CN112999837A - Composition for preparing desulfurizer, preparation method and application thereof - Google Patents
Composition for preparing desulfurizer, preparation method and application thereof Download PDFInfo
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- CN112999837A CN112999837A CN202110265253.1A CN202110265253A CN112999837A CN 112999837 A CN112999837 A CN 112999837A CN 202110265253 A CN202110265253 A CN 202110265253A CN 112999837 A CN112999837 A CN 112999837A
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/508—Sulfur oxides by treating the gases with solids
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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
- B01D53/81—Solid phase processes
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
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Abstract
The invention provides a composition for preparing a desulfurizing agent, the desulfurizing agent prepared from the composition, and a preparation method and application of the desulfurizing agent. The composition for preparing the desulfurizing agent provided by the invention comprises fly ash, calcium hydroxide and/or calcium oxide, an alkaline solution and a binder. The formed dry desulfurizer for flue gas treatment prepared by utilizing the fly ash as a resource has the advantages of good compressive strength, strong adsorption capacity to sulfur dioxide, high sulfur capacity, simple preparation process, wide source of fly ash raw materials and capability of utilizing the fly ash as a resource.
Description
Technical Field
The invention relates to a composition for preparing a desulfurizer, the desulfurizer, and a preparation method and application thereof.
Background
The Fly Ash is one of the most main solid wastes discharged by thermal power plants, is artificial volcanic Ash formed after high-temperature combustion of coal dust, is fine Ash collected from flue gas by a dust catching device of a coal-fired power plant, and is also called Fly Ash (Fly Ash). The fly ash is used as the current industrial waste residue with larger discharge amount, the stacking amount of the fly ash is increased year by year along with the steady development of the power industry, not only is wide land resource wasted, but also serious pollution is caused to the atmosphere, soil, water resources and the like, the earth home where people rely on to live is damaged, and even the health of the people is damaged. In 2019, the national development and improvement committee and the Ministry of industry and belief have united "notice about promoting the gathering and development of massive solid waste comprehensive utilization industry", which points out that the bottleneck problem of the comprehensive utilization area of the fly ash needs to be vigorously developed, namely that the real garbage does not exist in the world and only the resource is misplaced ". The 'non-waste city' of the department of ecological environment further promotes the source reduction and resource utilization of solid wastes such as fly ash and the like, and promotes the green development of cities by leading to a new development concept of innovation, coordination, greenness, openness and sharing.
The traditional desulfurizer for flue gas treatment mainly adopts lime, slaked lime, limestone, dolomite and the like, the mining of the resources needs to excavate the mine resources, the ground surface environment is damaged, the ecological damage of different degrees is caused, and lime ore, dolomite ore and the like belong to non-renewable resources.
In the process of using the calcium-based desulfurizer in the conventional dry desulfurization process, the problems of high calcium-sulfur ratio, low desulfurization activity, large desulfurizer consumption, low effective calcium utilization rate and the like exist, and the requirements of high-efficiency utilization of calcium and ultralow emission of sulfur dioxide are difficult to achieve better. The activity of the desulfurizing agent is generally determined by both physical properties including particle size, specific surface area, pore size, etc., and chemical properties including available calcium content, etc. The desulfurization activity of different calcium-based desulfurizing agents prepared under different process conditions can be greatly different. The higher the desulfurization activity is, the higher the utilization rate of the effective calcium in the desulfurizer is, the higher desulfurization effect can be realized, and the cost of the desulfurizer is reduced. Under the actual flue gas condition, the particle desulfurizer required to be prepared has certain physical strength due to large scale of the device. Therefore, it is also a problem that the development of the shaped granular desulfurizing agent having a corresponding strength must be solved. Therefore, the development of a forming dry desulfurizing agent which has wide raw material sources, easy forming, better compressive strength, high desulfurizing performance and good economic performance is a problem which needs to be solved in the field of flue gas desulfurization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a formed desulfurizer by utilizing fly ash as a resource and a formed dry desulfurizer prepared by the method.
