CN113750761A - Method for preparing wet desulfurizing agent by using semidry desulfurization ash and application - Google Patents

Method for preparing wet desulfurizing agent by using semidry desulfurization ash and application Download PDF

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Publication number
CN113750761A
CN113750761A CN202110912988.9A CN202110912988A CN113750761A CN 113750761 A CN113750761 A CN 113750761A CN 202110912988 A CN202110912988 A CN 202110912988A CN 113750761 A CN113750761 A CN 113750761A
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semi
wet
ash
desulfurizing agent
dry
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顾立群
杨晓域
王如意
黄亚继
王福栽
廖立
程群
林红英
周洋
张皓
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Baoshan Iron and Steel Co Ltd
Southeast University
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Baoshan Iron and Steel Co Ltd
Southeast University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/346—Controlling the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/507—Sulfur oxides by treating the gases with other liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03C1/00—Magnetic separation
    • B03C1/02—Magnetic separation acting directly on the substance being separated
    • B03C1/30—Combinations with other devices, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to a method for preparing a wet desulfurizing agent by using semi-dry desulfurization ash and application thereof. The method reduces the consumption of lime and limestone resources, improves the thermal efficiency of reaction tail gas, solves the problem that the semi-dry flue gas desulfurization byproduct cannot be effectively recycled, reduces the wet flue gas desulfurization cost, avoids secondary pollution caused by stockpiling and burying semi-dry flue gas desulfurization ash, and has important significance to social economy and ecology.

