CN114471143B - Defect alumina modified wide-temperature desulfurizer and preparation method and application thereof - Google Patents
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Abstract
The invention is suitable for the technical field of flue gas desulfurization and purification, and provides a wide-temperature desulfurizer with defect alumina tempering, which comprises the following raw materials in parts by weight: 40-80 parts of slaked lime powder, 10-40 parts of defect alumina, 2-25 parts of active component and 5-25 parts of binder; the preparation method of the defect aluminum oxide comprises the steps of calcining basic aluminum acetate at 200-400 ℃ for 2-4 hours, and naturally cooling to obtain the defect aluminum oxide, wherein the active component is one or more of ferric oxide, manganese dioxide, cobaltosic oxide and cerium dioxide, so that the desulfurizer product prepared from the raw materials has the characteristics of good desulfurization performance, long service life, high mass transfer rate, high mechanical strength, wide use temperature range (50-350 ℃) and the like.
Description
Technical Field
The invention relates to the technical field of flue gas desulfurization and purification, in particular to a wide-temperature desulfurizer for defective alumina tempering and a preparation method and application thereof.
Background
With the rapid development of economy, sulfur dioxide (SO) in industrial flue gas 2 ) Air pollution caused by emission is increasingly serious. In 7/1/2021, the fourteen-five cyclic economy development planning issued by the national development reform committee indicates that the cyclic economy is vigorously developed, the resource saving and intensive cyclic utilization are promoted, and the method has very important significance for guaranteeing the national resource safety, promoting the realization of carbon peak reaching and carbon neutralization and promoting the ecological civilization construction; in 4 months in 2019, the ecological environment department issued 'opinion on promoting implementation of ultra-low emission in the steel industry' gives SO 2 The requirement of ultra low emission limits is met. Therefore, under the large background of constructing a green low-carbon circular economy system, the low-carbon emission reduction treatment of sulfur dioxide in flue gas is a necessary choice.
At present, most domestic coal-fired power plants adopt a basically mature wet desulphurization technology to remove SO 2 However, the wet desulphurization technology causes secondary pollution problems such as equipment corrosion, waste water discharge, white smoke and white mist and the like, and more investment and technology are needed to solve the new problems caused by the wet desulphurization technology. The dry desulfurization technology represented by the SDS method has the characteristics of simple operation, high desulfurization efficiency and the like, but has poor adaptability to the fluctuation of the smoke volume and the smoke temperature, and can discharge a large amount of carbon dioxide in the treatment process. In the new situation, enterprises need a flue gas desulfurization technology which has low carbon characteristic and can realize waste recycling.
The new type solid base dry desulfurizing technology is that solid base desulfurizing agent with certain height and specific shape is filled inside fixed bed or moving bed reactor, and when flue gas passes through stationary desulfurizing agent bed layer or gradually downwards moving desulfurizing agent bed layer, SO in flue gas is eliminated 2 . Compared with the traditional wet method and the SDS dry method, the novel solid base dry-method desulfurization technology has the advantages of controllable desulfurization efficiency, simple operation process, small equipment quantity and low investment and operation cost. In addition, the technology is insensitive to flue gas flow and temperature fluctuation, the used desulfurizer can be used as building materials, the solid waste problem does not need to be worried about, and the problem of wastewater treatment does not exist subsequently.
The core of the novel solid base dry desulfurization is a desulfurizer. Most of the commercial desulfurizer has the problems of poor desulfurization performance, short service life, low mass transfer rate, poor mechanical strength and the like. Especially for industries with large flue gas emission temperature range span, such as industrial boilers, cement furnaces, garbage incinerators, steel metallurgy sintering furnaces, glass ceramic furnaces and the like, high-efficiency long-acting wide-temperature dry desulfurizing agent products are still lacked. Therefore, the development of the high-efficiency long-acting wide-temperature dry desulfurizing agent becomes the first choice of enterprises in the situation of low carbon emission reduction by adopting a fixed bed or moving bed flue gas dry desulfurizing process with low carbon characteristic.
