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CN108745282B - Metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification and preparation method thereof - Google Patents

Metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification and preparation method thereof Download PDF

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CN108745282B
CN108745282B CN201810517997.6A CN201810517997A CN108745282B CN 108745282 B CN108745282 B CN 108745282B CN 201810517997 A CN201810517997 A CN 201810517997A CN 108745282 B CN108745282 B CN 108745282B
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activated carbon
forming agent
desulfurization
flue gas
denitrification
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CN108745282A (en
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卢丽君
张垒
吴高明
付本全
李丽坤
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Wuhan Iron and Steel Co Ltd
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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Abstract

The invention discloses a metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification, which comprises the following components in percentage by mass: 65-80% of powdered activated carbon and 20-35% of a forming agent; wherein the forming agent is compounded by steel slag, slag and desulfurized fly ash. According to the invention, the gelling agent prepared based on metallurgical waste residues such as steel slag is used for forming the small-particle activated carbon or the powdered activated carbon after adsorption saturation, the steel slag, the slag and the desulfurization ash are compounded, the obtained forming agent and the powdered activated carbon have good bonding performance, the mechanical property, the desulfurization and denitrification performance and the like of the obtained activated carbon can be effectively improved, the problems that the specific surface of the existing inorganic formed activated carbon is low and the like are effectively solved, meanwhile, the comprehensive utilization added value of the metallurgical waste residues is improved, and the method has important economic and environmental benefits.

Description

Metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification and preparation method thereof
Technical Field
The invention belongs to the technical field of emission control of flue gas pollutants, and particularly relates to a formed activated carbon for flue gas desulfurization and denitrification based on metallurgical solid waste and a preparation method thereof.
Background
The sintering process is a large-scale pollution emission user in steel production, and SO which accounts for 70 percent of the emission of waste gas in steel production is discharged250% NOx. Controlling SO2The discharge technology mainly comprises a limestone-gypsum method, an ammonia method, a rotary spraying method, a circulating fluidized bed method, a double-alkali method and the like; the technologies for controlling NOx emission are mainly selective catalytic reduction, selective non-catalytic reduction, oxidation absorption, and the like. The control technology is adopted to control SO in the flue gas2NOx is removed, and desulfurization equipment and denitration equipment need to be connected in series, so that the problems of large occupied area, high operating cost and the like in the flue gas pollutant removal process are caused. Adopts the technology of simultaneous desulfurization and denitrificationThese problems can be avoided.
The technology of simultaneously desulfurizing and denitrating the active carbon has the advantages of small occupied area, no water consumption, capability of removing dioxin, heavy metal and the like; the activated carbon with saturated adsorption can be returned to the system for use after regeneration, and SO adsorbed by the activated carbon2Can also be used for preparing sulfuric acid, thereby generating considerable economic benefit. The active carbon flue gas control technology is a high-efficiency flue gas comprehensive treatment technology which can simultaneously remove various pollutants and can recover sulfur resources.
In the smoke control technology of the activated carbon, the activated carbon with saturated adsorption can be reused only by regeneration, the regeneration method comprises heating regeneration and water washing regeneration, the regenerated activated carbon recovers the pollutant absorption capacity, but in order to prevent the system from being blocked, the small-particle activated carbon cannot be reused. At 450m2For the integrated process system for desulfurization and denitrification of the activated carbon in the sintering flue gas, the loss of the activated carbon is 20%, and 1460 tons of small-particle activated carbon is produced every year when 20 tons of activity are supplemented every day. At present, small-particle activated carbon is generally used for boiler combustion, blast furnace combustion and the like, but the activated carbon has low combustion added value and can release various pollutants.
The active carbon for desulfurization and denitrification of the sintering flue gas is formed active carbon, the forming agent comprises organic and inorganic forming agents, the organic forming agent has better affinity with the active carbon, the active carbon with higher specific surface area can be prepared, but the mechanical strength is poorer; the inorganic forming agent can easily prepare high-strength activated carbon, but the prepared activated carbon has a low specific surface area, and the desulfurization and denitrification efficiency is low when the inorganic forming agent is used in a desulfurization and denitrification system.
