WO2023024391A1 - Desulfurizer composition and preparation method therefor - Google Patents

Desulfurizer composition and preparation method therefor Download PDF

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Publication number
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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French (fr)
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/en

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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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Abstract

Disclosed in the present invention are a desulfurizer composition and a preparation method therefor. The desulfurizer composition of the present invention comprises the following components: 30.2wt%-38.5wt% of Ca, 6.7wt%-10.8wt% of Fe, 0.8wt%-2.2wt% of Mg, 7.2wt%-12.4wt% of Al, 3wt%-6.2wt% of Na, 0wt%-2.5wt% of K, 5.5wt%-10.1wt% of Si, 1.8wt%-3.2wt% of H, and 20.6wt%-36.5wt% of O. The desulfurizer composition of the present invention is high in breakthrough sulfur capacity, large in saturation sulfur capacity, and high in compressive strength and abrasion resistance. The preparation method of the present invention is low in energy consumption and production cost, and is suitable for industrial application.

Description

脱硫剂组合物及其制备方法Desulfurizer composition and preparation method thereof 技术领域technical field
本发明涉及一种脱硫剂组合物及其制备方法。The invention relates to a desulfurizing agent composition and a preparation method thereof.
背景技术Background technique
烟气脱硫的方法大致分为三类：湿法，即采用液体吸收剂如水或碱液等洗涤烟气以除去二氧化硫；半干法，利用烟气湿热蒸发石灰浆液中的水分，同时石灰与二氧化硫反应生成干粉状亚硫酸钙，兼具湿法和干法特点；干法，即采用粉状或颗粒吸收剂、吸附剂或催化剂以除去二氧化硫。湿法脱硫工艺成熟，脱硫效率＞95％，但引起二次污染，并且脱除后的烟气中含水严重，容易损坏脱硫装置，导致投资成本大，运行费用高；半干法脱硫工艺的脱硫效率相对较低，且排烟为白雾，影响感官；干法脱硫工艺不存在二次污染、腐蚀、结露等问题，因而，近年来得到了迅速的发展和应用。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.
目前，干法脱硫工艺采用的脱硫剂存在机械强度差，易粉化，脱硫剂需进行500℃～1100℃高温焙烧，生产成本高等问题。At present, 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公开了一种生物质炭基脱硫催化剂的制备方法，包括以下步骤：(1)在惰性气氛保护下，将生物质原料在500～600℃下热处理2～3h，得到炭粉；(2)将由炭粉、粘接剂和分散剂构成的混合物进行造粒，得到第一前体；(3)在惰性气氛保护下，将第一前体在500～700℃下热处理2～6h，得到第二前体；(4)在含有活化气体的气氛中，将第二前体在800～900℃下热处理2～6h，即得到生物质炭基脱硫催化剂。该方法制备过程复杂，能耗及生产成本较高，且制得的生物质炭基脱硫催化剂的抗压强度较低(抗压强度大于等于160N/cm)，在运输和使用过程中，脱硫催化剂容易粉化。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公开了一种高硫容铁系脱硫剂的制备方法，包括如下步骤：(1)将硫酸亚铁溶液与氨水溶液置于超声环境下进行沉淀反应，经离心、微波处理，得到纳米氧化铁；(2)以纳米氧化铁作为主要活性组分，添加抗积炭助剂、硫化促进剂、强度增强剂、粘结剂和造孔剂，将各原料机械混合，然后置于30～80℃下干燥3～6h，再经混合机碾混，加水捏合，制成条状、粒状或片状的成型物；(3)将成型物置于50～80℃下隔夜烘干，然后置于600～900℃焙烧2～6h，得到高硫容铁系脱硫剂；其中，抗积炭助剂为微量的二氧化铈和轻质氧化镁，强度增强剂为SiO 2，硫化促进剂为微量NiO，粘结剂为粘土，造孔剂为淀粉。该脱硫剂的循环稳定性好，但其硫容仍需进一步提高(硫容为10.7～25.1％)。该脱硫剂的制备过程复杂，各步骤耗时较长，并且该方法在600～900℃下进行高温焙烧，能耗及生产成本较高，不适于工业化生产。 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 enhancer is SiO 2 , the vulcanization accelerator is trace amounts of NiO, and the sticky The binder is clay, and the pore-forming agent is starch. 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公开了一种烟气脱硫剂的制备方法，包括如下步骤：(1)采用表面活性剂对氢氧化钙进行处理，干燥、粉化后得到改性氢氧化钙；(2)将改性氢氧化钙、碳酸钙和添加剂混合，搅拌均匀得到混合粉料；(3)将混合粉料与粘结剂混合，搅拌均匀，加入适量水溶液进行充分混捏，得到捏合物固体；(4)将所述捏合物固体进行挤条、成型、干燥，得到烟气脱硫剂。该烟气脱硫剂的强度为90～118N/cm，硫容为31～39％，脱硫剂的强度及硫容均仍有待提高。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.