The first aspect of the invention provides a composition for preparing a desulfurizing agent, which comprises fly ash, calcium hydroxide and/or calcium oxide, an alkali solution and a binder.
According to some embodiments of the invention, the composition comprises, in parts by weight:
according to some embodiments of the invention, the mass ratio of the fly ash to the calcium hydroxide and/or calcium oxide is 1:3 to 5:1, and may be, for example, 1:2, 1:1, 2:1, 3:1, or 4: 1.
According to a preferred embodiment of the invention, the mass ratio of the fly ash to the calcium hydroxide and/or calcium oxide is 1:1-1: 3. According to some embodiments of the invention, the weight of the alkaline solution is 2-50 times, for example, 5 times, 6 times, 8 times, 10 times, 12 times, 15 times, 20 times, 30 times, 40 times, 50 times the sum of the weight of the fly ash and the weight of the calcium hydroxide and/or calcium oxide.
According to a preferred embodiment of the invention, the weight of the alkaline solution is 6-12 times the sum of the weight of the fly ash and the weight of the calcium hydroxide and/or calcium oxide.
According to some embodiments of the invention, the fly ash has a particle size of 100 mesh to 400 mesh.
According to some embodiments of the invention, the fly ash has a silica content of 60 wt% or less.
According to some embodiments of the invention, the mass content of alumina in the fly ash is ≧ 15%, such as 16%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, and the like.
According to the preferred embodiment of the invention, the mass content of the alumina in the fly ash is more than or equal to 28 percent.
According to some embodiments of the invention, the calcium hydroxide has a particle size of 100 mesh to 300 mesh.
According to some embodiments of the invention, the calcium oxide has a particle size of 120 mesh to 380 mesh.
According to some embodiments of the invention, the alkaline solution is selected from one or more of caustic soda solution, potassium hydroxide solution and ammonia water.
According to some embodiments of the invention, the total concentration of the alkaline solution is 5 to 40 wt%.
According to some embodiments of the invention, the total concentration of the alkaline solution is 5 to 30 wt%.
According to a preferred embodiment of the invention, the concentration of the caustic soda solution is between 12% and 25% by weight.
According to a preferred embodiment of the invention, the concentration of the potassium hydroxide solution is between 12% and 25% by weight.
According to some embodiments of the invention, the binder species includes, but is not limited to, one or more of activated sludge, sodium carboxymethyl cellulose, calcium bentonite, gelatinized starch, and cement.
In a second aspect, the present invention provides a desulfurizing agent prepared from the composition of the first aspect.
The third aspect of the present invention provides a method for preparing the desulfurizing agent according to the second aspect, comprising the steps of:
s1: mixing fly ash, calcium hydroxide and/or calcium oxide and an alkaline solution to obtain slurry, and carrying out hydro-thermal synthesis on the slurry to obtain hydro-thermally synthesized slurry;
s2: the slurry obtained in S1 after hydrothermal synthesis was subjected to solid-liquid separation, and the separated solid phase was subjected to heat treatment and pulverized.
According to some embodiments of the invention, the method further comprises
S3: mixing the crushed solid phase obtained in the step S2 with an aqueous solution containing a binder, and then performing granulation molding treatment to obtain molded particles;
s4: the molded particles obtained in S3 were subjected to heat treatment and then to a sieving treatment.
According to some embodiments of the invention, in step S1, the hydrothermal synthesis temperature is 40 ℃ to 180 ℃ for 2h to 20 h.
According to some embodiments of the invention, in step S1, the hydrothermal synthesis is a constant temperature hydrothermal synthesis.
According to some embodiments of the invention, the temperature of the heat treatment is 50 ℃ to 200 ℃ in step S2.
According to a preferred embodiment of the present invention, the heat treatment temperature is 88 ℃ to 148 ℃ in step S2.
According to some embodiments of the invention, the pressure of the granulation molding process in step S3 is 15MPa to 180 MPa.