In view of the above, the prior art is obviously inconvenient and disadvantageous in practical use, and needs to be improved.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a defect alumina modified wide-temperature desulfurizer and a preparation method and application thereof 2 The adsorption of (3) accelerates the dissociation and activation of oxygen and the generation of active oxygen in the desulfurization process, thereby accelerating SO 2 Is oxidized to SO 3 On the other hand, increase Ca (OH) 2 Is SO of 3 And Ca (OH) 2 The reaction of (2) provides enough space, and the calcium utilization rate of the desulfurizer is improved. In addition, the anchored metal oxide on the defect alumina also serves to enrich oxygen and strengthen SO 2 The catalytic oxidation effect, the wear resistance of the desulfurizer is enhanced, and the dust amount generated by the friction between the desulfurizer and the bed body in the moving process is reduced. The desulfurizer product prepared by adopting the raw materials has the characteristics of good desulfurization performance, long service life, high mass transfer rate, high mechanical strength, wide use temperature range (50-350 ℃) and the like.
In order to achieve the aim, the invention provides a defect alumina modified wide-temperature desulfurizer, which comprises the following raw materials in parts by weight: 40-80 parts of slaked lime powder, 10-40 parts of defect alumina, 2-25 parts of active component and 5-25 parts of binder; the preparation process of the defective alumina comprises the steps of calcining basic aluminum acetate at the temperature of 200-400 ℃ for 2-4 hours, and naturally cooling to obtain the defective alumina.
According to the defect alumina modified wide-temperature desulfurizer, the active component is one or more of ferric oxide, manganese dioxide, cobaltosic oxide and cerium dioxide.
According to the defect alumina modified wide-temperature desulfurizer, the binder comprises at least one of kaolin, diatomite, bentonite and attapulgite.
The preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer comprises the following steps of S1: 40-80 parts of slaked lime powder, 10-40 parts of defect aluminum oxide, 2-25 parts of active component and 5-25 parts of binder are placed into a stirring device for stirring, and the stirring process takes 10-30 minutes to fully and uniformly mix the materials to obtain mixed powder; step S2: putting the mixed raw materials into a ball mill for grinding until all the raw materials pass through a screen, and screening by adopting a screen with 60-300 meshes; and step S3: adding water into the mixed powder, stirring (the stirring time is 10-30 minutes), and extruding and forming to obtain a formed material; and step S4: and (3) drying the formed material in a drying box to obtain a finished product, and packaging to obtain the wide-temperature desulfurizer.
According to the preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer, in the step S1, the stirring process takes 10-30 minutes.
According to the preparation method of the defect alumina modified wide-temperature desulfurizer, in the step S2, a screen mesh with 60-300 meshes is adopted for screening in the screening process.
According to the preparation method of the defect alumina modified wide-temperature desulfurizer, in the step S3, the stirring time of the ground mixed powder and water is 10-30 minutes.
According to the preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer, in the step S3, the mass ratio of the ground mixed powder to water is 10: (1-4).
According to the preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer, in the step S4, the temperature in the drying process is maintained at 50-350 ℃, and the drying time is 1-10 hours.
The application of the defect alumina modified wide-temperature desulfurizing agent is characterized by being applied to desulfurization of fixed bed or moving bed process.
