WO2023024391A1 - Composition de désulfurant et son procédé de préparation - Google Patents

Composition de désulfurant et son procédé de préparation Download PDF

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WO2023024391A1
WO2023024391A1 PCT/CN2021/143497 CN2021143497W WO2023024391A1 WO 2023024391 A1 WO2023024391 A1 WO 2023024391A1 CN 2021143497 W CN2021143497 W CN 2021143497W WO 2023024391 A1 WO2023024391 A1 WO 2023024391A1
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Prior art keywords
desulfurizing agent
agent composition
desulfurizer
composition
sulfur capacity
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PCT/CN2021/143497
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English (en)
Chinese (zh)
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王春霞
张焜
魏闯
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中晶环境科技股份有限公司
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Publication of WO2023024391A1 publication Critical patent/WO2023024391A1/fr

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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
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • 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

Definitions

  • the invention relates to a desulfurizing agent composition and a preparation method thereof.
  • the methods of flue gas desulfurization are roughly divided into three categories: wet method, that is, using liquid absorbents such as water or lye to wash the flue gas to remove sulfur dioxide;
  • the reaction produces dry powdered calcium sulfite, which has the characteristics of both wet and dry methods;
  • the dry method uses powdery or granular absorbents, adsorbents or catalysts to remove sulfur dioxide.
  • the wet desulfurization process is mature, and the desulfurization efficiency is >95%, but it causes secondary pollution, and the desulfurized flue gas contains a lot of water, which is easy to damage the desulfurization device, resulting in large investment costs and high operating costs; the desulfurization of the semi-dry desulfurization process The efficiency is relatively low, and the exhaust smoke is white mist, which affects the senses; the dry desulfurization process does not have secondary pollution, corrosion, condensation and other problems, so it has been rapidly developed and applied in recent years.
  • the desulfurization agent used in the dry desulfurization process has poor mechanical strength and is easy to pulverize.
  • the desulfurization agent needs to be roasted at a high temperature of 500 ° C to 1100 ° C, and the production cost is high.
  • CN112206758A discloses a preparation method of a biomass charcoal-based desulfurization catalyst, comprising the following steps: (1) under the protection of an inert atmosphere, heat-treat the biomass raw material at 500-600° C. for 2-3 hours to obtain carbon powder; (2) Granulating the mixture composed of carbon powder, binder and dispersant to obtain the first precursor; (3) under the protection of an inert atmosphere, heat-treating the first precursor at 500-700°C for 2-6 hours to obtain the first precursor The second precursor; (4) heat-treating the second precursor at 800-900° C. for 2-6 hours in an atmosphere containing an activated gas to obtain a biomass charcoal-based desulfurization catalyst.
  • the preparation process of the method is complicated, energy consumption and production cost are high, and the compressive strength of the prepared biomass charcoal-based desulfurization catalyst is low (compressive strength is greater than or equal to 160N/cm), and in the process of transportation and use, the desulfurization catalyst Chalks up easily.
  • CN100537789A discloses a preparation method of a high-sulfur capacity iron-based desulfurizer, comprising the following steps: (1) placing ferrous sulfate solution and ammonia solution in an ultrasonic environment for precipitation reaction, centrifugation and microwave treatment to obtain nano-iron oxide ; (2) Using nano-iron oxide as the main active component, adding anti-coking additives, vulcanization accelerators, strength enhancers, binders and pore-forming agents, mechanically mixing the raw materials, and then placing them at 30-80°C Dry for 3 to 6 hours, then grind and knead with a mixer, and knead with water to make strips, granules or flakes; (3) Dry the molded product at 50-80°C overnight, and then place it at 600- Roasting at 900°C for 2 to 6 hours to obtain a high-sulfur capacity iron-based desulfurizer; among them, the anti-coking additives are trace amounts of ceria and light magnesium oxide, the strength
  • the cycle stability of the desulfurizer is good, but its sulfur capacity still needs to be further improved (the sulfur capacity is 10.7-25.1%).
  • the preparation process of the desulfurizer is complicated, and each step takes a long time, and the method requires high-temperature roasting at 600-900° C., which has high energy consumption and production costs, and is not suitable for industrial production.