According to a preferred embodiment of the present invention, in step S3, the pressure of the granulation molding process is 80MPa to 150 MPa.
According to some embodiments of the invention, the moisture content of the dried sample of shaped particles is ≦ 8% in step S4.
According to some embodiments of the invention, in step S4, the sized sample of shaped particles has less than or equal to 5.0% particles with a size of 1.5mm or less.
According to some embodiments of the invention, the desulfurizing agent has an outer diameter of 3mm to 12 mm.
According to some embodiments of the invention, the shape of the desulfurizing agent comprises one or more of a cylinder, a cylindrical hollow, a sphere, a quincunx, and a peach-pit.
According to some embodiments of the invention, the desulfurizing agent has a moisture content of 8% or less, a sulfur capacity of 8% or more in 4 hours, a pressure resistance of 120N or more, an effective utilization rate of calcium of 80% or more, a bulk density of 550g/L to 750g/L, a specific surface area of 20m2/g or more, and less than or equal to 5.0% of particles with a particle size of 1.5mm or less, and is not ignited.
The fourth aspect of the invention provides an application of the desulfurizing agent according to the second aspect or the desulfurizing agent obtained by the preparation method according to the third aspect in the field of flue gas desulfurization.
The invention has the following beneficial effects:
firstly, the fly ash is used as a main preparation raw material, the raw material is low in price and wide in source, the solid waste can be recycled, and the fly ash has a good industrial application prospect.
Secondly, the invention fully utilizes the solid waste fly ash as the main preparation raw material of the desulfurizer, because the fly ash contains a large amount of substances such as SiO2, Al2O3, CaO and other trace metal oxides, under proper process conditions, the fly ash and Ca (OH)2 generate hydrothermal synthesis reaction in an alkaline solution, the microstructure of the substances can be changed, the specific surface area and the porosity are increased, and products with high desulfurization activity and desulfurization capability are generated. The active calcium component is improved, the desulfurization activity is improved, the effective utilization rate of calcium can be improved to a great extent compared with the conventional calcium-based forming desulfurizer, and the performance of the conventional calcium-based forming desulfurizer is far surpassed. In addition, after the action of the binder is subjected to molding treatment, the physical strength of the hydro-thermal synthesis reactant can be improved, so that the engineering application of the prepared dry desulfurizing agent is met, and the application occasions of the desulfurizing agent are greatly widened.
The technical indexes of the formed dry desulfurizing agent prepared by the invention are as follows:
the method for preparing the molded desulfurizer by utilizing the fly ash as a resource and the dry desulfurizer prepared by the method are characterized in that: the water content is less than or equal to 8 percent, the bulk density is 450g/L-700g/L, the effective utilization rate of calcium is more than or equal to 80 percent, the specific surface area is more than or equal to 20m2/g, the pressure resistance is more than or equal to 120N, the sulfur capacity is more than or equal to 8 percent in 4 hours, the particle size which is less than or equal to 1.5mm is less than or equal to 5.0 percent, and the fire cannot.
Detailed Description
The present invention will be more fully understood by those skilled in the art by describing the present invention in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention in any way.
In the following examples, the fly ash is mainly characterized in that the content of SiO2 is not more than 60 wt%, the content of alumina is not less than 15 wt%, and the particle size of the fly ash is 100-400 meshes; the grain size of Ca (OH)2 is 100 meshes-400 meshes or the grain size of CaO is 120 meshes-380 meshes; types of binders include, but are not limited to, activated sludge, sodium carboxymethylcellulose, gelatinized starch, cement gum, and the like; the diameter of the desulfurizer after molding is 3mm-12mm, wherein the molded shape comprises but is not limited to a cylinder, a cylinder hollow, a sphere, a plum blossom shape, a peach kernel shape and the like; and the proportion of the particles with the diameter less than or equal to 1.5mm in the molded particle sample is less than or equal to 5.0 percent.