Disclosure of Invention
The invention mainly aims to solve the problem of high value utilization of small-particle or powder activated carbon generated by a regeneration unit in an activated carbon desulfurization and denitrification process system, the formed activated carbon is prepared by utilizing a gelling agent based on metallurgical solid waste, the obtained formed activated carbon can be returned to the original desulfurization and denitrification system for use, can show high-strength and high-adsorption characteristics, can effectively reduce the consumption of the activated carbon of the system, and realizes the purpose of low-cost operation, and the related preparation process is simple, has wide raw material sources, and has important economic and environmental benefits.
In order to achieve the purpose, the invention adopts the technical scheme that:
the formed activated carbon for flue gas desulfurization and denitration based on metallurgical solid waste comprises the following components in percentage by mass: 65-80% of powdered activated carbon and 20-35% of a forming agent; wherein the forming agent is compounded by steel slag, slag and desulfurized fly ash.
Preferably, in the formed activated carbon, the components and the mass percentages thereof comprise: 70-80% of powdered activated carbon and 20-30% of a forming agent; and the higher the content of the powdered activated carbon is, the better the indexes of the specific surface area, the desulfurization value and the denitration rate of the obtained molded activated carbon are.
In the scheme, the forming agent comprises the following components in percentage by mass: 22-35% of steel slag powder, 60-70% of slag powder and 4-8% of desulfurized ash.
In the scheme, the forming agent is formed by grinding and mixing steel slag powder, slag powder and desulfurization ash.
In the scheme, the specific surface area of the powdered activated carbon is 350m2More than 90% of the total iodine content, the particle diameter of less than 1mm, and the iodine adsorption value of more than 350m2/g。
In the scheme, the specific surface area of the steel slag powder is 300-550 m2The content of the particles with the particle size of less than 1mm is more than 90 percent, and the main chemical components and the mass percentage of the particles are as follows: 35-45% of CaO, 5-15% of MgO and SiO2 10～15％、Fe2O310～15％、MnO 1～5％。
In the scheme, the specific surface area of the slag powder is 400-600 m2Per gram, the content of the particles with the diameter of less than 1mm is more than 90 percent; the main chemical components and the mass percentage of the main chemical components are as follows: 35-45% of CaO, 5-15% of MgO and SiO2 30～40％、Al2O310～20％、Fe2O3 1～3％、MnO 1～3％。
The specific surface area of the desulfurized fly ash is 300-500 m2Per gram, the content of the particles with the diameter of less than 1mm is more than 90 percent; wherein CaSO4Not less than 50 wt%, CaSO3The content is not higher than 3%. .
The preparation method of the formed activated carbon for flue gas desulfurization and denitration based on metallurgical solid waste comprises the following steps:
1) weighing the raw materials according to the proportion, wherein the raw materials and the mass percentage of the raw materials comprise: 65-80% of powdered activated carbon and 20-35% of a forming agent, wherein the forming agent comprises the following components in percentage by mass: 20-28% of steel slag, 65-70% of slag and 4-8% of desulfurized ash;
2) uniformly mixing the weighed steel slag, slag and desulfurization, and grinding until the surface area reaches 450m2More than g, obtaining the forming agent for later use;
3) and uniformly mixing the weighed powdered activated carbon and a forming agent by a mixer, adding water accounting for 5-15% of the mass of the obtained solid mixture, stirring, pouring into a mold for compression forming, demolding, and curing to obtain the formed activated carbon.
In the above scheme, the stirring treatment step is: stirring at a speed of 400-800 r/min for 2-5 min, pausing for 1-3 min, and stirring at a speed of 200-400 r/min for 2-5 min.
Preferably, after the mixture obtained by the stirring treatment is poured into a mold, the mixture is lightly vibrated to remove the gas in the gap.
In the scheme, the pressing and forming step adopts a press machine, and the pressing and forming step is uniformly carried out for 1-3 min at the force speed of 10-30N/S.
The principle of the invention is as follows:
according to the invention, the gelling agent prepared based on metallurgical waste residues such as steel slag is used for forming the small-particle activated carbon or the powdered activated carbon after adsorption saturation, the steel slag, the slag and the desulfurization ash are compounded, the obtained forming agent and the powdered activated carbon have good bonding performance, oxides such as iron, manganese and the like in the forming agent are used as catalysts and the content of the catalysts is regulated and controlled, and the forming agent and the powdered activated carbon are matched to act, so that the mechanical property, the desulfurization and denitrification properties of the obtained activated carbon can be effectively improved, the problems of low specific surface area and the like of the existing inorganic formed activated carbon are solved, and meanwhile, the comprehensive utilization and side-added value of the.