  • CN112295395A discloses a preparation method of a flue gas desulfurizer, comprising the following steps: (1) treating calcium hydroxide with a surfactant, drying and pulverizing to obtain modified calcium hydroxide; (2) converting the modified hydrogen Calcium oxide, calcium carbonate and additives are mixed, and the mixed powder is obtained by stirring evenly; (3) the mixed powder is mixed with the binder, stirred evenly, and an appropriate amount of aqueous solution is added to fully knead to obtain a kneaded solid; (4) the The kneaded solid is extruded, shaped and dried to obtain a flue gas desulfurizer.
  • the strength of the flue gas desulfurizer is 90-118N/cm, and the sulfur capacity is 31-39%. Both the strength and the sulfur capacity of the desulfurizer still need to be improved.
  • an object of the present invention is to provide a desulfurizer composition with high strength and sulfur capacity. Further, the preparation process is simple, and the energy consumption and cost are low.
  • Another object of the present invention is to provide a method for preparing the above-mentioned desulfurizing agent composition, which takes less time and has lower energy consumption and production costs.
  • the present invention provides a desulfurizer composition, comprising:
  • the desulfurizing agent composition of the present invention preferably, it includes the following components:
  • the desulfurizing agent composition of the present invention preferably, it includes the following components:
  • the desulfurizing agent composition of the present invention preferably, it consists of the following components and unavoidable impurities:
  • the desulfurizing agent composition of the present invention preferably, it consists of the following components:
  • the sum of the weight percentages of the above-mentioned components is 100wt%.
  • the desulfurizing agent composition of the present invention is a cylinder with a diameter of 2-5 mm and a length of 8-15 mm.
  • the desulfurizing agent composition of the present invention preferably, has a breakthrough sulfur capacity ⁇ 80 mg/g, a saturated sulfur capacity ⁇ 35%, a compressive strength ⁇ 150 N/cm, and an abrasion resistance ⁇ 98%.
  • the desulfurizing agent composition of the present invention preferably, is obtained by heat-treating the granulated product at 300-380° C. for 1.5-3.5 hours.
  • the present invention provides a method for preparing the above-mentioned desulfurizing agent composition.
  • Lime powder, iron powder, bentonite, pore-forming agent, cement, white mud, clay and diatomaceous earth particles are mixed; then water is added for wet mixing, forming a mixed material; granulating the mixed material, and then heat-treating the granulated product at 300-380° C. for 1.5-3.5 hours to obtain a desulfurizing agent composition.
  • the pore-forming agent is selected from one or more of urea, carbon powder, graphite, carbon black, starch, polyvinyl alcohol, polyethylene glycol, straw, and rice husk;
  • the wet mixing time is 10-60 minutes; the stacking thickness of the granulated product is 15-40mm during heat treatment.
  • the desulfurizer composition of the present invention has a breakthrough sulfur capacity of ⁇ 80mg/g, a saturated sulfur capacity of ⁇ 35%, a compressive strength of ⁇ 150N/cm, and an abrasion resistance of ⁇ 98%.
  • the preparation method of the invention is simple, takes less time, has lower energy consumption and production cost, and is suitable for industrial application.
  • the saturated sulfur capacity means the maximum mass of sulfur that can be absorbed by a desulfurizer per unit mass.
  • Saturated sulfur capacity is an important index to measure desulfurizer, usually expressed in percentage.
  • the breakthrough sulfur capacity indicates the mass of sulfur that can be absorbed by the desulfurizer per unit mass when ensuring the process purification index.
  • the unit is usually mg/g.
  • Compressive strength indicates the ultimate load that a material can withstand per unit area.
  • the wear resistance is used to reflect the ability of the desulfurizer to resist mechanical wear. The higher the wear resistance value, the stronger the desulfurizer's ability to resist mechanical wear, and it is not easy to pulverize.
  • the desulfurizer composition may be in the form of strips, granules or flakes, preferably in the form of granules, and more preferably in the form of cylindrical granules.
  • white mud is a non-metallic mineral, a kind of clay and clay rock mainly composed of kaolinite clay minerals, and is also called dolomite because it is white and delicate.
  • white clay refers to active white clay, which is a naturally produced, fine-grained, high-adsorption soil-like substance, also known as bleaching earth.
  • the present invention surprisingly found that controlling the element ratio of the desulfurizer within a specific range can make the desulfurizer composition have higher breakthrough sulfur capacity, saturated sulfur capacity, compressive strength and wear resistance; and, the desulfurizer The agent composition can be prepared by low temperature heat treatment. Therefore, the present invention provides a desulfurizer composition, which is prepared by low-temperature heat treatment and has specific elemental composition and good performance parameters. Details are given below.
