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WO2012036336A1 - Agent de désulfuration et procédé de préparation de celui-ci - Google Patents

Agent de désulfuration et procédé de préparation de celui-ci Download PDF

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Publication number
WO2012036336A1
WO2012036336A1 PCT/KR2010/006598 KR2010006598W WO2012036336A1 WO 2012036336 A1 WO2012036336 A1 WO 2012036336A1 KR 2010006598 W KR2010006598 W KR 2010006598W WO 2012036336 A1 WO2012036336 A1 WO 2012036336A1
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Prior art keywords
slurry
weight
parts
desulfurization
composition
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Ceased
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English (en)
Korean (ko)
Inventor
류청걸
위영호
이중범
백점인
엄태형
류정호
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Korea Electric Power Corp
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Korea Electric Power Corp
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Priority to CN201080070145.9A priority Critical patent/CN103201028B/zh
Publication of WO2012036336A1 publication Critical patent/WO2012036336A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/024—Compounds of Zn, Cd, Hg
    • B01J20/0244—Compounds of Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3028—Granulating, agglomerating or aggregating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/104—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/25—Coated, impregnated or composite adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/56—Use in the form of a bed

Definitions

  • the present invention relates to a desulfurization agent capable of removing sulfur-containing components and a method for producing the same.
  • Desulfurization agent of the present invention for example, hot gas desulfurization for a fluidized bed or a high-speed fluidized bed to remove sulfur components such as H 2 S in fuel gas or synthesis gas generated from gasification of coal in a dry state at a high temperature. It can be effectively used in the process.
  • Hot gas desulfurization technology involves solid fossil fuels such as coal, or fuels containing carbon such as refinery and industrial wastes (eg petroleum coke, waste tires, solid waste (RDF)). It is a technique for removing sulfur components such as H 2 S, etc. in fuel gas or synthesis gas generated by gasification at a high temperature in a dry state.
  • the technique is advantageous in an environmental aspect that there is no problem of wastewater treatment as compared to low temperature wet desulfurization using an amine absorbent widely used in general chemical plants.
  • the technology is widely used in recent years because it can remove the sulfur component at high temperature when used in coal gas combined cycle (IGCC) and coal gas fuel cell (IGFC), it is possible to increase the thermal efficiency of the power generation and to reduce the sulfur emission concentration.
  • IGCC coal gas combined cycle
  • IGFC coal gas fuel cell
  • the process for high temperature dry desulfurization may be divided into a fixed bed, a moving bed, a fluidized bed.
  • the fluidized bed has a high contact rate between the gas and the solid, a high reactivity, a solid can be treated as a fluid, and easy to control the temperature during the exothermic reaction, it is widely used than the fixed bed and the moving bed.
  • US Patent No. 5,439,867 discloses a method of forming a desulfurization agent having a composition of zinc oxide, diatomaceous earth, alumina sol and nickel oxide precursor by using a granulator to apply the desulfurization agent for fluidized bed desulfurization process.
  • US Patent No. 6,056,871 discloses a method of manufacturing a desulfurizer using a granulator by dry mixing a desulfurizer raw material, and carrying a nickel oxide (NiO) precursor thereon to make a desulfurizer paste.
  • the antidetergents of U.S. Patent No. 5,439,867 and U.S. Patent No. 6,056,871 are inexpensive because they have to undergo grinding and screening of particles. In this case, the wear loss is large, and there is a problem in fluidization or solid circulation.
  • An object of the present invention is to increase the utilization of the active ingredient through the even distribution of the active ingredient, to provide a large specific surface area required for the reaction, and the shape and particle size suitable for high temperature drying, in particular fluidized bed or high-speed fluidized bed desulfurization process And to provide a desulfurizing agent composition having a degree of distribution, having a high wear resistance (strength), heat resistance and desulfurization ability (sulfur absorption) and a desulfurizing agent using the same.
  • Another object of the present invention is to provide a slurry composition comprising the desulfurizer composition and the solvent according to the present invention as a solid raw material.
  • the present invention as a means for solving the above problems, desulfurization active ingredient; A support containing alumina and calcium silicate; And an inorganic binder containing at least one of bentonite, boehmite, or pahlorskyite.
