization precipitation method, an incineration treatment method and the like are commonly adopted at present. The hydrolysis alkali absorption method generally comprises the steps of sending waste gas and waste liquid into a leaching tower, continuously washing the waste gas and the waste liquid by using a sodium hydroxide solution, filtering the waste gas and the waste liquid, externally transporting and burying the slag, sending the filtrate into a waste water treatment process for continuous treatment, but the method can generate a large amount of waste water and waste slag, particularly has high alkali consumption, and easily causes the equipment to be incapable of normally operating due to slag bonding; lime milk neutralization and precipitation methods also produce a large amount of waste residues, and chloride ions still exist in the solution and cannot be directly discharged, so that subsequent treatment is required.
The incineration treatment method is a new treatment technology, and toxic and difficult-to-treat chlorosilane is hydrolyzed at high temperature in an incinerator to generate an easily-treated substance. CN 111457400A discloses a waste gas and liquid incineration system and process containing organosilane, the system comprises a primary incineration chamber, a secondary incineration chamber and a tail gas purification device which are connected in sequence, the waste gas containing organosilane is sent into the primary incineration chamber through a waste gas pretreatment device, the waste liquid containing organosilane is sent into the primary incineration chamber through a high-pressure atomization device, the waste gas pretreatment device comprises a spraying washing tower, a condenser, a water-sealed tank and a flame arrester which are connected in sequence, waste gas containing organosilane is introduced into the spraying washing tower from a waste gas inlet I, a waste gas inlet II and a waste gas outlet I are connected with a waste gas buffer tank, a waste gas outlet II is connected with the condenser, and a waste gas outlet III is connected with an activated carbon adsorption tank; the condenser is connected with the activated carbon adsorption tank through a gas detector; the system and the process are complex in whole, the incineration treatment comprises two steps of operation, the pretreatment is carried out before the incineration treatment to recover partial components, and the treatment of nitrogen oxides is not involved.
CN 112628772A discloses a process for incinerating methyl chlorosilane production waste gas, which comprises the steps of adjusting the pressure of methyl chlorosilane production waste gas, sending the methyl chlorosilane production waste gas to an incinerator, removing nitric oxide from the incinerated smoke gas through NCR, then sending the burned smoke gas into a waste heat recovery device, sending the smoke gas after waste heat recovery into a quench tower, quenching and cooling the smoke gas, then sending the smoke gas into a hydrochloric acid absorption tower to remove most of hydrogen chloride, further removing chlorine through an alkali washing tower, finally removing dust through a wet electric dust collector, and then heating and discharging at high altitude. The temperature required by the step of removing the nitrogen oxides in the process is extremely high, and other side reactions are easy to occur after the incineration step, so that the recovery of other products is not facilitated.
In summary, for the treatment of waste gas and waste liquid containing chlorosilane, after incineration treatment, appropriate combination equipment needs to be selected to separate and recover various products and improve the utilization rate of system heat.
SUMMERY OF THE UTILITY MODEL
Problem to prior art existence, the utility model aims to provide a waste gas and waste liquid incineration and recovery processing device that contain chlorosilane, processing apparatus uses burning furnace as the source, burns the processing to waste gas and the waste liquid that contain chlorosilane, connects gradually equipment at different levels again and separates or retrieve reaction product and the heat that carries, has improved conventional method and has been difficult to the problem of getting rid of thoroughly and chloride ion to this type of waste disposal, and product and heat recovery rate are high, and can not cause secondary pollution.
To achieve the purpose, the utility model adopts the following technical proposal:
the utility model provides a waste gas and waste liquid incineration and recovery processing device containing chlorosilane, which comprises an incinerator, a waste heat boiler, a quench tower, a dust remover, a hydrochloric acid absorption tower, an alkali wash tower, a reheater, an SCR reactor and adsorption equipment which are connected in sequence; the top of the incinerator is provided with a burner, and an outlet of the burner is connected to a top inlet of the incinerator.
The utility model discloses in, in polycrystalline silicon production process, according to the selection of raw materials kind, can produce waste gas and the waste liquid that contains chlorosilane, through adopting burning furnace, through the pyrohydrolysis reaction, turn into easy to handle's SiO with chlorosilane 2 HCl and a small amount of Cl 2 And the generated smoke is subjected to heat recovery through a waste heat boiler, is subjected to quenching cooling to avoid generation of harmful byproducts such as dioxin, and then is subjected to dust remover and hydrochloric acid absorption tower to recover SiO respectively 2 Particles and HCl, and a caustic tower further removes the remaining small amount of HCl and Cl 2 After being heated by a reheater, SCR denitration treatment is carried out, and the denitrated flue gas is discharged after adsorption treatment; through the treatment, the problems that the conventional method is not thorough in treatment of the waste containing chlorosilane and chloride ions are difficult to remove can be effectively solved, the breaking rate and treatment effect of the waste containing chlorosilane can be greatly improved, and the recovery rate of waste heat and products is high; the treatment device has reasonable structural design, can not cause secondary pollution,is environment-friendly and economical.