发明内容Contents of the invention
有鉴于此，本发明的一个目的在于提供一种脱硫剂组合物，其具有较高的强度及硫容。进一步地，其制备过程简单，能耗和成本较低。In view of this, 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.
本发明的另一个目的在于提供一种上述脱硫剂组合物的制备方法，其耗时较短、能耗和生产成本较低。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.
一方面，本发明提供一种脱硫剂组合物，含有：In one aspect, the present invention provides a desulfurizer composition, comprising:
Figure PCTCN2021143497-appb-000001
Figure PCTCN2021143497-appb-000001
根据本发明的脱硫剂组合物，优选地，其包括如下成分：According to the desulfurizing agent composition of the present invention, preferably, it includes the following components:
Figure PCTCN2021143497-appb-000002
Figure PCTCN2021143497-appb-000002
根据本发明的脱硫剂组合物，优选地，其包括如下成分：According to the desulfurizing agent composition of the present invention, preferably, it includes the following components:
Figure PCTCN2021143497-appb-000003
Figure PCTCN2021143497-appb-000003
Figure PCTCN2021143497-appb-000004
Figure PCTCN2021143497-appb-000004
根据本发明的脱硫剂组合物，优选地，其由如下成分以及不可避免的杂质组成：According to the desulfurizing agent composition of the present invention, preferably, it consists of the following components and unavoidable impurities:
Figure PCTCN2021143497-appb-000005
Figure PCTCN2021143497-appb-000005
根据本发明的脱硫剂组合物，优选地，其由如下成分组成：According to the desulfurizing agent composition of the present invention, preferably, it consists of the following components:
Figure PCTCN2021143497-appb-000006
Figure PCTCN2021143497-appb-000006
上述各成分的重量百分比之和为100wt％。The sum of the weight percentages of the above-mentioned components is 100wt%.
根据本发明的脱硫剂组合物，优选地，所述脱硫剂组合物为圆柱体，其直径为2～5mm，其长度为8～15mm。According to the desulfurizing agent composition of the present invention, preferably, the desulfurizing agent composition is a cylinder with a diameter of 2-5 mm and a length of 8-15 mm.
根据本发明的脱硫剂组合物，优选地，所述脱硫剂组合物的穿透硫容≥80mg/g，饱和硫容≥35％，耐压强度≥150N/cm，耐磨强度≥98％。According to the desulfurizing agent composition of the present invention, preferably, the desulfurizing agent composition has a breakthrough sulfur capacity ≥ 80 mg/g, a saturated sulfur capacity ≥ 35%, a compressive strength ≥ 150 N/cm, and an abrasion resistance ≥ 98%.
根据本发明的脱硫剂组合物，优选地，所述脱硫剂组合物通过将造粒产物在300～380℃下热处理1.5～3.5h得到。According to the desulfurizing agent composition of the present invention, preferably, the desulfurizing agent composition is obtained by heat-treating the granulated product at 300-380° C. for 1.5-3.5 hours.
另一方面，本发明提供一种上述脱硫剂组合物的制备方法，将石灰粉、铁粉、膨润土、造孔剂、水泥、白泥、白土和硅藻土颗粒混合；然后加水进行湿混，形成混合物料；将混合物料造粒，然后将造粒产物在300～380℃下热处理1.5～3.5h，得到脱硫剂组合物。In another aspect, 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.
根据本发明的制备方法，优选地，所述造孔剂选自尿素、碳粉、石墨、炭黑、淀粉、聚乙烯醇、聚乙二醇、秸秆、稻壳中的一种或多种；湿混的时间为10～60min；热处理时造粒产物的堆叠厚度为15～40mm。According to the preparation method of the present invention, preferably, 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.
本发明的脱硫剂组合物的穿透硫容≥80mg/g，饱和硫容≥35％，耐压强度≥150N/cm，耐磨强度≥98％。本发明的制备方法简单耗时较短，能耗和生产成本较低，适于工业化应用。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.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步的说明，但本发明的保护范围并不限于此。The present invention will be further described below in combination with specific embodiments, but the protection scope of the present invention is not limited thereto.