  • the invention also provides a slurry composition comprising the desulfurizer composition and the solvent according to the invention as a solid raw material.
  • a step of preparing a homogenized slurry by mixing a solid raw material comprising a desulfurizing agent composition according to the invention with a solvent; Molding the slurry into granules; And it provides a method for producing a desulfurization agent comprising the step of drying and firing the granules.
  • the present invention also provides a dry fluidized bed desulfurization method comprising a desulfurization agent according to the present invention in a dry fluidized bed desulfurization method in which a gaseous fuel and a desulfurization absorbent are fluidized to remove sulfur components.
  • the even distribution of the active ingredient can increase the utilization of the active ingredient, provide a large specific surface area required for the reaction, and the shape, particle size and size suitable for high temperature drying, in particular fluidized bed or fast fluidized bed desulfurization process It is possible to provide a desulfurizing agent composition having a narrow particle distribution and improved wear resistance (strength), heat resistance, and desulfurization ability (sulfur absorption ability), a desulfurizing agent using the same, and a method of manufacturing the same.
  • 1 to 3 are industrial video micrographs of the high-strength zinc-based desulfurization agent prepared in accordance with an embodiment of the present invention.
  • the present invention is a desulfurization active ingredient; A support containing alumina and calcium silicate; And an inorganic binder containing at least one of bentonite, boehmite, or pahlorskyite.
  • the active ingredient may be any type of zinc oxide including any one or more of zinc oxide or a precursor thereof which may be converted into zinc oxide.
  • zinc sulfide, zinc sulfate, zinc Hydroxide, zinc carbonate, zinc acetate or zinc nitrate and the like can be used.
  • the active ingredient may be used in an amount of 30 to 70 parts by weight, and preferably 40 to 60 parts by weight based on the desulfurization agent composition. If the content of the active ingredient is less than 30 parts by weight based on the total weight of the composition, there is a risk that the desulfurization efficiency is lowered. , Spherical shape deformation, etc.) may be lowered.
  • a mixture containing alumina and calcium silicate can be used as the support.
  • the alumina contained in the support is not particularly limited, but an alumina of alpha ( ⁇ -Al 2 O 3 ) or gamma phase ( ⁇ -Al 2 O 3 ) may be used, and the alumina of gamma phase ( ⁇ -Al 2 O 3 ) may be used. Preference is given to using alumina.
  • the content of the alumina is not particularly limited, but may be 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 20 to 30 parts by weight with respect to the desulfurization agent composition.
  • the content of the calcium silicate contained in the support is also not particularly limited, but may be used 1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight relative to the desulfurizing agent composition Can be. If the content is less than 1 part by weight, it is difficult to obtain physical strength, and if the content is more than 30 parts by weight, the relative content of the active ingredient is lowered, which may cause a problem in performance deterioration.
  • the total content of the support is not particularly limited.
  • the total content of the support may be included in an amount of 20 to 60 parts by weight, and preferably 25 to 50 parts by weight with respect to the desulfurizing agent composition. If the content of the support is less than 20 parts by weight, a problem of lowering physical strength may occur, and if the content of the support is more than 60 parts by weight, the content of the relative active ingredient is lowered, which may lower performance.
  • the inorganic binder of the present invention can be densely packed between the desulfurizing agent composition to prepare a high-density desulfurizing agent, and serves to improve the strength of the desulfurizing agent by increasing the binding force between the active ingredient and the support, and can be applied to the present invention.
  • Inorganic binders may include one or more of bentonite, boehmite, aluminum oxyhydroxide, or palygorskite.
  • the bentonite may use any commercial bentonite, including natural sodium bentonite and synthetic sodium bentonite, but is not particularly limited thereto, and specific examples thereof include synthetic sodium bentonite (63.1% SiO 2 , 16.6% Al 2 O 3). , 3.28% Fe 2 O 3 , 3.07% CaO, 2.82% MgO, 3.86% Na 2 O, 8.11% moisture).