Following conduct the utility model discloses preferred technical scheme, nevertheless do not conduct the utility model provides a technical scheme's restriction, through following technical scheme, can reach and realize better the utility model discloses a technical purpose and beneficial effect.
As the utility model discloses preferred technical scheme, burn burning furnace and include vertical top combustion furnace, it is equipped with waste gas entry and waste liquid entry to burn to be equipped with, the waste liquid entrance is equipped with the nozzle.
As the preferable technical proposal of the utility model, natural gas and air are introduced into the inlet of the burner.
The utility model discloses in, burn burning furnace and select vertical top combustion furnace, its reason lies in: firstly, a great deal of SiO is generated by burning chlorosilane 2 The particles are high in melting point and still solid at high temperature, the horizontal incinerator is easy to block a flue gas outlet pipeline, and the vertical incinerator is favorable for ash removal; secondly, a vertical furnace is adopted, the waste liquid is sprayed from a furnace end after being atomized, the downward stroke is long, the full combustion can be realized, and the phenomena of incomplete combustion of the waste liquid and adhesion to a furnace wall are easy to occur in a horizontal furnace; the vertical furnace can save the land occupation;
the waste gas and the waste liquid have different phase states, so that the waste gas and the waste liquid can enter the incinerator in different modes, the waste gas can enter the waste gas buffer tank firstly, the pressure regulating valve controls the pressure of the waste gas, the waste liquid is atomized and sprayed when entering the incinerator through a pipeline, the incineration treatment is facilitated, steam is adopted for the atomized and sprayed as an atomized medium, on one hand, the viscosity of the waste liquid is reduced by steam heating, on the other hand, the hydrogen-to-hydrogen ratio in the incinerator is improved, and the generation of chlorine is inhibited; because the heat value of the waste gas and liquid is higher, the natural gas is introduced into the incinerator to raise the temperature of the hearth to about 1000 ℃ when the incinerator is in a driving working condition, then the waste gas and liquid is introduced gradually, and then the consumption of the natural gas is reduced, namely a large amount of natural gas is not needed to provide heat under a normal working condition, the natural gas is only used as fuel for combustion, air is used as combustion-supporting gas, and chlorosilane is hydrolyzed at high temperature fully in the combustion process.
As the utility model discloses preferred technical scheme, exhaust-heat boiler includes diaphragm type wall exhaust-heat boiler, burn the bottom export of burning furnace and link to each other through slope flue and exhaust-heat boiler's heat source entry, an ash discharge mouth of both sharings.
As the utility model discloses preferred technical scheme, quench tower's coolant includes the cooling water, gets into sharp heat transfer in the flue gas through atomizing spray gun atomizing back, atomizing steam and flue gas direct contact take away by the flue gas behind the heat transfer.
The utility model discloses in, quench tower's setting is mainly to carry out rapid cooling to the flue gas, avoids generating harmful substance such as dioxin at the flue gas under higher temperature, and through adopting above-mentioned coolant, the flue gas cooling is extremely fast, reduces hundreds of ℃ in one second, for example in 1s the flue gas temperature by 600 ℃ to 200 ℃.
As the preferred technical scheme of the utility model, the dust remover comprises a bag-type dust remover.
In the utility model, the bag dust collector is selected as the dust collector, wherein the bag can be selected as the polytetrafluoroethylene laminated bag, and the tolerance temperature can reach 250 ℃; SiO in the flue gas is removed by a dust remover 2 The particles are collected and enter an ash bin, the dust removal process is dry dust removal, the dust removal efficiency is high, a large amount of water resources are saved, waste water and waste residues are not generated, and the recycling of useful resources can be realized.
As the utility model discloses preferred technical scheme, processing apparatus still includes the cooling absorption tower, the cooling absorption tower sets up between dust remover and hydrochloric acid absorption tower.
The utility model discloses in, the flue gas temperature after the dust removal is still higher, and unsuitable HCl's direct absorption sets up the cooling absorption tower and carries out the secondary cooling, later retrieves the HCl in the flue gas through hydrochloric acid absorption tower, with hydrochloric acid absorption tower setting after the dust remover, the hydrochloric acid of recovery is comparatively clean, can regard as the product to use.