Compared with the prior art, the invention has the beneficial effects that:
1) the forming agent is prepared by compounding steel slag, slag and desulfurized ash, and is all from inorganic solid waste generated in each process of the metallurgical industry, the prepared forming agent is low in price, and high-added-value utilization of metallurgical solid waste such as steel slag, mineral powder desulfurized ash and the like is realized.
2) The desulfurized ash does not need to be oxidized, can be directly used in the forming agent, is beneficial to improving the effects of the forming agent such as strength and the like, and is easy to implement.
3) The method prepares the formed activated carbon from the byproduct raw powder activated carbon generated by desulfurization and denitrification, and reapplies the formed activated carbon in the activated carbon desulfurization and denitrification system, thereby reducing the consumption of fresh activated carbon, lowering the cost and realizing high-value utilization of the powder activated carbon.
4) The invention can prepare high-strength formed active carbon, and reduce the loss of the active carbon in a desulfurization and denitrification system, thereby reducing the consumption of fresh active carbon; in addition, the obtained forming agent is compounded, so that the desulfurization and denitrification efficiency is further improved.
5) The preparation method is simple and easy to implement, and has important economic and environmental benefits and strong market popularization value.
Detailed Description
The following examples further illustrate the invention in order that it may be better understood. However, the present invention is not limited to the following examples.
In the following examples, the steel slag powder used is steel slag obtained from a converter in a steelmaking process in a steel plant, wherein the specific surface area of the steel slag powder is 300 to 550m2The content of the particles with the particle diameter of less than 1mm is more than 90 percent, and the main chemical components and the content range are as follows: 42% of CaO, 12% of MgO and SiO2 14％、Fe2O3 13％、MnO 5％。
The slag powder is taken from blast furnace slag in an iron-making process, wherein the specific surface area of the slag powder is higher than 400-600 m2The content of the particles with the particle diameter of less than 1mm is more than 90 percent, and the main chemical components and the content range are as follows: CaO 38%, MgO 10%, SiO2 32％、Al2O311％、Fe2O3 3％、MnO 2％。
The semi-dry desulfurized fly ash is taken from the semi-dry of the sintering processThe specific surface area of the desulfurized ash is higher than 300-450 m2Per gram, the content of the particles with the diameter of less than 1mm is more than 90 percent; CaSO4Content 52.7%, CaSO3The content is 2 percent.
The powdered activated carbon is taken from activated carbon powder which is adsorbed and saturated in the activated carbon desulfurization and denitrification process, wherein the specific surface area of the powdered activated carbon is higher than 450m2Per g, the content of the particles with the diameter of less than 1mm is more than 90 percent, and the iodine adsorption value is more than 350m2/g。
Example 1
A metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification is prepared by the following steps:
1) weighing raw materials, wherein the raw materials and the mass percentage of the raw materials comprise: 70% of powdered activated carbon and 30% of forming agent, wherein the forming agent comprises the following components in percentage by mass: 25% of steel slag powder, 70% of slag powder and 5% of desulfurized ash;
2) the weighed steel slag, slag and desulfurized fly ash are respectively put into a 105 ℃ oven for drying, and then are respectively ground to control the specific surface area to be 450m2Kg (and the content of the particles with the diameter of less than 1mm is more than 90%); uniformly mixing the ground steel slag, slag and desulfurized fly ash to obtain a forming agent for later use;
3) weighing powdered activated carbon (specific surface area 400 m) according to the proportion2The content of the molding agent is more than 90 percent when the particle size is less than 1 mm) and the molding agent are poured into a mixer, water accounting for 8 percent of the total mass of the obtained solid mixture is poured into the mixer at the same time, the mixture is stirred quickly for 3 minutes at the stirring speed of 500r/min, the mixture is stopped for 1 minute, then the mixture is stirred slowly for 3 minutes at the stirring speed of 300r/min, the obtained stirring material is poured into a molding die, and the molding die is vibrated slightly to remove the gap gas; and then, uniformly pressing for 2 minutes at a force speed of 20N/S under a press machine for forming, demolding after one day, and putting the formed activated carbon after demolding into a standard curing box for curing for 28 days to obtain the carbon fiber.