  • the content of bentonite is not particularly limited, but may be included in an amount of 1 to 10 parts by weight, and preferably 2 to 8 parts by weight with respect to the desulfurization agent composition. If the content is less than 1 part by weight or more than 10 parts by weight, the physical strength may be lowered.
  • the boehmite has properties similar to alumina sol in water, acidic and basic aqueous solutions, and all types of boehmite can be used, but are not particularly limited thereto, and specific examples thereof include pseudo-Boehmite: Versal 900, size 60-65 micrometers) is mentioned.
  • the content of such boehmite is not particularly limited, but may be included in an amount of 2 to 20 parts by weight, and preferably 5 to 15 parts by weight, with respect to the desulfurization agent composition. If the content is less than 2 parts by weight or more than 20 parts by weight, there is a fear that the physical strength is lowered.
  • the palygorskite is clay in the form of magnesium aluminum silicate and can use all types of palygorskite.
  • the content of such palgolisky is not particularly limited, but may be included in an amount of 1 to 10 parts by weight, and preferably 2 to 8 parts by weight with respect to the desulfurization agent composition. When the content is less than 1 part by weight or more than 10 parts by weight, there is a fear that the physical strength is lowered.
  • the total content of the inorganic binder is not particularly limited.
  • the total amount of the inorganic binder may be included in an amount of 5 to 20 parts by weight, and may be included in an amount of 5 to 15 parts by weight. If the content of the inorganic binder is less than 5 parts by weight, there is a problem of physical properties deterioration due to a decrease in the bonding strength between the raw materials, if the content of more than 20 parts by weight, there is a concern that the performance of the active ingredient decreases relatively.
  • ceramics, natural or synthetic zeolites containing alumina and silica are added to the desulfurizing agent composition so that the active ingredient is well distributed in the desulfurizing agent particles to increase the utility of the active ingredient and provide a wide specific surface area for the reaction. 20 to 60 parts by weight may be further included.
  • the invention also relates to a slurry composition comprising the desulfurizer composition and the solvent according to the invention as a solid raw material.
  • the solvent is not particularly limited. Specifically, water or alcohols such as methanol and ethanol can be used, and water is preferably used.
  • the content of the solid raw material is not particularly limited, but is preferably 15 to 50 parts by weight based on the slurry composition. If the content of the solid raw material is less than 15 parts by weight, the amount of slurry for manufacturing the absorbent increases, so that the manufacturing efficiency of the absorbent decreases. If the content of the solid content exceeds 50 parts by weight, the spray drying is poor due to the increase in viscosity of the slurry. There is a difficult problem.
  • the solid raw material may further include a regeneration enhancer.
  • the regenerative promoter is used to prevent the desulfurization agent from degrading, and may include one or more selected from the group consisting of oxides or sulfides of Group 4 to 12 transition metals of the periodic table, and precursors that can be converted thereto.
  • nickel oxide (NiO) may be used.
  • the nickel oxide (NiO) include, but are not limited to, commercial nickel oxide NiO (green, ⁇ 99%, -325 mesh, Japanese Chemical industry Co, Ltd).
  • the content of the regenerating enhancer is not particularly limited, and may be included in an amount of 1 to 15 parts by weight, and preferably 5 to 10 parts by weight, based on the solid material. If the content of the regeneration accelerator is less than 1 part by weight, the effect of improving regeneration efficiency is insufficient, and if it exceeds 10 parts by weight, the physical strength may be lowered.
  • the slurry composition according to the present invention is for controlling the homogenization of the solid raw material, the concentration, viscosity, stability, flowability, strength or density of the slurry, and at least one organic additive selected from the group consisting of a dispersant, an antifoaming agent and an organic binder. It can be included as.
  • the dispersant is a high concentration of the slurry by adjusting the pH of the slurry, the charge, dispersion, and aggregation of the surface of the slurry, the dispersant is anionic, nonionic, cationic and both One or more selected from the group consisting of amphoteric or zwitterion dispersants can be used.
  • an anionic dispersant having good compatibility may be used, and for example, polycarboxylate anionics such as poly carboxylate ammonium salts and poly carboxylate amine salts Surfactant, naphthalene formalin condensed sulfonate, sodium silicate, fatty acid polyhydric alcohol, fluorosurfactant (Fluorosurfactant) and the like.