The invention provides a defect alumina quenched and tempered wide-temperature desulfurizer which comprises the following raw materials in parts by weight: 40-80 parts of slaked lime powder, 10-40 parts of defect alumina, 2-25 parts of active component and 5-25 parts of binder; the preparation process of the defective alumina comprises the steps of calcining basic aluminum acetate at the temperature of 200-400 ℃ for 2-4 hours, and naturally cooling to obtain the defective alumina. The preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer comprises the following steps of S1: 40-80 parts of slaked lime powder, 10-40 parts of defect aluminum oxide, 2-25 parts of active component and 5-25 parts of binder are placed into a stirring device for stirring, so that the materials are fully and uniformly mixed to obtain mixed powder; step S2: putting the mixed raw materials into a ball mill for grinding until all the raw materials pass through a screen; and step S3: adding water into the mixed powder, stirring, extruding and forming to obtain a formed material; and step S4: and (3) drying the formed material in a drying box to obtain a finished product, and packaging to obtain the wide-temperature desulfurizer. The invention makes full use of the unique structure, larger specific surface area and super-strong adsorption performance of defective alumina, and promotes SO on the one hand 2 The adsorption of (3) accelerates the dissociation and activation of oxygen and the generation of active oxygen in the desulfurization process, thereby accelerating SO 2 By oxidation to SO 3 On the other hand, increase Ca (OH) 2 Is SO 3 And Ca (OH) 2 The reaction of (2) provides enough space and improves the utilization rate of calcium of the desulfurizer. In addition, the anchored metal oxide on the defect alumina also serves to enrich oxygen and strengthen SO 2 The catalytic oxidation effect, the wear resistance of the desulfurizer is enhanced, and the dust amount generated by the friction between the desulfurizer and the bed body in the moving process is reduced. The desulfurizer product prepared by adopting the raw materials has the characteristics of good desulfurization performance, long service life, high mass transfer rate, high mechanical strength, wide use temperature range (50-350 ℃) and the like.
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FIG. 1 is a scanning electron micrograph of the surface of a desulfurizing agent;
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and embodiments, it being understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The invention provides a defect alumina quenched and tempered wide-temperature desulfurizer and a preparation method and application thereof, wherein the defect alumina quenched and tempered wide-temperature desulfurizer comprises the following raw materials in parts by weight: 40-80 parts of slaked lime powder, 10-40 parts of defect alumina, 2-25 parts of active component and 5-25 parts of binder; the preparation process of the defective alumina comprises the steps of calcining basic aluminum acetate at the temperature of 200-400 ℃ for 2-4 hours, and naturally cooling to obtain the defective alumina. The active component is one or more of ferric oxide, manganese dioxide, cobaltosic oxide and cerium dioxide. The binder includes at least one of kaolin, diatomaceous earth, bentonite, and attapulgite.
The preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer comprises the following steps of S1: 40-80 parts of slaked lime powder, 10-40 parts of defect aluminum oxide, 2-25 parts of active component and 5-25 parts of binder are put into a stirring device for stirring, so that the materials are fully and uniformly mixed to obtain mixed powder; step S2: putting the mixed raw materials into a ball mill for grinding until all the raw materials pass through a screen; and step S3: adding water (the mass ratio of the mixed powder to the water is 10-4) into the mixed powder, stirring, and extruding for molding to obtain a molded material; and step S4: and (3) drying the formed material in a drying box (the temperature is maintained at 50-350 ℃ and the drying time is 1-10 hours) to obtain a finished product, and packaging to obtain the wide-temperature desulfurizer.
In the first embodiment;
a defect alumina quenched and tempered wide-temperature flue gas dry desulfurizing agent is prepared from the following raw materials in parts by weight: 20 parts of defect aluminum oxide, 65 parts of slaked lime powder, 10 parts of active component and 5 parts of binder. The active component is ferric oxide, and the binder is bentonite. The preparation method of the flue gas desulfurizer comprises the following steps: the components are put into a stirring device to be stirred for 10 minutes, so that the components are fully and uniformly mixed; putting the mixed raw materials into a ball mill for further grinding until all the raw materials pass through a 300-mesh screen; adding water accounting for 10 percent of the weight of the ground mixed powder into the ground mixed powder, stirring for 20 minutes, and performing extrusion molding to obtain a molding material; drying the formed material in a drying oven at 100 ℃ for 6 hours; taking the formed material out of the drying oven, and then airing to room temperature to obtain a finished product of the flue gas desulfurizer, wherein the particle size is 4-5 mm.
In specific example two;
a defect alumina quenched and tempered wide-temperature flue gas dry desulfurizing agent is prepared from the following raw materials in parts by weight: 25 parts of defect aluminum oxide, 40 parts of slaked lime powder, 15 parts of active component and 20 parts of binder. The active components comprise 10 parts of manganese dioxide and 5 parts of cobaltosic oxide, and the binder comprises 5 parts of diatomite and 15 parts of bentonite. The preparation method of the flue gas desulfurizer comprises the following steps: the components are put into a stirring device to be stirred for 20 minutes, so that the components are fully and uniformly mixed; putting the mixed raw materials into a ball mill for further grinding until all the raw materials pass through a 200-mesh screen; adding water accounting for 20 percent of the weight of the ground mixed powder into the ground mixed powder, stirring for 30 minutes, and performing extrusion molding to obtain a molding material; drying the formed material in a drying oven at 50 ℃ for 10 hours; taking the formed material out of the drying box, and then airing to room temperature to obtain a finished product of the flue gas desulfurizer.