本发明中，饱和硫容表示单位质量脱硫剂所能吸收硫的最大质量。饱和硫容是衡量脱硫剂的一个重要指标，通常用百分比表示。穿 透硫容表示单位质量脱硫剂在确保工艺净化度指标时所能吸收硫的质量。单位通常为mg/g。耐压强度表示材料单位面积上所能承受的极限载荷。耐磨强度用于反应脱硫剂的抵抗机械磨损的能力。耐磨强度数值越高，脱硫剂的抗机械磨损的能力越强，不易粉化。In the present invention, 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.
本发明中，脱硫剂组合物可以为条状、粒状或片状，优选为粒状，更优选为圆柱体颗粒。In the present invention, 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.
本发明中，白泥是一种非金属矿产，是一种以高岭石族粘土矿物为主的粘土和粘土岩，因呈白色而又细腻，又称白云土。In the present invention, 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.
本发明中，白土是指活性白土，是一种天然产出的、细粒的、高吸附率的土状物质，也称漂白土。In the present invention, white clay refers to active white clay, which is a naturally produced, fine-grained, high-adsorption soil-like substance, also known as bleaching earth.
<脱硫剂组合物><Desulfurizer Composition>
本发明意外地发现，将脱硫剂的元素配比控制在特定范围内，可使脱硫剂组合物具有较高的穿透硫容、饱和硫容、耐压强度和耐磨强度；并且，该脱硫剂组合物可经低温热处理制得。因此，本发明提供一种脱硫剂组合物，该脱硫剂组合物经低温热处理制得，具有特定的元素组成和良好的性能参数。下面进行详细介绍。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.
本发明的脱硫剂组合物，含有如下元素：Ca、Fe、Mg、Al、Na、K、Si、H和O。当然，还可以含有不可避免的杂质。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.
本发明的脱硫剂组合物中，Ca的含量可以为30.2wt％～38.5wt％，优选为30.5wt％～37.5wt％，更优选为30.7wt％～37wt％。当Ca含量小于30.2wt％时，脱硫剂组合物的耐磨强度<93％；当Ca含量大于38.5wt％时，脱硫剂组合物的穿透硫容<80mg/g，饱和硫容<25％。In the desulfurizer composition of the present invention, the content of Ca may be 30.2wt%-38.5wt%, preferably 30.5wt%-37.5wt%, more preferably 30.7wt%-37wt%. When the Ca content is less than 30.2wt%, 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%. .
本发明的脱硫剂组合物中，Fe的含量可以为6.7wt％～10.8wt％，优选为7wt％～9.8wt％，更优选为7.1wt％～9.5wt％。当Fe含量小于6.7wt％时，脱硫剂组合物的硫容较低，脱硫效果不佳；当Fe含量大 于10.8wt％时，脱硫剂组合物的耐压强度较差。In the desulfurizer composition of the present invention, the content of Fe may be 6.7wt%-10.8wt%, preferably 7wt%-9.8wt%, more preferably 7.1wt%-9.5wt%. When 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.
本发明的脱硫剂组合物中，Mg的含量可以为0.8wt％～2.2wt％，优选为0.98wt％～2.1wt％，更优选为1.2wt％～2.1wt％。当Mg含量小于0.8wt％时，脱硫剂组合物的硫容较低，穿透硫容<76mg/g，饱和硫容<25％；当Mg含量大于2.2wt％时，脱硫剂组合物的饱和硫容<30％。In the desulfurizing agent composition of the present invention, the content of Mg may be 0.8wt%-2.2wt%, preferably 0.98wt%-2.1wt%, more preferably 1.2wt%-2.1wt%. When the Mg content is less than 0.8wt%, 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%.
本发明的脱硫剂组合物中，Al的含量可以为7.2wt％～12.4wt％，优选为8.1wt％～11.5wt％，更优选为9.1wt％～11wt％。当Al含量小于7.2wt％时，脱硫剂组合物的硫容较低，穿透硫容<80mg/g，饱和硫容<30％；当Al含量大于12.4wt％时，脱硫剂组合物的耐磨强度欠佳，仅为92％。In the desulfurizing agent composition of the present invention, the content of Al may be 7.2wt%-12.4wt%, preferably 8.1wt%-11.5wt%, more preferably 9.1wt%-11wt%. When the Al content is less than 7.2wt%, 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%.
本发明的脱硫剂组合物中，Na的含量可以为3wt％～6.2wt％，优选为3.5wt％～5.5wt％，更优选为3.8wt％～5.4wt％。In the desulfurizing agent composition of the present invention, the content of Na may be 3wt%-6.2wt%, preferably 3.5wt%-5.5wt%, more preferably 3.8wt%-5.4wt%.