  • the dispersant include an anionic polycarboxylate dispersant having no ash and excellent dispersibility and suitable for producing a high concentration slurry.
  • the content of such a dispersant is not particularly limited, but may be 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid raw material.
  • the defoamer may be used to suppress or remove bubbles (bubbles) that may occur in the course of the preparation of the slurry, and such defoamers are not particularly limited.
  • Specific examples of the antifoaming agent may include at least one selected from the group consisting of silicon, metal soap, amide, polyether, polyester, polyglycol, organophosphoric acid and alcohol, preferably Metal soap type and polyester type nonionic surfactant can be used.
  • the amount of such antifoaming agent is not particularly limited, but may be 0.01 to 1 parts by weight based on 100 parts by weight of the solid raw material.
  • the organic binder imparts plasticity and fluidity to the slurry and ultimately gives strength to the spherical desulfurizer granules granulated by spray-drying molding to facilitate handling of the granules prior to predrying and firing.
  • PVA polyvinyl alcohol
  • PEG polyethylene glycol
  • methyl cellulose a selected from the group consisting of polyvinyl alcohol (PVA), polyethylene glycol (PEG) and methyl cellulose.
  • the content of the organic binder is not particularly limited, but may be 0.5 to 5 parts by weight based on 100 parts by weight of the solid raw material.
  • the present invention also comprises the steps of (A) mixing a solid raw material comprising a desulfurization agent composition according to the invention with a solvent to prepare a homogenized slurry; (B) molding the slurry into granules; And (C) drying and calcining the granules.
  • Step (A) of preparing the slurry is a step of preparing a slurry by mixing the desulfurization agent composition according to the present invention with a solvent
  • the solvent used in the step A) can be used without limitation the above-described solvent, solid raw material (
  • the content of the solid content of the desulfurizing agent composition (hereinafter referred to as a solid raw material) is not particularly limited, and for example, 15 parts by weight to 50 parts by weight may be used based on 100 parts by weight of the solvent.
  • step (A) may further comprise the step of adding a regeneration enhancer.
  • a regeneration enhancer may be mixed with the desulfurization agent composition or a slurry to prepare a slurry in which a solid raw material, a regeneration enhancer, and a solvent are mixed.
  • the regeneration promoter may be used as the type and content of the above-mentioned regeneration accelerator.
  • the step (A) may further include adding at least one selected from the group consisting of a dispersant, an antifoaming agent and an organic binder, wherein the dispersant, the antifoaming agent and the organic binder are the above-mentioned dispersing agent, antifoaming agent And the same type and amount of organic binder.
  • step (A) may further comprise the step of grinding the particles in the slurry. More specifically, the grinding is to grind the particles in the mixture of the solid raw material and the solvent, can be performed using a wet mill, it is preferable to grind the particles in the slurry to a few microns ( ⁇ m) or less.
  • the particles pulverized by the above step are more homogeneously dispersed in the slurry, and the added dispersant suppresses the aggregation of the particles in the slurry, so that a homogeneous and stable slurry can be produced.
  • the grinding step may be repeated several times, and the flowability of the slurry may be adjusted by further adding a dispersant and an antifoaming agent between each grinding step.
  • an organic binder may be added to maintain the particle shape during spray drying.
  • the wet grinding process may be omitted.
  • the step (A) may further comprise the step of removing the foreign matter in the slurry after preparing the slurry.
  • the step of removing the foreign matter in the slurry after preparing the slurry may further comprise the step of removing the foreign matter in the slurry after preparing the slurry.
  • the step (B) of forming the granules may be performed by molding the above-described slurry into granules, and drying the homogenized slurry prepared above to form the granules.
  • the drying is not particularly limited, but, for example, the slurry may be formed into granules through spray drying.
  • the spray drying may use a conventional spray dryer, the spray method and the operating conditions of such a spray dryer may be applied to those commonly used in this field.
  • the spray method may use a countercurrent spray method that sprays in a direction opposite to the flow of drying air by using a pressurized nozzle.