As the utility model discloses preferred technical scheme, processing apparatus still includes the draught fan, the draught fan sets up between alkaline tower and reheater.
The utility model discloses in, according to above-mentioned processing apparatus's different stages, pressure in the device system also can be different, and the burning furnace that burns of front end can adopt combustion fan to establish the malleation, and the negative pressure is established by the draught fan in the middle section, the flow of the flue gas of being convenient for, draught fan optional glass steel material avoids taking place the problem of corruption, adopts the malleation again when rear end denitration treatment.
As the utility model discloses preferred technical scheme, the reheater includes heat exchanger or combustor, the combustor includes flue formula combustor.
The utility model discloses in, because flue gas cooling back temperature is less than the temperature of SCR denitration treatment, therefore need carry out reheat, then load SCR denitration catalyst in the SCR reactor to let in ammonia as reaction raw materials, react with the nitrogen oxide in the flue gas.
As the utility model discloses preferred technical scheme, adsorption equipment includes the activated carbon adsorption case.
As the utility model discloses preferred technical scheme, processing apparatus still includes the chimney, adsorption equipment's gas outlet links to each other with the chimney.
Compared with the prior art, the utility model discloses following beneficial effect has:
(1) processing apparatus uses burning furnace as the source, burns the processing to chlorosilane-containing waste gas and waste liquid, turns into easy-to-handle's SiO with chlorosilane 2 HCl and Cl 2 The substances are connected with equipment at all levels in sequence to separate or recycle the reaction product and the heat carried by the reaction product, and the SiO is obtained by recycling 2 The products such as hydrochloric acid and the like solve the problems that the conventional method is not thorough in treatment of the wastes and chloride ions are difficult to remove, greatly improve the removal rate of chlorosilane-containing products, and can reach more than 99.8%, and the recovery rate of the products and waste heat is high;
(2) processing apparatus structural design is reasonable, can not cause secondary pollution, environmental protection economy.
Drawings
FIG. 1 is a schematic structural diagram of a waste gas and waste liquid incineration and recovery treatment device containing chlorosilane provided in embodiment 1 of the present invention;
the method comprises the following steps of 1-incinerator, 2-combustor, 3-waste heat boiler, 4-quench tower, 5-dust remover, 6-cooling absorption tower, 7-hydrochloric acid absorption tower, 8-alkaline washing tower, 9-induced draft fan, 10-reheater, 11-SCR reactor, 12-adsorption equipment and 13-chimney.
Detailed Description
To better explain the technical solution of the present invention, it is convenient to understand the technical solution of the present invention, and the following is further detailed description of the present invention, but the following embodiments are only simple examples of the present invention, and do not represent or limit the protection scope of the present invention, and the protection scope of the present invention is subject to the claims.
The utility model provides a waste gas and waste liquid incineration and recovery processing device containing chlorosilane, which comprises an incinerator 1, a waste heat boiler 3, a quench tower 4, a dust remover 5, a hydrochloric acid absorption tower 7, an alkali wash tower 8, a reheater 10, an SCR reactor 11 and an adsorption device 12 which are connected in sequence; the top of the incinerator 1 is provided with a burner 2, and the outlet of the burner 2 is connected to the top inlet of the incinerator 1.
The following are typical but non-limiting examples of the present invention:
example 1:
the embodiment provides a waste gas and waste liquid incineration and recovery processing device containing chlorosilane, the structural schematic diagram of the processing device is shown in fig. 1, and the processing device comprises an incinerator 1, a waste heat boiler 3, a quench tower 4, a dust remover 5, a hydrochloric acid absorption tower 7, an alkaline washing tower 8, a reheater 10, an SCR reactor 11 and an adsorption equipment 12 which are connected in sequence; the top of the incinerator 1 is provided with a burner 2, and the outlet of the burner 2 is connected to the top inlet of the incinerator 1.
The incinerator 1 comprises a vertical top-fired furnace, a waste gas inlet and a waste liquid inlet are formed in the incinerator 1, and a nozzle is arranged at the waste liquid inlet.
Natural gas and air are introduced into the inlet of the combustor 2.
The waste heat boiler 3 comprises a membrane wall waste heat boiler, the bottom outlet of the incinerator 1 is connected with the heat source inlet of the waste heat boiler 3 through an inclined flue, and the bottom outlet and the heat source inlet share one ash discharge port.