Example 2
A metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification is prepared by the following steps:
1) weighing raw materials, wherein the raw materials and the mass percentage of the raw materials comprise: 75% of powdered activated carbon and 25% of forming agent, wherein the forming agent comprises the following components in percentage by mass: 28% of steel slag powder, 65% of slag powder and 7% of desulfurized ash;
2) the weighed steel slag, slag and desulfurized fly ash are respectively put into a 105 ℃ oven for drying, and then are respectively ground to control the specific surface area to be 480m2Per kg; uniformly mixing the ground steel slag, slag and desulfurized fly ash to obtain a forming agent for later use;
3) weighing powdered activated carbon (specific surface area 380 m) according to a proportion2(g, the content of the particles with the particle size of less than 1mm is more than 90 percent) and a forming agent are poured into a mixer, water accounting for 10 percent of the total mass of the obtained solid mixture is poured into the mixer at the same time, the mixture is stirred quickly for 2 minutes at the stirring speed of 600r/min, the mixture is stopped for 2 minutes, then the mixture is stirred slowly for 4 minutes at the stirring speed of 350r/min, the obtained stirring material is poured into a forming die, and the gap gas is removed by slight vibration; and then, uniformly pressing for 2 minutes at a force speed of 10N/S under a press machine for forming, demolding after one day, and putting the formed activated carbon after demolding into a standard curing box for curing for 28 days to obtain the carbon fiber.
Example 3
A metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification is prepared by the following steps:
1) weighing raw materials, wherein the raw materials and the mass percentage of the raw materials comprise: 80% of powdered activated carbon and 20% of forming agent, wherein the forming agent comprises the following components in percentage by mass: 30% of steel slag powder, 62% of slag powder and 8% of desulfurized ash;
2) the weighed steel slag, slag and desulfurized fly ash are respectively put into a 105 ℃ oven for drying, and then are respectively ground to control the specific surface area to be 500m2Kg (and the content of the particles with the diameter of less than 1mm is more than 90%); uniformly mixing the ground steel slag, slag and desulfurized fly ash to obtain a forming agent for later use;
3) weighing powdered activated carbon (the specific surface area is 420, the content of the particles with the particle size of less than 1mm is more than 90%) and a forming agent according to a proportion, pouring the powdered activated carbon and the forming agent into a mixer, simultaneously pouring water accounting for 10% of the total mass of the obtained solid mixture, quickly stirring at the stirring speed of 800r/min for 4 minutes, pausing for 2 minutes, slowly stirring at the stirring speed of 400r/min for 3 minutes, pouring the obtained stirring material into a forming die, and slightly vibrating to remove air in gaps; and then, uniformly pressing for 2 minutes at a force speed of 15N/S under a press machine for forming, demolding after one day, and putting the formed activated carbon after demolding into a standard curing box for curing for 28 days to obtain the carbon fiber.
Example 4
A metallurgical solid waste-based formed activated carbon for flue gas desulfurization and denitrification is prepared by the following steps:
1) weighing raw materials, wherein the raw materials and the mass percentage of the raw materials comprise: 65% of powdered activated carbon and 35% of forming agent, wherein the forming agent comprises the following components in percentage by mass: 35% of steel slag powder, 60% of slag powder and 5% of desulfurized ash;
2) the weighed steel slag, slag and desulfurized fly ash are respectively put into a 105 ℃ oven for drying, and then are respectively ground to control the specific surface area to be 500m2Kg (and the content of the particles with the diameter of less than 1mm is more than 90%); uniformly mixing the ground steel slag, slag and desulfurized fly ash to obtain a forming agent for later use;
3) weighing powdered activated carbon (the specific surface area is 350, the content of the powdered activated carbon is more than 90 percent below 1 mm) and a forming agent according to a proportion, pouring the powdered activated carbon and the forming agent into a mixer, simultaneously pouring water accounting for 13 percent of the total mass of the obtained solid mixture, quickly stirring at the stirring speed of 700r/min for 5 minutes, pausing for 2 minutes, slowly stirring at the stirring speed of 250r/min for 4 minutes, pouring the obtained stirring material into a forming die, and slightly vibrating to remove air in gaps; and then, uniformly pressing for 2 minutes at a force speed of 20N/S under a press machine for forming, demolding after one day, and putting the formed activated carbon after demolding into a standard curing box for curing for 28 days to obtain the carbon fiber.
Comparative example 1
The preparation method of the formed activated carbon for flue gas desulfurization and denitration is substantially the same as that of the formed activated carbon in the embodiment 1, and the difference is that: the forming agent comprises the following components in percentage by mass: 90% of commercial R42.5 cement and 10% of semi-dry desulfurized fly ash.