  • the operating conditions of the spray dryer are 260 ° C. to 300 ° C. and an outlet temperature. It is preferable that is 90 degreeC-150 degreeC.
  • the particle size distribution of the granules produced in the above step is preferably 30 ⁇ m to 300 ⁇ m.
  • Drying and firing step (C) in the present invention is a step of drying the granules obtained in the step (B), and then firing to prepare a desulfurization agent as a final material, 110 2 to 24 hours at 130 to 130 °C, the dried granules may be raised to 350 to 850 °C at a rate of 1 to 5 °C / min in a high temperature kiln and then fired for 2 to 10 hours to prepare a desulfurization agent. .
  • the dispersing agent, the antifoaming agent, and the organic binder introduced during the production of the slurry through the firing process is burned to bond the raw materials, thereby improving the strength of the particles.
  • the present invention is prepared by the method for producing a desulfurization agent according to the present invention
  • the wear index AI Air jet Index
  • the wear index AI is 40% or less, preferably 5 to 30%, more preferably 5 to 20, most preferably Preferably 5% to 15%.
  • the desulfurizing agent according to the present invention preferably has a packing density of 0.7 to 2.0 g / cc, an average particle size of 60 to 180 ⁇ m, and a particle distribution of 30 to 400 ⁇ m.
  • the packing density is less than 0.7 g / cc or more than 2.0 g / cc, the solid circulation efficiency in the fluidized bed process decreases, and even when the average particle size is less than 60 ⁇ m or exceeds 180 ⁇ m, the solids in the fluidized bed process If the particle distribution is less than 30 ⁇ m, there is a problem that the circulation efficiency is lowered, there is a problem that the amount of desulfurization agent is lost by scattering in the fluidized bed process, the solid circulation may be difficult if it exceeds 400 ⁇ m .
  • the present invention is a dry fluidized bed desulfurization method for removing sulfur components by fluidizing the gas fuel and the desulfurization absorbent,
  • the desulfurization absorbent provides a dry fluidized bed desulfurization method comprising the desulfurization agent according to the present invention.
  • Polyethylene glycol-based organic binder (PEG) organic binder was added to the colloid slurry in a composition as shown in Table 1 below, followed by stirring, followed by aging (aging) for at least 2 hours, and filtration through a sieve of 120 mesh / 400mesh to remove foreign substances.
  • the homogenized colloid slurry from which the foreign substances were removed was calcined at 650 ° C. for 2 hours or more at a temperature rising rate of 5 ° C./min in a furnace to prepare a high temperature dry desulfurization agent for a fluidized bed.
  • the high temperature dry desulfurization agent was prepared by maintaining isothermal at 200 ° C., 400 ° C. and 500 ° C. for about 1 hour before reaching the firing temperature.
  • the shape and surface structure were investigated by an industrial electron microscope, and the particle size and distribution were classified into 10g samples for 30 minutes using MEINZER-II Shaker and 13 kinds of standard bodies (38-355 ⁇ m) based on ASTM F-11. Calculated as arithmetic mean. Fill density was measured using AutoTap (Quantachrome) according to ASTM D 4164-88.
  • Attrition Resistance is one of the most important indicators required for fluidized bed or high speed fluidized bed desulfurization processes, and is a 3-hole wear measurement device manufactured in accordance with American Society for Testing Materials D5757-95. Attrition tester) was used according to the test method and procedure suggested in the specification. The calculation method is a correction calculated by subtracting the fine powder collected for the first hour from the 5-hour wear index (AJI or AI) and the fine powder collected for 5 hours, and subtracting the amount of fine powder collected for one hour from the sample volume. Abrasion index (CAI) was measured for 5 hours at a flow rate of 10 slm using 50 g of desulfurization agent.
  • FIGS. 1 to 3 are micrographs of the high-temperature dry desulfurization agent for the fluidized bed prepared by Examples 1 to 3, and as shown in FIGS. 1 to 3 and Table 2, the shape of the high-temperature dry desulfurization agent for the fluidized bed prepared , Particle size and distribution satisfy all the requirements of commercial fluidized bed desulfurization process.