The preparation method of the molding dry desulfurizing agent comprises the processes of material mixing, hydrothermal synthesis, solid-liquid separation, granulation molding, drying and screening treatment and the like. The material mixing process is a process of fully and uniformly mixing the fly ash and calcium hydroxide and/or calcium oxide, the hydrothermal synthesis is a process of putting the mixed material into an alkaline solution to carry out hydrothermal reaction under specific temperature and time conditions, the solid-liquid separation is a process of carrying out solid-liquid separation on slurry obtained after the hydrothermal reaction, the granulation molding is a process of carrying out granulation molding after crushing a solid phase obtained by the solid-liquid separation through heat treatment and then stirring and uniformly mixing the solid phase with water mixed with a binder, and the heat treatment screening process is a process of carrying out heat treatment and screening treatment on the granulated and molded material to ensure that the granulated and molded particles can meet required technical performance indexes, so that the molded dry desulfurizer product for the dry flue gas treatment is prepared.
The preparation process comprises the following specific steps:
the method comprises the following steps: selecting fly ash with the particle size of 100-300 meshes, the content of SiO2 being less than or equal to 60 wt% and the content of alumina being more than or equal to 15 wt%, Ca (OH)2 with the particle size of 100-400 meshes or CaO with the particle size of 120-380 meshes, uniformly mixing the fly ash and the CaO according to the formula, putting the mixture into an alkali solution with the weight 2-50 times of the total weight of the mixture, uniformly mixing the mixture to form slurry, putting the slurry into a water bath with the temperature of 40-180 ℃, and carrying out hydrothermal synthesis at constant temperature for 2-20 h;
step two: directly carrying out liquid-solid thermal state separation on the treated slurry, and crushing a solid phase after the separated solid phase is subjected to heat treatment at 50-200 ℃;
step three: mixing the crushed solid phase with a binder mixed in water according to a ratio, uniformly stirring, and then performing granulation molding treatment in molding equipment, wherein the molding pressure is 15MPa-180MPa, and the diameter range of the molded material is 3mm-12 mm;
step four: and (3) carrying out thermal treatment on the molded particles after granulation molding to ensure that the moisture content of the molded particle sample is less than or equal to 8%, and carrying out screening treatment on the molded particle sample to ensure that the content of particles with the particle size of less than or equal to 1.5mm is less than or equal to 5.0%, thus obtaining the molded dry desulfurizer product for dry flue gas treatment.
Example 1
Firstly, uniformly mixing 65 wt% of fly ash (wherein the content of alumina in the fly ash is 27%), 35 wt% of Ca (OH)2, then putting the mixed materials into 20 wt% of caustic soda solution which is 8 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 63 ℃, and carrying out hydrothermal synthesis for 10 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 5 wt% sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 25MPa pressure to obtain a cylindrical product with a diameter of 9 mm; finally, the mixture is placed at 115 ℃ for heat treatment until the water content is 7.5 percent, and is subjected to screening treatment, so that the particles with the size less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the formed columnar desulfurizer is prepared, the specific surface area is 87m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 2
Firstly, uniformly mixing 55 wt% of fly ash (wherein the content of alumina in the fly ash is 22%), 45 wt% of Ca (OH)2, then putting the mixed materials into 8 wt% of caustic soda solution with the weight 5 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 97 ℃, and carrying out hydrothermal synthesis for 6 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 1 wt% sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 16.5MPa with diameter of 9mm to obtain cylindrical shape; finally, the mixture is placed at 105 ℃ for heat treatment until the moisture content is 6.8 percent, and is subjected to screening treatment, so that the particles with the size less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the formed columnar desulfurizer is prepared, the specific surface area is 37m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 3
Firstly, uniformly mixing 31 wt% of fly ash (wherein the content of alumina in the fly ash is 16%) and 69 wt% of CaO, then putting the mixed materials into 5 wt% of caustic soda solution which is 12 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 130 ℃, and carrying out hydrothermal synthesis for 12 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 2.3 wt% sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 55MPa pressure to obtain a hollow cylindrical product with a diameter of 9 mm; finally, the mixture is placed at 115 ℃ for heat treatment until the water content is 7.5 percent, and is subjected to screening treatment, so that the particles with the size less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the formed columnar desulfurizer is prepared, the specific surface area is 46m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 4
Firstly, uniformly mixing 60 wt% of fly ash (wherein the content of alumina in the fly ash is 29%), 40 wt% of Ca (OH)2, then putting the mixed materials into 7 wt% of ammonia water which is 20 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 100 ℃, and carrying out hydrothermal synthesis for 6 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the crushed solid phase with 20 wt% of cement mixed with water, stirring, and performing extrusion forming under the pressure of 125MPa, wherein the diameter is 7mm, and the mixture is cylindrical; finally, drying the mixture at 105 ℃ until the water content is 6.9 percent, sieving the mixture to ensure that the particles with the diameter less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm to prepare the formed columnar desulfurizer, wherein the specific surface area is 32 square meters per gram, the desulfurization performance evaluation is carried out according to the GB/T35254 + 2017 standard, the 4-hour sulfur capacity is 8.41 percent, the compressive strength is 124N, the calcium utilization rate is 81.3 percent, the bulk density is 715g/L, and the columnar desulfurizer is not ignited.