  • the desulfurizer composition of the present invention contains the following elements: Ca, Fe, Mg, Al, Na, K, Si, H and O. Of course, unavoidable impurities may also be contained.
  • the content of Ca may be 30.2wt%-38.5wt%, preferably 30.5wt%-37.5wt%, more preferably 30.7wt%-37wt%.
  • the abrasion resistance of the desulfurizer composition is less than 93%; when the Ca content is greater than 38.5wt%, the breakthrough sulfur capacity of the desulfurizer composition is less than 80mg/g, and the saturated sulfur capacity is less than 25%. .
  • the content of Fe may be 6.7wt%-10.8wt%, preferably 7wt%-9.8wt%, more preferably 7.1wt%-9.5wt%.
  • the Fe content is less than 6.7wt%, the sulfur capacity of the desulfurizer composition is low, and the desulfurization effect is not good; when the Fe content is greater than 10.8wt%, the compressive strength of the desulfurizer composition is poor.
  • the content of Mg may be 0.8wt%-2.2wt%, preferably 0.98wt%-2.1wt%, more preferably 1.2wt%-2.1wt%.
  • the sulfur capacity of the desulfurizer composition is low, the breakthrough sulfur capacity ⁇ 76mg/g, and the saturated sulfur capacity ⁇ 25%; when the Mg content is greater than 2.2wt%, the desulfurizer composition is saturated Sulfur capacity ⁇ 30%.
  • the content of Al may be 7.2wt%-12.4wt%, preferably 8.1wt%-11.5wt%, more preferably 9.1wt%-11wt%.
  • the sulfur capacity of the desulfurizer composition is low, the breakthrough sulfur capacity ⁇ 80mg/g, and the saturated sulfur capacity ⁇ 30%; when the Al content is greater than 12.4wt%, the desulfurizer composition is resistant to The grinding strength is poor at only 92%.
  • the content of Na may be 3wt%-6.2wt%, preferably 3.5wt%-5.5wt%, more preferably 3.8wt%-5.4wt%.
  • the content of K may be 0wt%-2.5wt%, preferably 0.8wt%-2wt%, more preferably 1wt%-1.8wt%.
  • the content of Si may be 5.5wt%-10.1wt%, preferably 6.5wt%-10wt%, more preferably 7.5wt%-9.4wt%.
  • the breakthrough sulfur capacity of the desulfurizer composition is less than 80mg/g
  • the saturated sulfur capacity is less than 25%
  • the wear resistance is less than 96%
  • the Si content is greater than 10.1wt%
  • the desulfurizer composition The saturated sulfur capacity is ⁇ 30%, and the wear resistance is ⁇ 93%.
  • the content of H may be 1.8wt%-3.2wt%, preferably 2.0wt%-3.2wt%, more preferably 2.6wt%-3.2wt%.
  • the content of O may be 20.6wt%-36.5wt%, preferably 22.5wt%-33.5wt%, more preferably 22.5wt%-32.5wt%.
  • the desulfurizer composition contains: Ca 30.2wt%-38.5wt%, Fe 6.7wt%-10.8wt%, Mg 0.8wt%-2.2wt%, Al 7.2wt%-12.4wt%, Na 3wt% ⁇ 6.2wt%, K 0wt% ⁇ 2.5wt%, Si 5.5wt% ⁇ 10.1wt%, H 1.8wt% ⁇ 3.2wt%, and O 20.6wt% ⁇ 36.5wt%.
  • the desulfurizer composition contains: Ca 30.5wt%-37.5wt%, Fe 7wt%-9.8wt%, Mg 0.98wt%-2.1wt%, Al 8.1wt%-11.5wt%, Na 3.5wt% ⁇ 5.5wt%, K 0.8wt% ⁇ 2wt%, Si 6.5wt% ⁇ 10wt%, H 2.0wt% ⁇ 3.2wt% and O 22.5wt% ⁇ 33.5wt%.
  • the desulfurizer composition contains: Ca 30.7wt% to 37wt%, Fe 7.1wt% to 9.5wt%, Mg 1.2wt% to 2.1wt%, Al 9.1wt% to 11wt%, Na 3.8wt% ⁇ 5.4wt%, K 1wt% ⁇ 1.8wt%, Si 7.5wt% ⁇ 9.4wt%, H 2.6wt% ⁇ 3.2wt%, and O 22.5wt% ⁇ 32.5wt%.