Description

Method for preparing wet desulfurizing agent by using semidry desulfurization ash and application
Technical Field
The invention relates to the technical field of semi-dry desulfurization ash treatment, in particular to a method for preparing a wet desulfurizing agent by using semi-dry desulfurization ash and application thereof.
Background
The desulfurizer adopted by the semi-dry flue gas desulfurization process is usually calcium oxide or calcium hydroxide, and the byproduct semi-dry desulfurization ash after semi-dry desulfurization is a high-calcium high-sulfur mixture, and the main components of the semi-dry desulfurization ash comprise calcium sulfite, calcium sulfate, calcium oxide, calcium hydroxide and calcium carbonate, and also contain a small amount of chloride and heavy metal elements. The property and instability of the semi-dry desulfurized fly ash seriously affect the reapplication of the semi-dry desulfurized fly ash to other aspects such as buildings, soil, cement manufacture and the like. At present, the research on the comprehensive utilization of the desulfurized fly ash mainly focuses on the aspects of using the desulfurized fly ash as a cement retarder, improving soil and manufacturing artificial reefs, but the desulfurized fly ash is limited by the characteristics of high calcium and high sulfur and the transportation radius, so that the desulfurized fly ash has limited use amount and no market advantage. The desulfurized ash is mixed with other substances for use, such as cement or concrete, and the like, so that the desulfurized ash has certain feasibility, but the effect is limited by the condition of dosage, and the product quality is problematic when too much or too little, so that the potential safety hazard is caused. Therefore, the most common method for treating semi-dry desulfurized fly ash is direct landfill or stacking, but the method causes serious environmental pollution and land consumption and also generates waste of sulfur, calcium and metal resources.
The publication number is CNO4446247A, and the name is 'a method for preparing interior wall putty powder by using dry and semi-dry desulfurized fly ash', the semi-dry desulfurized fly ash is calcined and milled into powder and then is mixed with milled white cement, talcum powder, vae-type redispersible emulsion powder, hydroxypropyl methyl cellulose ether and other materials to be used for preparing interior wall putty powder, the related materials are more, the dosage of various components and the milled particle size are clearly specified, the hidden danger of product quality can be caused by too many or too few components, the operation requirement is higher, the operation is more troublesome, and the actual market application is very limited. The publication No. CN110436506A is named as a method for oxidizing semi-dry desulphurization ash by using industrial waste sulfuric acid, the industrial waste sulfuric acid is used for oxidizing the semi-dry desulphurization ash, the product is repeatedly washed and stood, and calcium oxide and calcium hydroxide which do not participate in desulphurization reaction and calcium sulfite which are more in the desulphurization ash are converted into calcium sulfate. The operation has certain dangerousness, the calcium-containing components in the semi-dry desulfurized fly ash are completely converted into the calcium sulfate, the calcium sulfate is not fully utilized according to the characteristics of the semi-dry desulfurized fly ash, partial resources in the semi-dry desulfurized fly ash are wasted to a certain extent, and the significance of the semi-dry desulfurized fly ash to practical application is not obvious.
In summary, the semidry desulfurization ash has complex components and large content fluctuation of each component, which causes the property to be extremely unstable, the dosage of each component needs to be strictly controlled when the semidry desulfurization ash is mixed with other substances, and meanwhile, because of the characteristics of high calcium and high sulfur, if the semidry desulfurization ash is directly buried, a large amount of calcium, sulfur and metal elements in the semidry desulfurization ash are wasted, so that an effective method for treating the semidry desulfurization ash is urgently needed, and the utilization rate is improved by recycling according to the characteristics.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a wet desulfurizing agent by using semi-dry desulfurization ash and application thereof, solves the problem of secondary pollution caused by stacking the semi-dry desulfurization ash, and realizes resource utilization of the semi-dry desulfurization ash.
The technical scheme adopted by the invention is as follows:
a method for preparing a wet desulfurizing agent by using semidry desulfurization ash comprises the following steps:
s1: firstly, drying semi-dry desulphurization ash which is a semi-dry desulphurization byproduct to remove water contained in the semi-dry desulphurization ash; then screening and removing large-particle impurities in the semi-dry desulfurization ash;
s2: feeding the treated semi-dry desulfurized fly ash into a boiler furnace, returning part of tail gas generated by high-temperature reaction into the furnace, promoting the high-temperature reaction of the semi-dry desulfurized fly ash, wherein solid reaction products comprise calcium oxide and ferric oxide; meanwhile, the residual tail gas generated by the high-temperature reaction is discharged after dust removal and gas washing;
s3: separating calcium oxide and ferric oxide in the solid reaction product by a magnetic separation process;
s4: adding water into the separated calcium oxide, and filtering impurities to prepare the desulfurizer which can be used for the wet desulphurization process.
In the S1, the temperature of the drying treatment is 100-180 ℃; in the S2, the reaction temperature in the boiler furnace is 900 ℃, and the reaction process is as follows: and decomposing calcium hydroxide, calcium sulfite, calcium sulfate and ferrous oxide in the semidry desulfurization ash at high temperature, and reacting with the tail gas introduced into the hearth to generate calcium oxide and ferric oxide.
In the S3, the magnetic separation process is carried out before the reaction product is cooled.
An application method of a wet desulfurizing agent prepared by using semidry desulfurization ash comprises the following steps:
when the inlet of the wet desulphurization tower is S02The concentration is 1000mg/m3When the desulfurizing agent prepared from the S4 is used alone, the mass of the desulfurizing agent is 1.3 times of that of the limestone raw material, and the outlet S0 of the wet desulfurization tower is used2The concentration is controlled at 10mg/m3The content of the compound is less than the content of the compound;