Example 5
Firstly, uniformly mixing 75 wt% of fly ash (wherein the content of alumina in the fly ash is 49%), 25 wt% of Ca (OH)2, then putting the mixed materials into 9 wt% of caustic soda solution which is 12 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 100 ℃, and carrying out hydrothermal synthesis for 16 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 3.5 wt% of gelatinized starch dissolved in water, stirring, and extrusion-molding under 20MPa pressure to obtain a cylindrical shape with a diameter of 9 mm; finally, the mixture is placed at 105 ℃ for heat treatment until the water content is 6.9 percent, and is subjected to screening treatment, so that the particles with the diameter less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the formed columnar desulfurizer is prepared, the specific surface is 37 square meters per gram, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 6
Firstly, uniformly mixing 45 wt% of fly ash (wherein the content of alumina in the fly ash is 20%) and 55 wt% of CaO, then putting the mixed materials into 9 wt% of alkali mixed solution (caustic soda solution, potassium hydroxide solution and ammonia water) which is 9 times of the total weight of the fly ash, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 160 ℃, and carrying out hydrothermal synthesis for 3.0 h; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the crushed solid phase and 28 wt% of activated sludge in water, mixing, stirring, and performing extrusion molding under the pressure of 98MPa, wherein the shape is peach-shaped, and the outer diameter is about 10 mm; finally, the mixture is placed at 105 ℃ for heat treatment until the water content is 7.3 percent, and is subjected to screening treatment, so that the particles with the size less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the peach-shaped desulfurizer is prepared, the specific surface area is 31m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 7
Firstly, uniformly mixing 30 wt% of fly ash (wherein the content of alumina in the fly ash is 32%), 70 wt% of Ca (OH)2, then putting the mixed materials into 20 wt% of potassium hydroxide solution which is 12 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 60 ℃, and carrying out hydrothermal synthesis for 10 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 5 wt% of sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 25MPa pressure to obtain a hollow cylindrical product with diameter of 7 mm; finally, the mixture is placed at 115 ℃ for heat treatment until the water content is 6.9 percent, and is sieved, so that the particles with the diameter less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the molded hollow columnar desulfurizer is prepared, the specific surface area is 34 square meters per gram, the desulfurization performance evaluation is carried out according to the GB/T35254-2017 standard, and the 4-hour sulfur capacity is 13. 7 percent, compressive strength of 134N, calcium utilization rate of 83.1 percent, bulk density of 580g/L and no fire.