  • the desulfurizer composition is composed of the following components and unavoidable impurities (such as carbon): Ca 30.2wt% ⁇ 38.5wt%, Fe 6.7wt% ⁇ 10.8wt%, Mg 0.8wt% ⁇ 2.2wt %, Al 7.2wt% ⁇ 12.4wt%, Na 3wt% ⁇ 6.2wt%, K 0wt% ⁇ 2.5wt%, Si 5.5wt% ⁇ 10.1wt%, H 1.8wt% ⁇ 3.2wt% and O 20.6wt% ⁇ 36.5 wt%.
  • unavoidable impurities such as carbon
  • the desulfurizer composition is composed of the following components: Ca 30.2wt% to 38.5wt%, Fe 6.7wt% to 10.8wt%, Mg 0.8wt% to 2.2wt%, Al 7.2wt% to 12.4wt% %, Na 3wt% ⁇ 6.2wt%, K 0wt% ⁇ 2.5wt%, Si 5.5wt% ⁇ 10.1wt%, H 1.8wt% ⁇ 3.2wt% and O 20.6wt% ⁇ 36.5wt%; the weight of the above components The sum of the percentages is 100 wt%.
  • the desulfurizer composition contains: Ca 30.2wt% to 36wt%, Fe 6.7wt% to 10.8wt%, Mg 0.8wt% to 2.2wt%, Al 7.2wt% to 12.4wt%, Na 3wt% % ⁇ 6.2wt%, K 0wt% ⁇ 2.5wt%, Si 5.5wt% ⁇ 8.5wt%, H 1.8wt% ⁇ 3.2wt%, and O 20.6wt% ⁇ 36.5wt%.
  • the desulfurizer composition contains: Ca 31wt% to 38.5wt%, Fe 6.7wt% to 10.8wt%, Mg 0.8wt% to 2.2wt%, Al 7.2wt% to 12.4wt%, Na 3wt% ⁇ 6.2wt%, K 0.5wt% ⁇ 2.5wt%, Si 6.5wt% ⁇ 10.1wt%, H 2.6wt% ⁇ 3.2wt%, and O 20.6wt% ⁇ 26.8wt%.
  • the desulfurizer composition of the present invention may be in the form of strips, granules or flakes, preferably granules, more preferably cylindrical granules.
  • the diameter of the cylindrical particles may be 2-5 mm, preferably 2-4.5 mm, more preferably 2.5-4 mm.
  • the length of the cylindrical particles may be 8-15 mm, preferably 9-14 mm, more preferably 10-13 mm.
  • the desulfurizer composition with this shape and size can not only provide higher sulfur capacity during use, but also be convenient for replacement and storage.
  • the desulfurizing agent composition of the present invention has relatively high penetration sulfur capacity, saturated sulfur capacity, compressive strength and wear resistance, and has the advantages of good desulfurization effect, high mechanical strength, not easy to pulverize, and the like.
  • the breakthrough sulfur capacity of the desulfurizer composition is ⁇ 80 mg/g, preferably ⁇ 90 mg/g, more preferably ⁇ 100 mg/g.
  • the saturated sulfur capacity of the desulfurizer composition is ⁇ 35%, preferably ⁇ 40%, more preferably ⁇ 45%.
  • the compressive strength of the desulfurizer composition is ⁇ 150N/cm, preferably ⁇ 210N/cm, more preferably ⁇ 250N/cm.
  • the abrasion resistance of the desulfurizer composition is ⁇ 96%, preferably ⁇ 98%.
  • the breakthrough sulfur capacity of the desulfurizer composition is ⁇ 80 mg/g, the saturated sulfur capacity is ⁇ 35%, the compressive strength is ⁇ 150 N/cm, and the wear resistance is ⁇ 96%. In some embodiments, the breakthrough sulfur capacity of the desulfurizer composition is ⁇ 90 mg/g, the saturated sulfur capacity is ⁇ 40%, the compressive strength is ⁇ 210 N/cm, and the wear resistance is ⁇ 98%. In other embodiments, the breakthrough sulfur capacity of the desulfurizer composition is ⁇ 100 mg/g, the saturated sulfur capacity is ⁇ 45%, the compressive strength is ⁇ 250 N/cm, and the wear resistance is ⁇ 98%.
  • the desulfurizing agent composition of the present invention is obtained by heat-treating the granulated product under low temperature conditions.