本发明的脱硫剂组合物中，K的含量可以为0wt％～2.5wt％，优选为0.8wt％～2wt％，更优选为1wt％～1.8wt％。In the desulfurizing agent composition of the present invention, the content of K may be 0wt%-2.5wt%, preferably 0.8wt%-2wt%, more preferably 1wt%-1.8wt%.
本发明的脱硫剂组合物中，Si的含量可以为5.5wt％～10.1wt％，优选为6.5wt％～10wt％，更优选为7.5wt％～9.4wt％。当Si含量小于5.5wt％时，脱硫剂组合物的穿透硫容<80mg/g，饱和硫容<25％，耐磨强度<96％；当Si含量大于10.1wt％时，脱硫剂组合物的饱和硫容<30％，耐磨强度<93％。In the desulfurizing agent composition of the present invention, the content of Si may be 5.5wt%-10.1wt%, preferably 6.5wt%-10wt%, more preferably 7.5wt%-9.4wt%. When the Si content is less than 5.5wt%, the breakthrough sulfur capacity of the desulfurizer composition is less than 80mg/g, the saturated sulfur capacity is less than 25%, and the wear resistance is less than 96%; when the Si content is greater than 10.1wt%, the desulfurizer composition The saturated sulfur capacity is <30%, and the wear resistance is <93%.
本发明的脱硫剂组合物中，H的含量可以为1.8wt％～3.2wt％，优选为2.0wt％～3.2wt％，更优选为2.6wt％～3.2wt％。In the desulfurizing agent composition of the present invention, the content of H may be 1.8wt%-3.2wt%, preferably 2.0wt%-3.2wt%, more preferably 2.6wt%-3.2wt%.
本发明的脱硫剂组合物中，O的含量可以为20.6wt％～36.5wt％，优选为22.5wt％～33.5wt％，更优选为22.5wt％～32.5wt％。In the desulfurizing agent composition of the present invention, the content of O may be 20.6wt%-36.5wt%, preferably 22.5wt%-33.5wt%, more preferably 22.5wt%-32.5wt%.
根据本发明的一些实施方式，脱硫剂组合物含有：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％和O 20.6wt％～36.5wt％。According to some embodiments of the present invention, 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%.
根据本发明的另一些实施方式，脱硫剂组合物含有：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％和O 22.5wt％～33.5wt％。According to other embodiments of the present invention, 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%.
根据本发明的再一些实施方式，脱硫剂组合物含有：Ca 30.7wt％～37wt％，Fe 7.1wt％～9.5wt％，Mg 1.2wt％～2.1wt％，Al 9.1wt％～11wt％，Na 3.8wt％～5.4wt％，K 1wt％～1.8wt％，Si 7.5wt％～9.4wt％，H 2.6wt％～3.2wt％和O 22.5wt％～32.5wt％。According to some other embodiments of the present invention, 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%.
在某些实施方式中，脱硫剂组合物由以下成分以及不可避免的杂质(例如碳)组成：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％和O 20.6wt％～36.5wt％。In some embodiments, 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%.
在某些实施方式中，脱硫剂组合物由如下成分组成：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％和O 20.6wt％～36.5wt％；上述各成分的重量百分比之和为100wt％。In some embodiments, 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%.
在一些实施方式中，该脱硫剂组合物含有：Ca 30.2wt％～36wt％，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％～8.5wt％，H 1.8wt％～3.2wt％和O 20.6wt％～36.5wt％。In some embodiments, 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%.
在另一些实施方式中，该脱硫剂组合物含有：Ca 31wt％～38.5wt％，Fe 6.7wt％～10.8wt％，Mg 0.8wt％～2.2wt％，Al 7.2wt％～12.4wt％，Na 3wt％～6.2wt％，K 0.5wt％～2.5wt％，Si 6.5wt％～ 10.1wt％，H 2.6wt％～3.2wt％和O 20.6wt％～26.8wt％。In other embodiments, 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%.
本发明的脱硫剂组合物可以为条状、粒状或片状，优选为粒状，更优选为圆柱体颗粒。圆柱体颗粒的直径可以为2～5mm，优选为2～4.5mm，更优选为2.5～4mm。圆柱体颗粒的长度可以为8～15mm，优选为9～14mm，更优选为10～13mm。该形貌、尺寸的脱硫剂组合物在使用过程中，不仅能够提供更高的硫容，而且便于更换和储存。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.
本发明的脱硫剂组合物具有较高的穿透硫容、饱和硫容、耐压强度和耐磨强度，具有脱硫效果好、机械强度高、不易粉化等优点。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.
