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CN-122006460-A - Energy-saving composite desulfurizing agent and production process thereof

CN122006460ACN 122006460 ACN122006460 ACN 122006460ACN-122006460-A

Abstract

The invention provides an energy-saving composite desulfurizing agent and a production process thereof, which belong to the technical field of gas purification and comprise the following steps of S1 preparing slurry for spray drying by adopting deionized water, CTAB (thermal energy coefficient of performance), PMMA (polymethyl methacrylate) microsphere emulsion, tannic acid, first ferric nitrate nonahydrate, zinc salt, second ferric nitrate nonahydrate, cerium salt, zirconium salt, manganese salt and pseudo-boehmite, S2 preparing intermediate by spray drying and roasting, and S3 preparing the intermediate by adopting LiCl/KCl mixed salt solution for soaking and mixing, drying and roasting to obtain the energy-saving composite desulfurizing agent. The invention can realize the purposes of high-efficiency desulfurization and energy consumption reduction of the energy-saving composite desulfurizing agent.

Inventors

  • GUO XIAOCHEN
  • HE YUQING
  • GUO RUOBING
  • YANG ZHIXIANG

Assignees

  • 山西炬华新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260415

Claims (10)

  1. 1. The production process of the energy-saving composite desulfurizing agent is characterized by comprising the following steps of: s1, adding CTAB into deionized water, stirring and dissolving, adding PMMA nano microsphere emulsion, continuously stirring, adding tannic acid and first ferric nitrate nonahydrate, stirring and dissolving, then adding zinc salt, second ferric nitrate nonahydrate, cerium salt, zirconium salt and manganese salt, stirring and dissolving; step S2, spray drying is carried out by adopting slurry for spray drying to obtain precursor microsphere powder, and roasting is carried out in air atmosphere to obtain an intermediate; and S3, soaking and mixing the intermediate by adopting LiCl/KCl mixed salt solution, drying and roasting to obtain the energy-saving composite desulfurizing agent.
  2. 2. The production process of the energy-saving composite desulfurizing agent according to claim 1, wherein the solid content of the PMMA nano microsphere emulsion is 10-30wt%, and the average particle size of the PMMA nano microsphere is 50-500nm.
  3. 3. The process for producing the energy-saving composite desulfurizing agent according to claim 1, wherein the zinc salt is zinc nitrate hexahydrate, the cerium salt is cerium nitrate hexahydrate, the zirconium salt is zirconium oxynitrate, the manganese salt is manganese nitrate tetrahydrate, and the pseudo-boehmite is added in batches for 2-6 times.
  4. 4. The production process of the energy-saving composite desulfurizing agent according to claim 1, wherein the spray drying slurry comprises, by weight, 2500 parts of deionized water, 5-25 parts of CTAB (cta), 110-135 parts of PMMA (polymethyl methacrylate) nanoparticle emulsion, 1-3 parts of tannic acid, 0.8-1.8 parts of first ferric nitrate nonahydrate, 297-298 parts of zinc nitrate hexahydrate, 99-100 parts of second ferric nitrate nonahydrate, 10-11 parts of cerium nitrate hexahydrate, 6.6-6.7 parts of zirconium oxynitrate, 3.1-3.2 parts of manganese nitrate tetrahydrate and 100 parts of pseudo-boehmite.
  5. 5. The process for producing the energy-saving composite desulfurizing agent according to claim 1, wherein in the step S1, the concentration of ammonia water is 20-30wt%, the aging time is 60-180min, and the washing is carried out for 2-5 times by adopting deionized water at 40-80 ℃.
  6. 6. The process for producing an energy-saving composite desulfurizing agent according to claim 1, wherein in the step S2, centrifugal atomization is adopted for spray drying, the rotation speed of an atomizing disc is 10000-14000rpm, the temperature of air inlet is 200-240 ℃, the temperature of air outlet is 100-120 ℃, and the feeding rate is 20-40mL/min.
  7. 7. The process for producing an energy-saving composite desulfurizing agent according to claim 1, wherein in the step S2, the temperature rising rate of the calcination is 1-5 ℃ per minute, and the temperature is 300-400 ℃.
  8. 8. The process for producing an energy-saving composite desulfurizing agent according to claim 1, wherein in the step S3, the mass ratio of LiCl/KCl is (0.5-1.2): 1, and the mass fraction of mixed salt in the mixed salt solution is 10-30wt%.
  9. 9. The process for producing an energy-saving composite desulfurizing agent according to claim 1, wherein in the step S3, the drying temperature is 90-130 ℃, the time is 3-8 hours, the temperature rising rate of roasting is 1-5 ℃ per minute, and the temperature is 450-550 ℃.
  10. 10. An energy-saving composite desulfurizing agent, which is characterized by being prepared by adopting the production process of the energy-saving composite desulfurizing agent as claimed in any one of claims 1 to 9.