  • the heat treatment temperature may be 300-380°C, preferably 310-370°C, more preferably 320-360°C. This temperature can not only ensure that the desulfurizer composition has higher sulfur capacity and strength, but also does not generate excessive energy consumption.
  • the heat treatment time may be 1.5-3.5 hours, preferably 2-3.5 hours, more preferably 2.5-3.2 hours.
  • the heat treatment time can not only ensure the high sulfur capacity and strength of the desulfurizer composition, but also help to improve production efficiency and reduce production cost.
  • the granulated product is heat-treated at 300-380° C. for 1.5-3.5 hours to prepare a desulfurizing agent composition. According to some other embodiments of the present invention, the granulated product is heat-treated at 310-370° C. for 2-3.5 hours to prepare a desulfurizing agent composition. According to some other embodiments of the present invention, the granulated product is heat-treated at 320-360° C. for 2.5-3.2 hours to prepare a desulfurizing agent composition.
  • the desulfurizer composition contains: Ca 30.2wt%-38.5wt%, Fe 6.7wt%-10.8wt%, Mg 0.8wt%-2.2wt%, Al 7.2wt%-12.4wt%, Na 3wt% ⁇ 6.2wt%, K 0wt% ⁇ 2.5wt%, Si 5.5wt% ⁇ 10.1wt%, H 1.8wt% ⁇ 3.2wt%, and O 20.6wt% ⁇ 36.5wt%.
  • the desulfurizer composition is prepared by heat-treating the granulated product at 300-380° C. for 1.5-3.5 hours.
  • the desulfurizer composition contains: Ca 30.5wt% to 37.5wt%, Fe 7wt% to 9.8wt%, Mg 0.98wt% to 2.1wt%, Al 8.1wt% to 11.5wt%, Na 3.5wt% ⁇ 5.5wt%, K 0.8wt% ⁇ 2wt%, Si 6.5wt% ⁇ 10wt%, H 2.0wt% ⁇ 3.2wt% and O 22.5wt% ⁇ 33.5wt%.
  • the desulfurizing agent composition is prepared by heat-treating the granulated product at 310-370° C. for 2-3.5 hours.
  • the desulfurizer composition contains: Ca 30.7wt% to 37wt%, Fe 7.1wt% to 9.5wt%, Mg 1.2wt% to 2.1wt%, Al 9.1wt% to 11wt%, Na 3.8wt% ⁇ 5.4wt%, K 1wt% ⁇ 1.8wt%, Si 7.5wt% ⁇ 9.4wt%, H 2.6wt% ⁇ 3.2wt%, and O 22.5wt% ⁇ 32.5wt%.
  • the desulfurizing agent composition is prepared by heat-treating the granulated product at 320-360° C. for 2.5-3.2 hours.
  • the present invention also provides a preparation method of the above-mentioned desulfurizing agent composition, which includes the following steps: raw material mixing, granulation and heat treatment.
  • the method has the advantages of simple process, short time consumption, energy saving and environmental protection, and low production cost, and is suitable for industrialized production. Details are given below.
  • the mixing of raw materials includes a dry mixing step and a wet mixing step.
  • lime powder, iron powder, bentonite, pore-forming agent, cement, lime mud, clay and diatomaceous earth particles are mixed through a dry mixing process to obtain a mixed material A.
  • the dry mixing process can use conventional stirring equipment, such as a mixer and a kneader, preferably a kneader.
  • the dry mixing time may be 5-30 min, preferably 5-20 min, more preferably 5-10 min. Dry mixing helps to mix the powdery materials evenly, which is beneficial to improve the performance of the desulfurizer composition.
  • the state of the mixed material B is preferably pasty.
  • Wet mixing can be carried out in conventional stirring equipment, preferably in a kneader.
  • the wet mixing time may be 10-60 min; preferably 20-50 min; more preferably 25-40 min.
  • the invention obtains the mixed material B suitable for extrusion by controlling the wet mixing time, which is beneficial to improving the desulfurization performance and strength of the desulfurizer composition.
  • Lime powder can be 40-80 parts by weight, iron powder can be 2-25 parts by weight, bentonite can be 0.5-10 parts by weight, pore-forming agent can be 2-20 parts by weight, cement can be 2-20 parts by weight, white Mud, clay and diatomaceous earth can be 0.3-5 parts by weight respectively.
  • the particle size of the lime powder may be 150-350 mesh, preferably 180-300 mesh, more preferably 200-250 mesh.