本发明中，脱硫剂组合物的穿透硫容≥80mg/g，优选为≥90mg/g，更优选为≥100mg/g。脱硫剂组合物的饱和硫容≥35％，优选为≥40％，更优选为≥45％。脱硫剂组合物的耐压强度≥150N/cm，优选为≥210N/cm，更优选为≥250N/cm。脱硫剂组合物的耐磨强度≥96％，优选为≥98％。In the present invention, 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%.
在某些实施方式中，脱硫剂组合物的穿透硫容≥80mg/g，饱和硫容≥35％，耐压强度≥150N/cm，耐磨强度≥96％。在一些实施方式中，脱硫剂组合物的穿透硫容≥90mg/g，饱和硫容≥40％，耐压强度≥210N/cm，耐磨强度≥98％。在另一些实施方式中，脱硫剂组合物的穿透硫容≥100mg/g，饱和硫容≥45％，耐压强度≥250N/cm，耐磨强度≥98％。In some embodiments, 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%.
本发明的脱硫剂组合物通过将造粒产物在低温条件下热处理得到。热处理温度可以为300～380℃，优选为310～370℃，更优选为320～360℃。该温度既能保证脱硫剂组合物具有较高的硫容和强度，又不会产生过多的能耗。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.
本发明中，热处理时间可以为1.5～3.5h，优选为2～3.5h，更优选为2.5～3.2h。该热处理时间既能保证脱硫剂组合物具有较高的硫容和强度，又有助于提高生产效率，降低生产成本。In the present invention, 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.
根据本发明的一些实施方式，将造粒产物在300～380℃下热处理1.5～3.5h，制备脱硫剂组合物。根据本发明的又一些实施方式，将造粒产物在310～370℃下热处理2～3.5h，制备脱硫剂组合物。根据本发明的再一些实施方式，将造粒产物在320～360℃下热处理2.5～3.2h，制备脱硫剂组合物。According to some embodiments of the present invention, 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.
根据本发明的一些实施方式，脱硫剂组合物含有：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％和O 20.6wt％～36.5wt％。该脱硫剂组合物是将造粒产物在300～380℃下热处理1.5～3.5h制得。According to some embodiments of the present invention, 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.
根据本发明的又一些实施方式，脱硫剂组合物含有：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％和O 22.5wt％～33.5wt％。该脱硫剂组合物是将造粒产物在310～370℃下热处理2～3.5h制得。According to some other embodiments of the present invention, 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.
根据本发明的再一些实施方式，脱硫剂组合物含有：Ca 30.7wt％～37wt％，Fe 7.1wt％～9.5wt％，Mg 1.2wt％～2.1wt％，Al 9.1wt％～11wt％，Na 3.8wt％～5.4wt％，K 1wt％～1.8wt％，Si 7.5wt％～9.4wt％，H 2.6wt％～3.2wt％和O 22.5wt％～32.5wt％。该脱硫剂组合物是将造粒产物在320～360℃下热处理2.5～3.2h制得。According to some other embodiments of the present invention, 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.
<脱硫剂组合物的制备＞<Preparation of desulfurizing agent composition>
本发明还提供上述脱硫剂组合物的制备方法，包括如下步骤：原料混合、造粒和热处理。该方法的工艺简单、耗时较短、节能环保、且生产成本较低，适于工业化生产。下面进行详细介绍。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.
原料混合raw material mixing
本发明中，原料混合包括干混步骤和湿混步骤。In the present invention, the mixing of raw materials includes a dry mixing step and a wet mixing step.
首先，通过干混工艺将石灰粉、铁粉、膨润土、造孔剂、水泥、白泥、白土和硅藻土颗粒混合，得到混合物料A。干混工艺可以采用常规的搅拌设备，例如搅拌机和混捏机，优选为混捏机。干混时间可以为5～30min，优选为5～20min，更优选为5～10min。干混有助于将各粉状物料混合均匀，利于提高脱硫剂组合物的各项性能。Firstly, 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.
向混合物料A中加入水，进行湿混，得到混合物料B。混合物料B的状态优选为糊状。湿混可以在常规的搅拌设备中进行，优选为在混捏机中进行。湿混时间可以为10～60min；优选为20～50min；更优选为25～40min。本发明通过控制湿混时间，得到适合挤出状态的混合物料B，有利于改善脱硫剂组合物的脱硫性能和强度。Add water to the mixed material A, and perform wet mixing to obtain the mixed material B. 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.