Description

Energy-saving composite desulfurizing agent and production process thereof Technical Field The invention relates to the technical field of gas purification, in particular to an energy-saving composite desulfurizing agent and a production process thereof. Background The existing flue gas or industrial tail gas desulfurization mainly comprises wet method (such as limestone-gypsum method), semi-dry method (spray drying absorption), dry spraying (sodium bicarbonate, slaked lime and the like) and solid adsorption/catalytic oxidation (active coke, active carbon, metal oxide bed layer and the like) routes. The technology has the common pressure of energy consumption, consumable material or by-product treatment in industrial application, that is, a wet method system needs to be provided with a circulating slurry, flue gas reheating or corrosion prevention system, the water consumption and the pump/fan power consumption are higher, the utilization rate of a dry/semi-dry base absorbent is limited, the dust load is large, the reaction temperature is often required to be increased or the addition amount is increased to meet the ultra-low emission requirement, the metal oxide bed layer sulfur remover has the advantages that the reaction rate is high, the multi-metal active component is difficult to be uniformly dispersed on a carrier, the sintering and the inactivation are easy in the roasting or running process, meanwhile, the internal diffusion resistance of the traditional granulating/extruding particles is large, the utilization rate of active sites is reduced, and the pressure drop is increased. The defects in the prior art are mainly characterized in that (1) the removal efficiency of SO 2 in a low-temperature area (such as a downstream temperature area of a dust remover/a denitration device) is insufficient, the flue gas is often heated to maintain the reaction rate to cause additional energy consumption, (2) the adaptability of a single active component to complex flue gas components (O 2、H2O、NOx, dust and the like) is poor, the problems of sulfate crystallization pore blocking, surface acidosis, mechanical strength reduction and the like are easy to occur, (3) the metal salt and carrier particles are easy to generate local enrichment in the preparation process of a multi-metal synergistic system to cause insufficient accessible active sites and increased material consumption, (4) part of high-activity material preparation depends on high-temperature solid phase reaction or multiple high-temperature roasting, and the production energy consumption is high and the amplification stability is poor. Therefore, it is desirable to provide an energy-saving composite desulfurizing agent and a production process thereof, so as to solve the problems in the prior art. Disclosure of Invention In view of the above, the invention provides an energy-saving composite desulfurizing agent and a production process thereof, which can realize the purposes of high-efficiency desulfurization and energy consumption reduction of the energy-saving composite desulfurizing agent. In order to achieve the above purpose, the invention provides a production process of an energy-saving composite desulfurizing agent, which comprises the following steps: s1, adding CTAB into deionized water, stirring and dissolving, adding PMMA nano microsphere emulsion, continuously stirring, adding tannic acid and first ferric nitrate nonahydrate, stirring and dissolving, then adding zinc salt, second ferric nitrate nonahydrate, cerium salt, zirconium salt and manganese salt, stirring and dissolving; step S2, spray drying is carried out by adopting slurry for spray drying to obtain precursor microsphere powder, and roasting is carried out in air atmosphere to obtain an intermediate; and S3, soaking and mixing the intermediate by adopting LiCl/KCl mixed salt solution, drying and roasting to obtain the energy-saving composite desulfurizing agent. The tannic acid and Fe 3+ in the first ferric nitrate nonahydrate form a polyphenol-metal coordination network preferentially, a coordination layer is built on the surfaces of pseudo-boehmite and PMMA (polymethyl methacrylate) nanometer microspheres gradually, a relatively uniform in-situ immobilization and dispersion environment is provided for the polymetallic components such as Zn, fe, ce, zr, mn and the like, and by combining ammonia water pH adjustment and aging treatment, each metal ion can form a polymetallic hydroxyl/oxyhydroxide precursor relatively stably, local enrichment, advanced precipitation and agglomeration phenomena caused by hydrolysis rate difference are reduced, so that the dispersion degree, interface contact opportunity and synergistic effect exertion of active components of the composite oxide after roasting are improved, and a relatively good foundation is provided for adsorption, conversion and fixation of sulfur oxides in the subsequent desulfurization process. The cooperative coordination of CT