  • the particle size distribution (38 ⁇ 180 ⁇ m) is very narrow and density is about 0.83-0.92g / cc, so that fluidization and Solid circulation is good, and there is an effect that can control the excess heat due to the exothermic reaction in the regeneration reaction process.
  • the high-temperature dry desulfurization agent for the fluidized bed of Examples 1 to 3 of the present invention using alumina and calcium silicate mixtures as a support uses diatomaceous earth (celite) as a support and alumina as an inorganic binder.
  • abrasion resistance (AI) and modified wear resistance (CAI) values were found to be very low.
  • the wear resistance is greatly improved, so that the loss of desulfurization agent due to abrasion due to rapid solid circulation in the fluidized bed process is reduced, so that the desulfurization agent can be reduced, and the sulfur absorption ability is high, so that the amount of desulfurization agent can be used relatively little. It is economical because it can be simplified.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne une composition d'agent de désulfuration et un procédé de préparation de celle-ci. La présente invention utilise un mélange d'alumine et de silicate de calcium en tant que support, et un liant inorganique comprenant un ou plusieurs composés choisis parmi la bentonite, la boehmite ou la palygorskite, de manière à produire une composition d'agent de désulfuration recyclable qui peut augmenter l'utilisation de substances actives par distribution uniforme de substances actives et produire une surface spécifique nécessaire à la réaction, a la forme, la taille de particule et la granulométrie adaptées pour un gaz chaud, en particulier un lit fluidisé ou des procédés de désulfuration sur lit fluidisé ou sur lit fluidisé haute vitesse, et a une résistance à l'abrasion, une résistance à la chaleur et une capacité de désulfuration (absorption de soufre) améliorées, et un procédé de préparation de celle-ci.
PCT/KR2010/006598 2010-09-14 2010-09-28 Agent de désulfuration et procédé de préparation de celui-ci Ceased WO2012036336A1 (fr)

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CN102627341A (zh) * 2012-04-17 2012-08-08 西北师范大学 用于吸附水相中木质素磺酸盐的坡缕石黏土复合絮凝剂及其制备
CN113372894A (zh) * 2021-06-11 2021-09-10 四川正蓉上之登科技有限公司 一种高效快速可溶性除硫缓蚀剂及其制备方法
WO2023024389A1 (fr) * 2021-08-27 2023-03-02 中晶环境科技股份有限公司 Absorbeur destiné à la désulfuration de gaz de combustion, son procédé de préparation et utilisation de la composition
CN115845924A (zh) * 2022-12-22 2023-03-28 河北络合科技有限公司 一种用于沼气脱硫的催化剂及其制备方法和应用
CN118217798A (zh) * 2024-05-23 2024-06-21 上海轩鼎冶金科技集团有限公司 一种用于纯干法脱硫工艺的多边形的脱硫剂及其制备方法

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CN110681374A (zh) * 2018-07-05 2020-01-14 金昌红泉膨润土有限责任公司 一种凹凸棒黏土固体酸化剂
CN109126801A (zh) * 2018-08-28 2019-01-04 山东泰和水处理科技股份有限公司 一种脂肪醇叔胺化负载型催化剂及其制备方法和应用
CN111330545B (zh) * 2020-05-18 2021-02-09 山东新诺新材料有限公司 一种具有指示功能的高效脱硫剂及其制备方法

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CN113372894A (zh) * 2021-06-11 2021-09-10 四川正蓉上之登科技有限公司 一种高效快速可溶性除硫缓蚀剂及其制备方法
WO2023024389A1 (fr) * 2021-08-27 2023-03-02 中晶环境科技股份有限公司 Absorbeur destiné à la désulfuration de gaz de combustion, son procédé de préparation et utilisation de la composition
CN115845924A (zh) * 2022-12-22 2023-03-28 河北络合科技有限公司 一种用于沼气脱硫的催化剂及其制备方法和应用
CN118217798A (zh) * 2024-05-23 2024-06-21 上海轩鼎冶金科技集团有限公司 一种用于纯干法脱硫工艺的多边形的脱硫剂及其制备方法

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