In specific example three;
a defect alumina quenched and tempered wide-temperature flue gas dry desulfurizing agent is prepared from the following raw materials in parts by weight: 10 parts of defect alumina, 75 parts of slaked lime powder, 5 parts of active component and 10 parts of binder. The active component is cerium oxide, and the binder is attapulgite. The preparation method of the flue gas desulfurizer comprises the following steps: putting the components into a stirring device, and stirring for 20 minutes to fully and uniformly mix the components; putting the mixed raw materials into a ball mill for further grinding until all the raw materials pass through a 300-mesh screen; adding water accounting for 30% of the weight of the ground mixed powder into the ground mixed powder, stirring for 10 minutes, and performing extrusion molding to obtain a molding material; drying the formed material in a drying oven at 50 ℃ for 10 hours; taking the formed material out of the drying box and then airing to room temperature to obtain a finished product of the flue gas desulfurizer.
In specific example four;
a defect alumina quenched and tempered wide-temperature flue gas dry desulfurizing agent is prepared from the following raw materials in parts by weight: 15 parts of defect aluminum oxide, 45 parts of slaked lime powder, 15 parts of active component and 25 parts of binder. The active components comprise 7 parts of ferric oxide, 3 parts of cerium oxide and 5 parts of cobaltosic oxide, and the binder comprises 10 parts of diatomite, 10 parts of bentonite and 5 parts of attapulgite. The preparation method of the flue gas desulfurizer comprises the following steps: putting the components into a stirring device, and stirring for 30 minutes to fully and uniformly mix the components; putting the mixed raw materials into a ball mill for further grinding until all the raw materials pass through a 300-mesh screen; adding water accounting for 20 percent of the weight of the ground mixed powder into the ground mixed powder, stirring for 10 minutes, and performing extrusion molding to obtain a molding material; drying the formed material in a drying oven at 200 ℃ for 3 hours; taking the formed material out of the drying box and then airing to room temperature to obtain a finished product of the flue gas desulfurizer.
In specific example five;
a defect alumina quenched and tempered wide-temperature flue gas dry desulfurizing agent is prepared from the following raw materials in parts by weight: 25 parts of defect aluminum oxide, 50 parts of slaked lime powder, 10 parts of active component and 15 parts of binder. The active components comprise 3 parts of ferric oxide and 7 parts of cerium oxide, and the binder comprises 5 parts of kaolin and 10 parts of diatomite. The preparation method of the flue gas desulfurizer comprises the following steps: putting the components into a stirring device, and stirring for 30 minutes to fully and uniformly mix the components; putting the mixed raw materials into a ball mill for further grinding until all the raw materials pass through a 200-mesh screen; adding water accounting for 30 percent of the weight of the ground mixed powder into the ground mixed powder, stirring for 30 minutes, and performing extrusion molding to obtain a molding material; drying the formed material in a drying oven at 100 ℃ for 3 hours; taking the formed material out of the drying box and then airing to room temperature to obtain a finished product of the flue gas desulfurizer.
In specific example six;
a defect alumina quenched and tempered wide-temperature flue gas dry desulfurizing agent is prepared from the following raw materials in parts by weight: 40 parts of defect aluminum oxide, 45 parts of slaked lime powder, 5 parts of active component and 10 parts of binder. The active component is 10 parts of manganese dioxide, and the binder is 5 parts of kaolin. The preparation method of the flue gas desulfurizer comprises the following steps: the components are put into a stirring device to be stirred for 10 minutes, so that the components are fully and uniformly mixed; putting the mixed raw materials into a ball mill for further grinding until all the raw materials pass through a 300-mesh screen; adding water accounting for 20% of the weight of the ground mixed powder into the ground mixed powder, stirring for 20 minutes, and performing extrusion molding to obtain a molding material; drying the formed material in a drying oven at 50 ℃ for 10 hours; taking the formed material out of the drying box, and then airing to room temperature to obtain a finished product of the flue gas desulfurizer. The scanning electron micrograph of the surface of the desulfurizing agent is shown in FIG. 1, and it can be seen that the sample has a developed pore structure.