  • the particle size of other raw materials is ⁇ 200 mesh, preferably 10-200 mesh, more preferably 20-180 mesh.
  • the selection of raw materials in this particle size range is beneficial to uniform mixing of the raw materials and at the same time ensures the strength of the desulfurizer composition.
  • the pore forming agent can be selected from one or more of urea, carbon powder, graphite, carbon black, starch, polyvinyl alcohol, polyethylene glycol, straw, rice husk; preferably urea, carbon powder, One or more of graphite, carbon black, starch, polyvinyl alcohol, and polyethylene glycol; more preferably one or more of urea, carbon powder, graphite, carbon black, and starch.
  • Urea is used as a pore-forming agent, and the pore size distribution of the desulfurization agent composition is relatively uniform, which helps to improve the desulfurization performance of the desulfurization agent composition.
  • the mixed material B is granulated to obtain a granulated product.
  • the granulated product can be produced by a granulator.
  • the granulated product may be in the form of strips, granules or flakes, preferably granules, more preferably cylindrical granules.
  • the diameter of the cylindrical particles may be 2-5 mm, preferably 2-4.5 mm, more preferably 2.5-4 mm.
  • the length of the cylindrical particles may be 8-15 mm, preferably 9-14 mm, more preferably 10-13 mm.
  • the granulated product is heat-treated to obtain a desulfurizing agent composition.
  • the heat treatment temperature may be 300-380°C, preferably 310-370°C, more preferably 320-360°C.
  • the heat treatment temperature is lower than 300°C, the pore size distribution of the desulfurizer composition is poor, and the specific surface area is small, resulting in a breakthrough sulfur capacity of the desulfurizer composition ⁇ 100mg/g, and a saturated sulfur capacity ⁇ 35%; when the heat treatment temperature is high
  • the temperature is 380°C, the energy consumption is large, and the production cost is high, so it is not suitable for industrial production.
  • the heat treatment time may be 1.5-3.5 hours, preferably 2-3.5 hours, more preferably 2.5-3.2 hours.
  • the heat treatment time is less than 1.5h, the pore size distribution of the desulfurizing agent composition is poor, and the specific surface area is small, resulting in the breakthrough sulfur capacity of the desulfurizing agent composition ⁇ 100mg/g, the saturated sulfur capacity ⁇ 35%, and the compressive strength ⁇ 130N/cm, wear resistance ⁇ 90%; when the heat treatment time is longer than 3.5h, it takes a long time, consumes a lot of energy, and the production cost is high, so it is not suitable for industrial production.
  • the heat treatment process can be carried out in an oven.
  • the granulated products are stacked into an oven for heat treatment.
  • the stacked thickness of the granulated product may be 15-40 mm, preferably 20-35 mm, more preferably 25-30 mm. Within this range, energy consumption and production costs can be saved, and the granulated product can be heated evenly to obtain a desulfurizer composition with consistent product quality and high sulfur capacity.
  • the desulfurization and denitrification absorbent in the test conditions shown in Table 1, and use the flue gas analyzer to test the concentration of simulated flue gas pollutant SO2 , where the test end point of the breakthrough sulfur capacity is: the outlet concentration of SO2
  • the test end point of saturated sulfur capacity is: the outlet concentration of SO 2 is 2800mg/ Nm 3 .
  • Test Conditions parameter initial SO 2 2800mg/ Nm3 temperature 140°C Simulated flue gas moisture content 10% Simulated flue gas oxygen content 14% material contact time 7s
  • Sample preparation randomly select 20 samples with smooth surface, regularity and aspect ratio not less than 1;
  • Wear resistance test refer to GB/T 30202.3-2013 "Test method for coal-based granular activated carbon for desulfurization and denitrification" for wear resistance test;
  • Element content test use X-ray fluorescence spectrometer to test.
  • % means percentage by weight and is recorded as wt%.
  • Lime powder, iron powder, bentonite, pore-forming agent (urea), cement, lime mud, clay and diatomaceous earth particles were placed in a kneader, and mixed dry for 6 minutes to obtain a mixed material A; add water to the mixed material A, wet Mix and knead for 30min to obtain the mixed material B;
  • the granulated product was stacked to a thickness of 30 mm, and heat-treated to obtain a desulfurizing agent composition.
  • the element composition and product performance of the desulfurizer composition were measured, and the results are shown in Table 2-3.