when the inlet of the wet desulphurization tower is S02The concentration is 1500mg/m3When the temperature of the water is higher than the set temperature,when the desulfurizing agent prepared by the S4 and the limestone raw material are mixed and used, the mass of the desulfurizing agent prepared by the S4 is 1.7 times that of the limestone raw material, so that the outlet S0 of a wet desulfurization tower is2The concentration is controlled at 30mg/m3；
When the inlet of the wet desulphurization tower is S02The concentration is 2000mg/m3When the desulfurizing agent prepared by the S4 is mixed with the limestone raw material, the mass of the desulfurizing agent prepared by the S4 is 2 times of that of the limestone raw material, so that the outlet S0 of the wet desulfurization tower is2The concentration is controlled at 50mg/m3Within.
The invention has the following beneficial effects:
the invention realizes the pyrolysis of the semi-dry desulfurized fly ash by using the tail gas as the catalyst, thereby improving the thermal efficiency. The resource utilization of the semi-dry desulfurization ash is realized, the prepared desulfurizer is used for the wet desulfurization process, the original desulfurization efficiency is improved compared with the method of directly using the semi-dry desulfurization ash for the wet desulfurization, the semi-dry desulfurization ash can replace the conventional wet desulfurization raw material limestone, the problem of cost rise caused by the rise of the price of the limestone in the wet desulfurization is solved, the safe and stable operation of the wet desulfurization is ensured, and the reliability is high. Meanwhile, the problem of secondary pollution caused by stacking of the semi-dry desulfurization ash is solved, and unnecessary resource waste is avoided. Has good social benefit and economic benefit. In addition, the reaction product of the invention has higher temperature, thus enhancing the magnetism of the iron and being beneficial to magnetic separation.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the present invention.
Detailed Description
The following describes embodiments of the present invention with reference to the drawings.
The method for preparing the wet desulfurizing agent by using the semidry desulfurization ash, as shown in fig. 1, comprises the following steps:
s1: firstly, drying semi-dry desulphurization ash which is a semi-dry desulphurization byproduct to remove water contained in the semi-dry desulphurization ash; then screening and removing large-particle impurities in the semi-dry desulfurization ash;
wherein the temperature of the drying treatment is preferably 100-180 ℃;
s2: feeding the treated semi-dry desulfurized fly ash into a boiler furnace, returning part of tail gas generated by high-temperature reaction into the furnace, promoting the high-temperature reaction of the semi-dry desulfurized fly ash, wherein solid reaction products comprise calcium oxide and ferric oxide; meanwhile, the residual tail gas generated by the high-temperature reaction is discharged after dust removal and gas washing;
wherein, the reaction temperature in the boiler furnace is preferably 900 ℃, and the reaction process is as follows: decomposing calcium hydroxide, calcium sulfite, calcium sulfate and ferrous oxide in the semidry desulfurization ash at high temperature, and reacting with tail gas introduced into a hearth to generate calcium oxide and ferric oxide; c0 in the tail gas can be used as a catalyst to promote pyrolysis of semi-dry desulfurized ash;
s3: separating calcium oxide and ferric oxide in the solid reaction product by a magnetic separation process; the magnetic separation is facilitated because the magnetic property of iron can be enhanced at a higher temperature, so that the magnetic separation process is carried out before the reaction product is cooled, and the magnetic separation process is not carried out after the reaction product is completely cooled.
S4: adding water into the separated calcium oxide, and filtering impurities to prepare the desulfurizer which can be used for the wet desulphurization process.
According to the application method of the wet desulfurizing agent prepared by the method for preparing the wet desulfurizing agent by using the semidry desulfurization ash, the desulfurizing agent prepared in the step S4 is used independently or is mixed with a conventional wet desulfurizing agent. The conventional wet desulfurizing agent includes lime, limestone or carbide slag, etc., and the dosage of the desulfurizing agent prepared from the semi-dry desulfurizing ash is slightly higher than that of the conventional lime, limestone or carbide slag in the application process because the impurity content in the semi-dry desulfurizing ash is relatively high and the content of the effective calcium component is relatively low. Specifically, the dosage of the desulfurizing agent prepared from the semidry desulfurization ash (or converted into slurry concentration) and the dosage of the conventional wet desulfurizing agent (or converted into lime slurry concentration) are determined according to S0 in the inlet and outlet flue gas of the wet desulfurization2The concentration of (a) varies as follows:
when the inlet of the wet desulphurization tower is S02The concentration is 1000mg/m3When the above-mentioned step S4 system is used aloneThe mass of the obtained desulfurizing agent is 1.3 times of that of the limestone raw material, and the outlet S0 of the wet desulfurization tower is used2The concentration is controlled at 10mg/m3The content of the compound is less than the content of the compound;
when the inlet of the wet desulphurization tower is S02The concentration is 1500mg/m3In the case of using the desulfurizing agent prepared in the above step S4 in combination with a limestone raw material, the mass of the desulfurizing agent prepared in the above step S4 is 1.7 times that of the limestone raw material, and the outlet S0 of the wet desulfurization tower is made to be a small amount2The concentration is controlled at 30mg/m3；
When the inlet of the wet desulphurization tower is S02The concentration is 2000mg/m3In the case of using the desulfurizing agent prepared in the above step S4 in combination with a limestone raw material, the mass of the desulfurizing agent prepared in the above step S4 is 2 times that of the limestone raw material, and the outlet S0 of the wet desulfurization tower is made to be a large amount2The concentration is controlled at 50mg/m3Within.