石灰粉可以为40～80重量份，铁粉可以为2～25重量份，膨润土可以为0.5～10重量份，造孔剂可以为2～20重量份，水泥可以为2～20重量份，白泥、白土和硅藻土可以分别为0.3～5重量份。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.
本发明中，石灰粉的粒度可以为150～350目，优选为180～300目，更优选为200～250目。其他原料的粒度≤200目，优选为10～200目，更优选为20～180目。选用该粒度范围的原料，有利于将各原料混合均匀，同时保证脱硫剂组合物的强度。In the present invention, 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.
本发明中，造孔剂可以选自尿素、碳粉、石墨、炭黑、淀粉、聚乙烯醇、聚乙二醇、秸秆、稻壳中的一种或多种；优选为尿素、碳粉、石墨、炭黑、淀粉、聚乙烯醇、聚乙二醇中的一种或多种；更优选为尿素、碳粉、石墨、炭黑、淀粉中的一种或多种。将尿素作为造孔剂，脱硫剂组合物的孔径分布较为均匀，有助于提高脱硫剂组合物的脱硫性能。In the present invention, 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.
造粒granulation
将混合物料B进行造粒，得到造粒产物。造粒产物可以通过造粒机制得。造粒产物可以为条状、粒状或片状，优选为粒状，更优选为圆柱体颗粒。圆柱体颗粒的直径可以为2～5mm，优选为2～4.5mm，更优选为2.5～4mm。圆柱体颗粒的长度可以为8～15mm，优选为9～14mm，更优选为10～13mm。当造粒产物为圆柱体颗粒时，制备的脱硫剂组合物具有较高的硫容，且便于更换和储存。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. When the granulated product is cylindrical granules, the prepared desulfurizer composition has a high sulfur capacity and is easy to replace and store.
热处理heat treatment
将造粒产物进行热处理，得到脱硫剂组合物。The granulated product is heat-treated to obtain a desulfurizing agent composition.
本发明中，热处理温度可以为300～380℃，优选为310～370℃，更优选为320～360℃。当热处理温度低于300℃时，脱硫剂组合物的孔径分布较差，比表面积较小，导致脱硫剂组合物的穿透硫容<100mg/g，饱和硫容<35％；当热处理温度高于380℃时，能耗较大，且生产成本较高，不适于工业化生产。In the present invention, the heat treatment temperature may be 300-380°C, preferably 310-370°C, more preferably 320-360°C. When 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 When the temperature is 380°C, the energy consumption is large, and the production cost is high, so it is not suitable for industrial production.
本发明中，热处理时间可以为1.5～3.5h，优选为2～3.5h，更优选为2.5～3.2h。当热处理时间少于1.5h时，脱硫剂组合物的孔径分布较差，比表面积较小，导致脱硫剂组合物的穿透硫容<100mg/g，饱和硫容<35％，且耐压强度<130N/cm，耐磨强度<90％；当热处理时间多于3.5h时，耗时较长，能耗较大，生产成本较高，不适于工业化生产。In the present invention, the heat treatment time may be 1.5-3.5 hours, preferably 2-3.5 hours, more preferably 2.5-3.2 hours. When 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.
本发明中，热处理过程可以在烘箱中进行。热处理时，将造粒产物堆叠至烘箱内进行热处理。造粒产物的堆叠厚度可以为15～40mm，优选为20～35mm，更优选为25～30mm。在此范围内，既可以节省能耗和生产成本，又可以保证造粒产物受热均匀，得到产品质量一致的、高硫容的脱硫剂组合物。In the present invention, the heat treatment process can be carried out in an oven. During heat treatment, 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.
下面介绍测试方法：The test method is described below:
(1)硫容测试：(1) Sulfur capacity test:
将脱硫脱硝吸收剂置于表1所示的测试条件中，利用烟气分析仪对模拟烟气污染物SO 2的浓度进行测试，其中，穿透硫容的测试终点为：SO 2的出口浓度为35mg/Nm 3；饱和硫容的测试终点为：SO 2的出口浓度为2800mg/Nm 3。 Put 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 .