The cooling medium of the quenching tower 4 is industrial cooling water.
The dust remover 5 is a bag-type dust remover, and the bag is made of polytetrafluoroethylene.
The treatment device further comprises a cooling absorption tower 6, wherein the cooling absorption tower 6 is arranged between the dust remover 5 and the hydrochloric acid absorption tower 7.
The treatment device further comprises an induced draft fan 9, and the induced draft fan 9 is arranged between the alkaline tower 8 and the reheater 10.
The reheater 10 is a flue burner.
The adsorption equipment 12 is an activated carbon adsorption tank.
The treatment device further comprises a chimney 13, and the gas outlet of the adsorption equipment 12 is connected with the chimney 13.
Example 2:
the embodiment provides a waste gas and waste liquid incineration and recovery treatment device containing chlorosilane, which comprises an incinerator 1, a waste heat boiler 3, a quench tower 4, a dust remover 5, a hydrochloric acid absorption tower 7, an alkaline washing tower 8, a reheater 10, an SCR reactor 11 and an adsorption device 12 which are connected in sequence; the top of the incinerator 1 is provided with a burner 2, and the outlet of the burner 2 is connected to the top inlet of the incinerator 1.
The incinerator 1 comprises a vertical top-fired furnace, a waste gas inlet and a waste liquid inlet are formed in the incinerator 1, and a nozzle is arranged at the waste liquid inlet.
Natural gas and air are introduced into the inlet of the combustor 2.
The waste heat boiler 3 comprises a membrane wall waste heat boiler, the bottom outlet of the incinerator 1 is connected with the heat source inlet of the waste heat boiler 3 through an inclined flue, and the bottom outlet and the heat source inlet share one ash discharge port.
The dust remover 5 is a bag-type dust remover, and the bag is made of ceramic fibers.
The treatment device further comprises an induced draft fan 9, and the induced draft fan 9 is arranged between the alkaline tower 8 and the reheater 10.
The reheater 10 is a shell and tube heat exchanger.
The adsorption equipment 12 is an activated carbon adsorption tank.
The treatment device further comprises a chimney 13, and the gas outlet of the adsorption equipment 12 is connected with the chimney 13.
Example 3:
the embodiment provides a waste gas and waste liquid incineration and recovery treatment device containing chlorosilane, which comprises an incinerator 1, a waste heat boiler 3, a quench tower 4, a dust remover 5, a hydrochloric acid absorption tower 7, an alkaline washing tower 8, a reheater 10, an SCR reactor 11 and an adsorption device 12 which are connected in sequence; the top of the incinerator 1 is provided with a burner 2, and the outlet of the burner 2 is connected to the top inlet of the incinerator 1.
The incinerator 1 comprises a vertical top-fired furnace, a waste gas inlet and a waste liquid inlet are formed in the incinerator 1, and a nozzle is arranged at the waste liquid inlet.
Natural gas and air are introduced into the inlet of the combustor 2.
The waste heat boiler 3 comprises a fire tube waste heat boiler, and the bottom outlet of the incinerator 1 is connected with the heat source inlet of the waste heat boiler 3 through an inclined flue.
The dust remover 5 is an electric dust remover.
The treatment device further comprises a cooling absorption tower 6, wherein the cooling absorption tower 6 is arranged between the dust remover 5 and the hydrochloric acid absorption tower 7.
The treatment device further comprises an induced draft fan 9, and the induced draft fan 9 is arranged between the alkaline tower 8 and the reheater 10.
The reheater 10 is a flue burner.
The adsorption equipment 12 is an activated carbon adsorption tank.
The treatment device further comprises a chimney 13, and the gas outlet of the adsorption equipment 12 is connected with the chimney 13.
The device in the embodiment is adopted to treat waste gas and waste liquid containing chlorosilane discharged in the production process of polycrystalline silicon, and mainly comprises the following operation processes:
the waste gas and waste liquid containing chlorosilane are respectively sent into an incinerator 1 through pipelines, natural gas and combustion-supporting air are adopted in the incinerator 1, and chlorosilane is generated into SiO which is easy to treat through high-temperature hydrolysis reaction 2 HCl and a small amount of Cl 2 And the like; height of generationThe warm flue gas recovers heat through a waste heat boiler 3; in order to prevent the generation of dioxin in the flue gas, the flue gas at the outlet of the waste heat boiler 3 enters a quenching tower 4 for quenching, and the temperature of the flue gas can be reduced to 200 ℃ from 600 ℃ within 1 s; the flue gas enters a dust remover 5 after coming out of the quench tower 4, and SiO in the flue gas is removed 2 The particles are collected and enter an ash bin; the dedusted flue gas enters a cooling absorption tower 6 for secondary cooling, and then HCl in the flue gas is recovered through a hydrochloric acid absorption tower 7; small amount of HCl and Cl remaining in the flue gas 2 After being removed by an alkaline washing tower 8, the flue gas is sent to a flue type reheater 10 by an induced draft fan 9 to be heated and then subjected to SCR denitration treatment, and the denitrated flue gas is absorbed by activated carbon and then discharged into a chimney 13.