The physical properties and desulfurization performance of the desulfurization agent samples obtained in examples 1 to 6 were measured using a chemical analyzer and a desulfurization evaluation mechanism, and the inlet flue gas SO 2 The concentration is 35-2000 mg/Nm 3 The contact time of the flue gas and the flue gas desulfurizer is 6.0 seconds. The flue gas temperature is in the range of 50-350 ℃, 3 temperature values are selected, and the physicochemical properties and the flue gas desulfurization purification efficiency of the desulfurizer prepared by the method are shown in table 1.
TABLE 1 flue gas desulfurization agent Performance index test results
As can be seen from the detection data of the examples 1-6, the flue gas desulfurizing agent provided by the invention has small bulk density (0.61-0.80 g/cm) 3 ) High radial compressive strength: (>100N/cm), large porosity (46-61%), wide application temperature (50-350 ℃). When the desulfurizer provided by the invention is used for fixed bed or moving bed process desulfurization, the SO content is higher at 50 ℃, 150 ℃ and 350 DEG C 2 The desulfurization efficiency can effectively solve the problems of low desulfurization efficiency, poor mechanical strength, narrow applicable temperature range and the like after the existing desulfurizer is molded.
In conclusion, the invention provides a defect alumina quenched and tempered wide-temperature desulfurizer which comprises the following components in parts by weightComprises the following raw materials: 40-80 parts of slaked lime powder, 10-40 parts of defect alumina, 2-25 parts of active component and 5-25 parts of binder; the preparation process of the defective alumina comprises the steps of calcining basic aluminum acetate at the temperature of 200-400 ℃ for 2-4 hours, and naturally cooling to obtain the defective alumina. The preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer comprises the following steps of S1: 40-80 parts of slaked lime powder, 10-40 parts of defect aluminum oxide, 2-25 parts of active component and 5-25 parts of binder are put into a stirring device for stirring, so that the materials are fully and uniformly mixed to obtain mixed powder; step S2: putting the mixed raw materials into a ball mill for grinding until all the raw materials pass through a screen; and step S3: adding water into the mixed powder, stirring, and performing extrusion molding to obtain a molding material; and step S4: and (3) drying the formed material in a drying box to obtain a finished product, and packaging to obtain the wide-temperature desulfurizer. The invention makes full use of the unique structure, larger specific surface area and super-strong adsorption performance of defective alumina, and promotes SO on the one hand 2 The adsorption of (3) accelerates the dissociation and activation of oxygen and the generation of active oxygen in the desulfurization process, thereby accelerating SO 2 Is oxidized to SO 3 On the other hand, increase Ca (OH) 2 Is SO 3 And Ca (OH) 2 The reaction of (2) provides enough space, and the calcium utilization rate of the desulfurizer is improved. In addition, the anchored metal oxide on the defect alumina also serves to enrich oxygen and strengthen SO 2 The catalytic oxidation effect, the wear resistance of the desulfurizer is enhanced, and the dust amount generated by the friction between the desulfurizer and the bed body in the moving process is reduced. The desulfurizer product prepared by adopting the raw materials has the characteristics of good desulfurization performance, long service life, high mass transfer rate, high mechanical strength, wide use temperature range (50-350 ℃) and the like.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The wide-temperature desulfurizer for conditioning defective alumina is characterized by comprising the following raw materials in parts by weight: 40-80 parts of slaked lime powder, 10-40 parts of defect alumina, 2-25 parts of active component and 5-25 parts of binder; the preparation process of the defective alumina comprises the steps of calcining basic aluminum acetate at 200-400 ℃ for 2-4 hours, and naturally cooling to obtain defective alumina;
the active component is one or more of ferric oxide, manganese dioxide, cobaltosic oxide and cerium dioxide;
the binder includes at least one of kaolin, diatomaceous earth, bentonite, and attapulgite.