表1Table 1
测试条件Test Conditions 参数parameter
初始SO 2 initial SO 2 2800mg/Nm 3 2800mg/ Nm3
温度temperature 140℃140°C
模拟烟气含水量Simulated flue gas moisture content 10％10%
模拟烟气含氧量Simulated flue gas oxygen content 14％14%
物料接触时间material contact time 7s7s
(2)耐压强度测试：采用GB/T 30202.3-2013《脱硫脱硝用煤质颗粒活性炭试验方法》进行测试，具体测试方法如下：(2) Compressive strength test: GB/T 30202.3-2013 "Test method for coal-based granular activated carbon for desulfurization and denitrification" is used for testing. The specific test method is as follows:
1)样品准备：随机抽取表面光滑，规则和长径比不小于1的20粒试料；1) Sample preparation: randomly select 20 samples with smooth surface, regularity and aspect ratio not less than 1;
2)仪器预备：调节耐压强度仪的零点；2) Instrument preparation: adjust the zero point of the compressive strength tester;
3)样品测试：将各试料沿圆柱轴向方向放置于下夹具V型槽内，开启耐压强度测定仪，记录试样压碎瞬间的压力值，压力值大于50daN(力学单位，1daN＝10N)时以50daN计；3) Sample test: Place each sample in the V-shaped groove of the lower fixture along the axial direction of the cylinder, turn on the compressive strength tester, and record the pressure value at the moment the sample is crushed. The pressure value is greater than 50daN (mechanical unit, 1daN= 10N) is calculated as 50daN;
4)强度计算：20次测定平均值即为所求强度。4) Calculation of strength: The average value of 20 measurements is the desired strength.
(3)耐磨强度测试：参照GB/T 30202.3-2013《脱硫脱硝用煤质颗粒活性炭试验方法》进行耐磨强度测试；(3) 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;
(4)元素含量测试：采用X射线荧光光谱仪进行测试。(4) Element content test: use X-ray fluorescence spectrometer to test.
除非特别声明，％表示重量百分比，记为wt％。Unless otherwise stated, % means percentage by weight and is recorded as wt%.
实施例1～2和对比例1～6Embodiment 1～2 and comparative example 1～6
将石灰粉、铁粉、膨润土、造孔剂(尿素)、水泥、白泥、白土和硅藻土颗粒置于混捏机中，干混6min，得到混合物料A；向混合物料A中加水，湿混捏合30min，得到混合物料B；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;
将混合物料B输送至造粒机中进行造粒，制成直径为3mm，长度为10mm的圆柱形造粒产物；Transport the mixed material B to a granulator for granulation to make a cylindrical granulated product with a diameter of 3mm and a length of 10mm;
将造粒产物堆叠至厚度为30mm，热处理得到脱硫剂组合物。测定脱硫剂组合物的元素组成及产品性能，结果如表2-3所示。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.
表2Table 2
Figure PCTCN2021143497-appb-000007
Figure PCTCN2021143497-appb-000007
表3table 3
序号serial number 穿透硫容(mg/g)Breakthrough sulfur capacity (mg/g) 饱和硫容(％)Saturated sulfur capacity (%) 耐压强度(N/cm)Compressive strength (N/cm) 耐磨强度(％)Abrasion Strength (%)
实施例1Example 1 107107 3838 214214 9898
实施例2Example 2 118118 4848 255255 9898
比较例1Comparative example 1 7575 24twenty four 152152 9595
比较例2Comparative example 2 8181 2727 187187 9292
比较例3Comparative example 3 9797 3434 244244 9696
比较例4Comparative example 4 106106 3838 215215 9898
比较例5Comparative Example 5 9696 3333 128128 8989
比较例6Comparative example 6 110110 4343 216216 9898
由表可知，实施例1～2制备的脱硫剂组合物的元素组成满足：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％，因而脱硫剂组合物的穿透硫容≥107mg/g，饱和硫容≥38％，耐压强度≥214N/cm，耐磨强度≥98％。对比例1～2制备的脱硫剂组合物不在上述元素组成范围内，导致脱硫剂组合物的饱和硫容<30％，耐压强度<190N/cm，耐磨强度<95％。It can be seen from the table that 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%.
对比例3和对比例5，由于制备过程中的热处理温度过低或热处理时间过短，制备的脱硫剂组合物的饱和硫容<35％，耐磨强度<97％。对比例4和对比例6制备的脱硫剂组合物虽然硫容和强度性能较好，但制备过程中的热处理温度较高、热处理时间较长，能耗较大，生产成本较高，不利于工业化生产。In Comparative Example 3 and Comparative Example 5, due to the low heat treatment temperature or short heat treatment time during the preparation process, the saturated sulfur capacity of the prepared desulfurizer composition was <35%, and the wear resistance was <97%. Although the desulfurizer compositions prepared in Comparative Example 4 and Comparative Example 6 have good sulfur capacity and strength properties, the heat treatment temperature in the preparation process is high, the heat treatment time is long, the energy consumption is large, and the production cost is high, which is not conducive to industrialization Production.
本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。The present invention is not limited to the above-mentioned embodiments. Without departing from the essence of the present invention, any deformation, improvement, and replacement conceivable by those skilled in the art fall within the scope of the present invention.