It can be seen from the above-mentioned embodiment that synthesize processing apparatus uses burning furnace as the source, burns the processing to chlorosilane-containing waste gas and waste liquid, turns into easy-to-handle SiO with chlorosilane 2 HCl and Cl 2 The substances are connected with equipment at all levels in sequence to separate or recycle the reaction product and the heat carried by the reaction product, and the SiO is obtained by recycling 2 The products such as hydrochloric acid and the like solve the problems that the conventional method is not thorough in treatment of the wastes and chloride ions are difficult to remove, greatly improve the removal rate of chlorosilane-containing products, and can reach more than 99.8%, and the recovery rate of the products and waste heat is high; the treatment device has reasonable structural design, does not cause secondary pollution, and is environment-friendly and economical.
The present invention is described in the above embodiments, but the present invention is not limited to the above detailed device, i.e. the present invention must rely on the above detailed device to implement. It should be clear to those skilled in the art that any improvement of the present invention, to the addition of the equivalent replacement and auxiliary devices of the present invention, the selection of the specific mode, etc., all fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. The device for incinerating and recycling the waste gas and the waste liquid containing chlorosilane is characterized by comprising an incinerator, a waste heat boiler, a quench tower, a dust remover, a hydrochloric acid absorption tower, an alkali wash tower, a reheater, an SCR (selective catalytic reduction) reactor and adsorption equipment which are sequentially connected; the top of the incinerator is provided with a burner, and the outlet of the burner is connected to the top inlet of the incinerator.
2. The apparatus for incineration and recycling of chlorosilane-containing waste gas and liquid as claimed in claim 1, wherein the incinerator comprises a vertical top-fired furnace, the incinerator is provided with a waste gas inlet and a waste liquid inlet, and the waste liquid inlet is provided with a nozzle.
3. The incineration and recovery treatment device for chlorosilane-containing waste gas and liquid according to claim 1, wherein natural gas and air are introduced into the inlet of the combustor.
4. The incineration and recovery treatment device for chlorosilane-containing waste gas and liquid according to claim 1, wherein the exhaust-heat boiler comprises a membrane wall exhaust-heat boiler, and the bottom outlet of the incinerator is connected with the heat source inlet of the exhaust-heat boiler through an inclined flue, and the bottom outlet and the heat source inlet share an ash discharge port.
5. The incineration and recovery treatment device for waste gas and liquid containing chlorosilane as claimed in claim 1, wherein the dust remover includes a bag-type dust remover.
6. The incineration and recovery treatment device for chlorosilane-containing waste gas and liquid according to claim 1, further comprising a cooling absorption tower, wherein the cooling absorption tower is arranged between the dust remover and the hydrochloric acid absorption tower.
7. The incineration and recovery treatment device for chlorosilane-containing waste gas and liquid according to claim 1, further comprising an induced draft fan, wherein the induced draft fan is arranged between the alkaline tower and the reheater.
8. The apparatus for incineration and recovery of chlorosilane-containing waste gas and liquid according to claim 1, wherein the reheater comprises a heat exchanger or a burner, and the burner comprises a flue burner.
9. The incineration and recovery treatment device for chlorosilane-containing waste gas and liquid according to claim 1, wherein the adsorption equipment comprises an activated carbon adsorption tank.
10. The incineration and recovery treatment device for chlorosilane-containing waste gas and liquid according to claim 1, wherein the treatment device further comprises a chimney, and the gas outlet of the adsorption equipment is connected with the chimney.
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| CN202220902531.XU CN217235616U (en) | 2022-04-19 | 2022-04-19 | Waste gas and waste liquid incineration and recovery processing device containing chlorosilane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117146286A (en) * | 2023-10-30 | 2023-12-01 | 上海朗蔚环保科技有限公司 | Silane waste gas treatment process by combustion washing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117146286A (en) * | 2023-10-30 | 2023-12-01 | 上海朗蔚环保科技有限公司 | Silane waste gas treatment process by combustion washing method |
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