Comparative example 2
The preparation method of the formed activated carbon for flue gas desulfurization and denitrification based on metallurgical solid waste is substantially the same as that of the formed activated carbon in the embodiment 1, and is different from the following steps: the forming agent comprises the following components in percentage by mass: 10% of commercial R42.5 cement, 80% of slag powder and 10% of desulfurized ash.
The results of quality testing of the formed activated carbon obtained in examples 1 to 4 and comparative example are shown in Table 1.
TABLE 1 data of quality test of formed activated carbon obtained in examples 1 to 4 and comparative example
Figure BDA0001674211560000051
The results show that the mechanical system performance, the desulfurization and denitration performance and the like of the formed activated carbon meet the corresponding national standard requirements, are remarkably superior to the national standard requirements and conventional gel forming products, can realize high-side value-added utilization of metallurgical solid wastes such as steel slag, mineral powder, desulfurized ash, small-particle activated carbon and the like, and have important economic and environmental benefits.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (9)

1. The formed activated carbon for flue gas desulfurization and denitration based on metallurgical solid waste comprises the following components in percentage by mass: 65-80% of powdered activated carbon and 20-35% of a forming agent; wherein the forming agent is compounded by steel slag powder, slag powder and desulfurized fly ash;
the forming agent comprises the following components in percentage by mass: 22-35% of steel slag powder, 60-70% of slag powder and 4-8% of desulfurized ash.
2. The formed activated carbon for flue gas desulfurization and denitration according to claim 1, characterized in that the components and the mass percentages thereof comprise: 70-80% of powdered activated carbon and 20-30% of a forming agent.
3. The shaped activated carbon for desulfurization and denitrification of flue gas according to claim 1, wherein the powdered activated carbon has a specific surface area of 350m2More than one gram, the content of the particles with the particle diameter of less than 1mm is more than 90 percent, and the iodine adsorption value is more than 350 mg/g.
4. The formed activated carbon for flue gas desulfurization and denitration according to claim 1, wherein the specific surface area of the steel slag powder is 300-550 m2The content of the particles with the particle size of less than 1mm is more than 90 percent, and the main chemical components and the mass percentage of the particles are as follows: 35-45% of CaO, 5-15% of MgO and SiO2 10～15％、Fe2O3 10～15％、MnO 1～5％。
5. The formed activated carbon for desulfurization and denitrification of flue gas according to claim 1, wherein the specific surface area of the slag powder is 400-600 m2Per gram, the content of the particles with the diameter of less than 1mm is more than 90 percent; the main chemical components and the mass percentage of the main chemical components are as follows: 35-45% of CaO, 5-15% of MgO and SiO2 30～40％、Al2O3 10～20％、Fe2O3 1～3％、MnO 1～3％。
6. The formed activated carbon for desulfurization and denitrification of flue gas according to claim 1, wherein the specific surface area of the desulfurization ash is 300 to 500m2Per gram, the content of the particles with the diameter of less than 1mm is more than 90 percent; wherein CaSO4Not less than 50% of CaSO3The content is not higher than 3%.
7. A preparation method of a formed activated carbon for flue gas desulfurization and denitrification based on metallurgical solid waste is characterized by comprising the following steps:
1) weighing the raw materials according to the proportion, wherein the raw materials and the mass percentage of the raw materials comprise: 65-80% of powdered activated carbon and 20-35% of a forming agent, wherein the forming agent comprises the following components in percentage by mass: 20-28% of steel slag, 65-70% of slag and 4-8% of desulfurized ash;
2) uniformly mixing the weighed steel slag, slag and desulfurization, and grinding until the surface area reaches 450m2More than g, obtaining the forming agent for later use;
3) and uniformly mixing the weighed powdered activated carbon and the forming agent by using a mixer, adding water accounting for 5-15% of the mass of the obtained solid mixture, stirring, pouring into a mold for compression forming, demolding and maintaining to obtain the formed activated carbon.
8. The production method according to claim 7, wherein the stirring treatment step is: stirring at a speed of 400-800 r/min for 2-5 min, pausing for 1-3 min, and stirring at a speed of 200-400 r/min for 2-5 min.
9. The preparation method according to claim 7, wherein the press forming step adopts a press machine, and the press forming is carried out at a force speed of 10-30N/S for 1-3 min.
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