Claims (10)

  1. 一种脱硫剂组合物，其特征在于，其包括如下成分：A desulfurizer composition, characterized in that it comprises the following components:
    Figure PCTCN2021143497-appb-100001
    Figure PCTCN2021143497-appb-100001
  2. 根据权利要求1所述的脱硫剂组合物，其特征在于，其包括如下成分：The desulfurizing agent composition according to claim 1, characterized in that it comprises the following components:
    Figure PCTCN2021143497-appb-100002
    Figure PCTCN2021143497-appb-100002
  3. 根据权利要求1所述的脱硫剂组合物，其特征在于，其包括如下成分：The desulfurizing agent composition according to claim 1, characterized in that it comprises the following components:
    Figure PCTCN2021143497-appb-100003
    Figure PCTCN2021143497-appb-100003
    Figure PCTCN2021143497-appb-100004
    Figure PCTCN2021143497-appb-100004
  4. 根据权利要求1所述的脱硫剂组合物，其特征在于，其由如下成分以及不可避免的杂质组成：The desulfurizer composition according to claim 1, characterized in that it consists of the following components and unavoidable impurities:
    Figure PCTCN2021143497-appb-100005
    Figure PCTCN2021143497-appb-100005
  5. 根据权利要求1所述的脱硫剂组合物，其特征在于，其由如下成分组成：The desulfurizing agent composition according to claim 1, characterized in that it consists of the following components:
    Figure PCTCN2021143497-appb-100006
    Figure PCTCN2021143497-appb-100006
    Figure PCTCN2021143497-appb-100007
    Figure PCTCN2021143497-appb-100007
    上述各成分的重量百分比之和为100wt％。The sum of the weight percentages of the above-mentioned components is 100wt%.
  6. 根据权利要求1所述的脱硫剂组合物，其特征在于，所述脱硫剂组合物为圆柱体，其直径为2～5mm，其长度为8～15mm。The desulfurizing agent composition according to claim 1, wherein the desulfurizing agent composition is a cylinder with a diameter of 2-5 mm and a length of 8-15 mm.
  7. 根据权利要求1～6任一项所述的脱硫剂组合物，其特征在于，所述脱硫剂组合物的穿透硫容≥80mg/g，饱和硫容≥35％，耐压强度≥150N/cm，耐磨强度≥98％。The desulfurizing agent composition according to any one of claims 1 to 6, characterized in that, the desulfurizing agent composition has a breakthrough sulfur capacity ≥ 80 mg/g, a saturated sulfur capacity ≥ 35%, and a compressive strength ≥ 150 N/g cm, wear resistance ≥ 98%.
  8. 根据权利要求1～6任一项所述的脱硫剂组合物，其特征在于，所述脱硫剂组合物通过将造粒产物在300～380℃下热处理1.5～3.5h得到。The desulfurizing agent composition according to any one of claims 1-6, characterized in that the desulfurizing agent composition is obtained by heat-treating the granulated product at 300-380° C. for 1.5-3.5 hours.
  9. 根据权利要求1～8任一项所述的脱硫剂组合物的制备方法，其特征在于，将石灰粉、铁粉、膨润土、造孔剂、水泥、白泥、白土和硅藻土颗粒混合；然后加水进行湿混，形成混合物料；将混合物料造粒，然后将造粒产物在300～380℃下热处理1.5～3.5h，得到脱硫剂组合物。The preparation method of the desulfurizing agent composition according to any one of claims 1-8, characterized in that lime powder, iron powder, bentonite, pore-forming agent, cement, white mud, clay and diatomaceous earth particles are mixed; Water is then added for wet mixing to form a mixed material; the mixed material is granulated, and then the granulated product is heat-treated at 300-380° C. for 1.5-3.5 hours to obtain a desulfurizing agent composition.
  10. 根据权利要求9所述的脱硫剂组合物的制备方法，其特征在于，所述造孔剂选自尿素、碳粉、石墨、炭黑、淀粉、聚乙烯醇、聚乙二醇、秸秆、稻壳中的一种或多种；湿混的时间为10～60min；热处理时造粒产物的堆叠厚度为15～40mm。The preparation method of the desulfurizing agent composition according to claim 9, characterized in that, the pore-forming agent is selected from urea, carbon powder, graphite, carbon black, starch, polyvinyl alcohol, polyethylene glycol, straw, rice One or more of the shells; the wet mixing time is 10-60 minutes; the stacking thickness of the granulated product during heat treatment is 15-40mm.
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