Example 8
Firstly, uniformly mixing 65 wt% of fly ash (wherein the content of alumina in the fly ash is 15%) and 35 wt% of CaO, then putting the mixed materials into a mixed solution of 18 wt% of potassium hydroxide and ammonia water which is 12 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 75 ℃, and carrying out hydrothermal synthesis for 4.5 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 5 wt% sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 25MPa to obtain plum blossom shape; finally, the mixture is placed at 85 ℃ for heat treatment until the water content is 7.8 percent, and is subjected to screening treatment, so that the particles with the particle size of less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the quincunx desulfurizing agent is prepared, the specific surface area is 28m2/g, the 4-hour sulfur capacity is 8.41 percent, the compressive strength is 140N, the calcium utilization rate is 88.9 percent, the bulk density is 562g/L and the mixture does not catch fire when the desulfurization performance evaluation is carried out according to the GB/T35254 one-year 2017 standard.
Example 9
Firstly, uniformly mixing 35 wt% of fly ash (wherein the content of alumina in the fly ash is 21%), 65 wt% of Ca (OH)2, then putting the mixed materials into 5 wt% of caustic soda solution with the weight 20 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 50 ℃, and carrying out hydrothermal synthesis for 10 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 3.5 wt% of sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 140MPa to obtain a spherical-like material with a particle size of 10 mm; finally, the mixture is dried at 140 ℃ until the moisture content is 7.5 percent, and is subjected to screening treatment, so that the particles with the particle size of less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the formed desulfurizer is prepared, the specific surface area is 41m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 10
Firstly, uniformly mixing 50 wt% of fly ash (wherein the content of alumina in the fly ash is 46%), 50 wt% of Ca (OH)2, then putting the mixed materials into 30 wt% of caustic soda solution which is 2 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 135 ℃, and carrying out hydrothermal synthesis for 5 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 2.8 wt% sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 125MPa with diameter of 8mm to obtain cylindrical shape; finally, drying the mixture at 105 ℃ until the water content is 8 percent, sieving the mixture to ensure that the particles with the diameter less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm to prepare the formed columnar desulfurizer, the specific surface area of the formed columnar desulfurizer is 26m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 11
Firstly, uniformly mixing 62 wt% of fly ash (wherein the content of alumina in the fly ash is 34%), 38 wt% of Ca (OH)2, then putting the mixed materials into 25 wt% of caustic soda solution which is 15 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 120 ℃, and carrying out hydrothermal synthesis for 6 hours; then carrying out solid-liquid separation on the hot slurry, carrying out heat treatment on the separated solid phase at 120-200 ℃, and then crushing; mixing the pulverized solid phase with 2 wt% of sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 37MPa pressure to obtain a hollow cylindrical product with a diameter of 9 mm; finally, drying the mixture at 140 ℃ until the water content is 7.8 percent, sieving the mixture to ensure that the particles with the diameter less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm to prepare the hollow columnar desulfurizer, the specific surface area of the hollow columnar desulfurizer is 48m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Example 12
Firstly, uniformly mixing 65 wt% of fly ash (wherein the content of alumina in the fly ash is 16%), 35 wt% of Ca (OH)2, then putting the mixed materials into 25 wt% of caustic soda solution which is 2 times of the total weight of the mixed materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 65 ℃, and carrying out hydrothermal synthesis for 2 hours; then carrying out solid-liquid separation on the hot slurry, and carrying out heat treatment on the separated solid phase at 130 ℃ and then crushing; mixing the pulverized solid phase with 25% calcium bentonite, stirring, and extrusion-molding under 45MPa pressure, wherein the diameter is 8mm, and the mixture is cylindrical; finally, the mixture is dried at 135 ℃ until the moisture content is 6.2 percent, and is subjected to screening treatment, so that the particles with the size less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, and the formed columnar desulfurizer is prepared, the specific surface area is 32m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-.