2. The preparation method of the defect alumina quenched and tempered wide-temperature desulfurizer as described in claim 1, comprising:
step S1: 40-80 parts of slaked lime powder, 10-40 parts of defect aluminum oxide, 2-25 parts of active component and 5-25 parts of binder are put into a stirring device for stirring, so that the materials are fully and uniformly mixed to obtain mixed powder;
step S2: putting the mixed raw materials into a ball mill for grinding until all the raw materials pass through a screen;
and step S3: adding water into the mixed powder, stirring, and performing extrusion molding to obtain a molding material;
and step S4: and (3) drying the formed material in a drying box to obtain a finished product, and packaging to obtain the wide-temperature desulfurizer.
3. The method for preparing the defective alumina quenched and tempered wide-temperature desulfurizer according to claim 2, wherein the stirring process takes 10 to 30 minutes in the step S1.
4. The method for preparing the defective alumina quenched and tempered wide-temperature desulfurizer according to claim 2, wherein in the step S2, a sieve of 60 to 300 meshes is adopted for sieving in the sieving process.
5. The method for preparing the defective alumina quenched and tempered wide-temperature desulfurizer according to claim 2, wherein in the step S3, the time for stirring the ground mixed powder with water is 10 to 30 minutes.
6. The method for preparing the defect alumina quenched and tempered wide-temperature desulfurizer according to claim 2, wherein in the step S3, the mass ratio of the ground mixed powder to water is 10: (1 to 4).
7. The method for preparing the wide-temperature desulfurizer for defective alumina conditioning according to claim 2, wherein in the step S4, the temperature in the drying process is maintained at 50 to 350 ℃, and the drying time is 1 to 10 hours.
8. The use of the defective alumina conditioning wide temperature desulfurization agent of claim 1, wherein the wide temperature desulfurization agent is used in fixed bed or moving bed desulfurization.
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| JPH0431313A (en) * | 1990-05-28 | 1992-02-03 | Teika Corp | Production of fine particle of alumina |
| CN1087321A (en) * | 1992-08-12 | 1994-06-01 | 巴西石油公司 | Modified aluminas and the application in the FCC catalyzer thereof |
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| CN110683777A (en) * | 2019-11-14 | 2020-01-14 | 天津水泥工业设计研究院有限公司 | Powder desulfurizing agent for cement kiln and preparation method and application thereof |
| CN111514748A (en) * | 2020-04-30 | 2020-08-11 | 南京中研科技有限公司 | Wide-temperature flue gas dry desulfurizing agent for moving bed process and preparation method thereof |
| CN112619388A (en) * | 2020-11-17 | 2021-04-09 | 天津浩创节能环保设备有限公司 | Preparation method of flue gas desulfurizing agent |
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2021
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| JPH0431313A (en) * | 1990-05-28 | 1992-02-03 | Teika Corp | Production of fine particle of alumina |
| CN1087321A (en) * | 1992-08-12 | 1994-06-01 | 巴西石油公司 | Modified aluminas and the application in the FCC catalyzer thereof |
| CN104445322A (en) * | 2014-12-13 | 2015-03-25 | 湖南科技大学 | Method for preparing porous alumina particles from aluminum hydroxide extracted from slag |
| CN105771617A (en) * | 2016-03-22 | 2016-07-20 | 天津滨环化学工程技术研究院有限公司 | Flue gas desulfurization and denitrification method |
| CN110683777A (en) * | 2019-11-14 | 2020-01-14 | 天津水泥工业设计研究院有限公司 | Powder desulfurizing agent for cement kiln and preparation method and application thereof |
| CN111514748A (en) * | 2020-04-30 | 2020-08-11 | 南京中研科技有限公司 | Wide-temperature flue gas dry desulfurizing agent for moving bed process and preparation method thereof |
| CN112619388A (en) * | 2020-11-17 | 2021-04-09 | 天津浩创节能环保设备有限公司 | Preparation method of flue gas desulfurizing agent |
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