  • the element composition of the desulfurizer composition prepared in Examples 1-2 satisfies: Ca 30.2wt%-38.5wt%, Fe 6.7wt%-10.8wt%, Mg 0.8wt%-2.2wt%, Al 7.2wt% % ⁇ 12.4wt%, Na 3wt% ⁇ 6.2wt%, K 0wt% ⁇ 2.5wt%, Si5.5wt% ⁇ 10.1wt%, H 1.8wt% ⁇ 3.2wt%, O 20.6wt% ⁇ 36.5wt%, so
  • the penetrating sulfur capacity of the desulfurizer composition is more than 107 mg/g, the saturated sulfur capacity is more than 38%, the compressive strength is more than 214N/cm, and the wear resistance is more than 98%.
  • the desulfurizer compositions prepared in Comparative Examples 1-2 are not within the above-mentioned element composition range, resulting in a saturated sulfur capacity of the desulfurizer composition ⁇ 30%, a compressive strength of ⁇ 190N/cm, and an abrasion resistance of ⁇ 95%.

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne une composition de désulfurisant et son procédé de préparation. La composition de désulfurant de la présente invention comprend les composants suivants : 30,2 % en poids à 38,5 % en poids de Ca, 6,7 % en poids à 10,8 % en poids de Fe, 0,8 % en poids à 2,2 % en poids de Mg, 7,2 % en poids à 12,4 % en poids d'Al, 3 % en poids à 6,2 % en poids de Na, 0 % en poids à 2,5 % en poids de K, 5,5 % en poids à 10,1 % en poids de Si, 1,8 % en poids à 3,2 % en poids de H, et 20,6 % en poids à 36,5 % en poids de O. La composition de désulfurant de la présente invention présente une capacité de percée élevée en soufre, une grande capacité de saturation en soufre, et une résistance à la compression et une résistance à l'abrasion élevées. Le procédé de préparation de la présente invention est faible en termes de consommation d'énergie et de coût de production, et est approprié pour une application industrielle.
PCT/CN2021/143497 2021-08-27 2021-12-31 Composition de désulfurant et son procédé de préparation WO2023024391A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11221432A (ja) * 1998-02-04 1999-08-17 Nittetsu Mining Co Ltd 石灰石系脱硫剤およびその製造方法
CN101293170A (zh) * 2008-01-12 2008-10-29 中国海洋大学 一种复合材料二氧化硫脱硫剂及其制备方法
CN107812441A (zh) * 2017-12-07 2018-03-20 中晶环境科技股份有限公司 基于赤泥的烟气干法脱硫脱硝方法
CN213286346U (zh) * 2020-09-24 2021-05-28 中晶新材料有限公司 具有移动床反应装置的烟气脱硫系统及胶结料生产系统
CN113663491A (zh) * 2021-08-27 2021-11-19 中晶环境科技股份有限公司 脱硫剂组合物及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047221A (en) * 1986-11-07 1991-09-10 Board Of Regents, The University Of Texas System Processes for removing sulfur from sulfur-containing gases
GB0804572D0 (en) * 2008-03-12 2008-04-16 Johnson Matthey Plc Preparation of desulphurisation materials
CN101643664A (zh) * 2009-06-29 2010-02-10 金堆城钼业股份有限公司 一种重整原料油脱硫剂及其制备方法
CN105771620A (zh) * 2016-05-05 2016-07-20 张锐 一种高效脱硫剂及其制备方法
CN112915744B (zh) * 2019-12-05 2022-04-19 武汉科林化工集团有限公司 一种粉煤灰与烟尘灰制备烟气精脱硫剂的方法
CN111330424B (zh) * 2020-01-20 2020-11-27 北京宝聚能源科技有限公司 一种烟气脱硫剂及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11221432A (ja) * 1998-02-04 1999-08-17 Nittetsu Mining Co Ltd 石灰石系脱硫剤およびその製造方法
CN101293170A (zh) * 2008-01-12 2008-10-29 中国海洋大学 一种复合材料二氧化硫脱硫剂及其制备方法
CN107812441A (zh) * 2017-12-07 2018-03-20 中晶环境科技股份有限公司 基于赤泥的烟气干法脱硫脱硝方法
CN213286346U (zh) * 2020-09-24 2021-05-28 中晶新材料有限公司 具有移动床反应装置的烟气脱硫系统及胶结料生产系统
CN113663491A (zh) * 2021-08-27 2021-11-19 中晶环境科技股份有限公司 脱硫剂组合物及其制备方法

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