Comparative example 1
Firstly, uniformly mixing 65 wt% of fly ash and 35 wt% of Ca (OH)2, then putting the mixed materials into an aqueous solution with the weight 8 times of the total weight of the materials, uniformly mixing, putting the uniformly mixed slurry into a constant-temperature water bath at 65 ℃, and carrying out hydrothermal synthesis for 4 hours; then carrying out solid-liquid separation on the hot slurry, and drying and crushing the separated solid phase at 90 ℃; mixing the pulverized solid phase with 3.2 wt% of sodium carboxymethylcellulose dissolved in water, stirring, and extrusion-molding under 40MPa pressure to obtain a peach-shaped product with particle diameter of 6 mm; finally, the mixture is dried at 85 ℃ until the moisture content is 5.8 percent, and is subjected to screening treatment, so that the particles with the particle size of less than or equal to 1.5mm are less than or equal to 5.0 percent and less than or equal to 1.5mm, the specific surface area of the formed walnut-shaped desulfurizer is 19m2/g, the desulfurization performance evaluation is carried out according to the GB/T35254-2017 standard, the 4-hour sulfur capacity is 7.9 percent, the compressive strength is 89N, the calcium utilization rate is 67.9 percent, the bulk density is 597g/L, and the formed walnut-shaped desulfurizer does not catch fire.
Comparative example 2
Firstly, uniformly mixing 65 wt% of fly ash and 35 wt% of Ca (OH)2, then putting the mixed materials into 20 wt% of caustic soda solution with the weight 8 times of the total weight of the materials, uniformly mixing, mixing the uniformly mixed slurry with 5 wt% of sodium carboxymethyl cellulose dissolved in water, stirring, and then carrying out extrusion forming under the pressure of 25MPa, wherein the diameter is 9mm, and the mixture is cylindrical; finally, the mixture is dried at 115 ℃ until the water content is 8 percent, and is sieved, so that the particle size less than or equal to 1.5mm is less than or equal to 5.0 percent and less than or equal to 1.5mm, and the formed columnar desulfurizer is prepared, the specific surface area is 12m2/g, and the desulfurization performance evaluation is carried out according to the GB/T35254-.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The invention has been described with reference to an exemplary embodiment, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the appended claims, and changes can be made thereto without departing from the spirit and scope of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A composition for preparing a desulfurizing agent comprises fly ash, calcium hydroxide and/or calcium oxide, an alkaline solution and a binder.
2. The composition of claim 1, wherein the composition comprises, in parts by weight:
3. the composition according to claim 1 or 2, characterized in that the weight ratio of the fly ash to the calcium hydroxide and/or calcium oxide is 1:3-5:1, preferably 1:1-1: 3; and/or
The weight of the alkaline solution is 2-50 times, preferably 6-12 times of the sum of the weight of the fly ash and the weight of the calcium hydroxide and/or the calcium oxide.
4. The composition as claimed in any one of claims 1 to 3, wherein the fly ash has a particle size of 100 mesh to 400 mesh, preferably the fly ash has a silica content of 60 wt.% or less; and/or the content of alumina in the fly ash is more than or equal to 15 percent, preferably more than or equal to 28 percent; and/or
The particle size of the calcium hydroxide is 100-300 meshes; and/or the particle size of the calcium oxide is 120-380 meshes; and/or
The alkaline solution is selected from one or more of caustic soda solution, potassium hydroxide solution and ammonia water, and preferably, the total concentration of the alkaline solution is 5-30 wt%; more preferably, the concentration of the caustic soda solution and/or the potassium hydroxide solution is 12 wt% to 25 wt%; and/or
The binder comprises one or more of activated sludge, sodium carboxymethyl cellulose, calcium bentonite, gelatinized starch and clay.
5. A desulfurizing agent prepared from the composition of any one of claims 1-4.
6. A method for preparing the desulfurizing agent of claim 5, comprising the steps of:
s1: mixing fly ash, calcium hydroxide and/or calcium oxide and an alkaline solution to obtain slurry, and carrying out hydro-thermal synthesis on the slurry to obtain hydro-thermally synthesized slurry;
s2: performing solid-liquid separation on the slurry obtained in the step S1 after the hydrothermal synthesis, and performing heat treatment and crushing on the separated solid phase;
preferably, the method further comprises
S3: mixing the crushed solid phase obtained in the step S2 with an aqueous solution containing a binder, and then performing granulation molding treatment to obtain molded particles;
s4: the molded particles obtained in S3 were subjected to heat treatment and then to a sieving treatment.