Claims (4)

1. A method for preparing a wet desulfurizing agent by using semidry desulfurization ash is characterized by comprising the following steps:
s1: firstly, drying semi-dry desulphurization ash which is a semi-dry desulphurization byproduct to remove water contained in the semi-dry desulphurization ash; then screening and removing large-particle impurities in the semi-dry desulfurization ash;
s2: feeding the treated semi-dry desulfurized fly ash into a boiler furnace, returning part of tail gas generated by high-temperature reaction into the furnace, promoting the high-temperature reaction of the semi-dry desulfurized fly ash, wherein solid reaction products comprise calcium oxide and ferric oxide; meanwhile, the residual tail gas generated by the high-temperature reaction is discharged after dust removal and gas washing;
s3: separating calcium oxide and ferric oxide in the solid reaction product by a magnetic separation process;
s4: adding water into the separated calcium oxide, and filtering impurities to prepare the desulfurizer which can be used for the wet desulphurization process.
2. The method for preparing a wet desulfurization agent using semi-dry desulfurization ash according to claim 1, wherein the temperature of the drying process in S1 is 100 to 180 ℃; in the S2, the reaction temperature in the boiler furnace is 900 ℃, and the reaction process is as follows: and decomposing calcium hydroxide, calcium sulfite, calcium sulfate and ferrous oxide in the semidry desulfurization ash at high temperature, and reacting with the tail gas introduced into the hearth to generate calcium oxide and ferric oxide.
3. The method for preparing a wet desulfurization agent using semidry desulfurization ash according to claim 1, wherein in the step S3, the magnetic separation process is performed before the reaction product is cooled.
4. An application method of the wet desulfurizing agent prepared by the method of claim 1,
when the inlet SO of the wet desulphurization tower is used2The concentration is 1000mg/m3When the desulfurizing agent prepared from the S4 is used alone, the mass of the desulfurizing agent is 1.3 times of that of the limestone raw material, SO that the SO at the outlet of the wet desulfurization tower is used2The concentration is controlled at 10mg/m3The content of the compound is less than the content of the compound;
when the inlet SO of the wet desulphurization tower is used2The concentration is 1500mg/m3When the desulfurizing agent prepared by the S4 is mixed with the limestone raw material, the mass of the desulfurizing agent prepared by the S4 is 1.7 times of that of the limestone raw material, SO that the SO at the outlet of the wet desulfurization tower2The concentration is controlled at 30mg/m3；
When the inlet SO of the wet desulphurization tower is used2The concentration is 2000mg/m3When the desulfurizing agent prepared by the S4 is mixed with the limestone raw material, the mass of the desulfurizing agent prepared by the S4 is 2 times of that of the limestone raw material, so that the outlet S0 of the wet desulfurization tower is2The concentration is controlled at 50mg/m3Within.
CN202110912988.9A 2021-08-10 2021-08-10 Method for preparing wet desulfurizing agent by using semidry desulfurization ash and application Pending CN113750761A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096707A (en) * 2014-06-27 2014-10-15 武汉钢铁(集团)公司 Resource utilization method of half-dry desulfurized fly ash
CN106731635A (en) * 2017-01-20 2017-05-31 上海龙净环保科技工程有限公司 The method and control system of control fume desulfurizing agent supply
CN110404936A (en) * 2019-07-30 2019-11-05 江苏省沙钢钢铁研究院有限公司 Comprehensive treatment method for semi-dry desulfurized fly ash
CN213275482U (en) * 2020-07-06 2021-05-25 宝钢湛江钢铁有限公司 Mixed desulfurizer wet flue gas desulfurization performance test device
CN113083015A (en) * 2021-03-25 2021-07-09 南京圣创科技有限公司 Resource utilization method for flue gas desulfurization slag by semidry process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104096707A (en) * 2014-06-27 2014-10-15 武汉钢铁(集团)公司 Resource utilization method of half-dry desulfurized fly ash
CN106731635A (en) * 2017-01-20 2017-05-31 上海龙净环保科技工程有限公司 The method and control system of control fume desulfurizing agent supply
CN110404936A (en) * 2019-07-30 2019-11-05 江苏省沙钢钢铁研究院有限公司 Comprehensive treatment method for semi-dry desulfurized fly ash
CN213275482U (en) * 2020-07-06 2021-05-25 宝钢湛江钢铁有限公司 Mixed desulfurizer wet flue gas desulfurization performance test device
CN113083015A (en) * 2021-03-25 2021-07-09 南京圣创科技有限公司 Resource utilization method for flue gas desulfurization slag by semidry process

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