7. The preparation method according to claim 6, wherein in step S1, the temperature of the hydrothermal synthesis is 40-180 ℃ and the time is 2-20 h; preferably, the hydrothermal synthesis is constant-temperature hydrothermal synthesis; and/or
In step S2, the temperature of the heat treatment is 50-200 ℃, preferably 88-148 ℃; and/or
In step S3, the pressure of the granulation molding treatment is 15MPa to 180MPa, preferably 80MPa to 150 MPa; and/or in step S4, the moisture content of the dried shaped particle sample is less than or equal to 8%; and/or
In step S4, in the molded particle sample after the sieving treatment, the particles with the diameter less than or equal to 1.5mm are less than or equal to 5.0 percent.
8. The production method according to claim 6 or 7, wherein the desulfurizing agent has an outer diameter of 3mm to 12 mm; and/or the shape of the desulfurizing agent comprises one or more of a cylinder, a cylindrical hollow, a sphere, a quincunx and a peach-pit.
9. The preparation method according to any one of claims 6 to 8, wherein the desulfurizing agent has a moisture content of 8% or less, a 4-hour sulfur capacity of 8% or more, a pressure resistance of 120N or more, an effective utilization rate of calcium of 80% or more, a bulk density of 550g/L to 750g/L, a specific surface area of 20m2/g or more, and less than or equal to 5.0% of particles having a diameter of 1.5mm or less.
10. Use of the desulfurization agent according to claim 5 or the desulfurization agent obtained by the preparation method according to any one of claims 6 to 9 in the field of flue gas desulfurization.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115888347A (en) * | 2021-08-03 | 2023-04-04 | 曹妃甸慧宇环境工程有限公司 | A dry desulfurizer for coke oven flue gas and its preparation method |
| CN115920819A (en) * | 2023-01-18 | 2023-04-07 | 北京清新环境技术股份有限公司 | Fly ash-based desulfurizer preparation device for low-sulfur flue gas and preparation method thereof |
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| US5047222A (en) * | 1986-11-07 | 1991-09-10 | Board Of Regents, The University Of Texas System | Process for removing sulfur from sulfur-containing gases: high calcium fly-ash |
| JP2002113361A (en) * | 2000-10-10 | 2002-04-16 | Japan Science & Technology Corp | Absorbing agent for desulfurization and method of manufacturing desulfurizing agent |
| CN101559317A (en) * | 2008-04-16 | 2009-10-21 | 宇星科技发展(深圳)有限公司 | Fly ash calcium based flue gas desulfurizer and method for manufacturing same |
| CN101569828A (en) * | 2009-06-10 | 2009-11-04 | 河北工业大学 | Solid particle used for jetting bed flue gas desulfurization process and preparation method |
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| US5047222A (en) * | 1986-11-07 | 1991-09-10 | Board Of Regents, The University Of Texas System | Process for removing sulfur from sulfur-containing gases: high calcium fly-ash |
| JP2002113361A (en) * | 2000-10-10 | 2002-04-16 | Japan Science & Technology Corp | Absorbing agent for desulfurization and method of manufacturing desulfurizing agent |
| CN101559317A (en) * | 2008-04-16 | 2009-10-21 | 宇星科技发展(深圳)有限公司 | Fly ash calcium based flue gas desulfurizer and method for manufacturing same |
| CN101569828A (en) * | 2009-06-10 | 2009-11-04 | 河北工业大学 | Solid particle used for jetting bed flue gas desulfurization process and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115888347A (en) * | 2021-08-03 | 2023-04-04 | 曹妃甸慧宇环境工程有限公司 | A dry desulfurizer for coke oven flue gas and its preparation method |
| CN115920819A (en) * | 2023-01-18 | 2023-04-07 | 北京清新环境技术股份有限公司 | Fly ash-based desulfurizer preparation device for low-sulfur flue gas and preparation method thereof |
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