KR20120028046A - Desulfurization sorbent and manufacturing method thereof - Google Patents

Abstract

PURPOSE: A desulfurizing agent and a method for preparing the same are provided to improve abrasion resistance characteristic, heat resistance characteristic, and desulfurizing capability of the desulfurizing agent. CONSTITUTION: A composition for a desulfurizing agent contains desulfurizing active components, a support, and inorganic binder. The support contains alumina and calcium silicate. The inorganic binder contains one or more of bentonite, boehmite, or palygorskite. The active components are one or more selected form zinc sulfite, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate, and zinc nitrate. The support contains 5-30 parts by weight of alumina and 1-30 parts by weight of calcium silicate. The inorganic binder contains 1-10 parts by weight of bentonite, 2-20 weight% of boehmite, or 1-10 parts by weight of palygorskite.

Description

Desulfurization agent and its manufacturing method

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.

In addition, the process for high temperature dry desulfurization may be divided into a fixed bed, a moving bed, a fluidized bed. In particular, 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.

Patent Literature 1 discloses a method of forming a desulfurization agent having a composition of zinc oxide, diatomaceous earth, alumina sol, and a nickel oxide precursor by using a granulator to apply the desulfurization agent for a fluidized bed. Patent document 2 discloses a method of manufacturing a desulfurization agent by dry mixing a desulfurization agent raw material, carrying a nickel oxide (NiO) precursor thereon to form a desulfurization agent paste, and using a granulator. However, the antidetergents of Patent Documents 1 and 2 are inexpensive because they have to go through the crushing and sorting of the particles, and the shape of the selected desulfurizing agent is irregular rather than spherical. There is also a problem with solid circulation.

As described above, in the fluidized bed process, the high sulfur absorption capacity and the spherical shape, the fast reaction speed, the proper particle size and the narrow particle distribution, and the excellent wear resistance, which are necessary for repeated use after the absorption and regeneration of sulfur in the fluidized bed process, are known. There is a problem that is not suitable for mass production technology.

US Patent No. 5,439,867 US Patent No. 6,056,871

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.

It is yet another object of the present invention to provide an efficient process for the desulfurization agent.

It is also an object of the present invention to provide a fluidized bed desulfurization method for removing sulfur components by fluidizing the desulfurizing agent according to the present invention.

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.

Furthermore, as another means for solving the above problems, 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.

In addition, as another means for solving the above problems, it provides a desulfurization agent prepared by the method for producing a desulfurization agent according to the present invention and the wear index AI (Air jet Index) is greater than 0 and 40% or less.

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.

In the present invention, 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.

Hereinafter, the desulfurizing agent composition of the present invention will be described in detail.

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.

Hereinafter, the components of each of the desulfurization agent composition of the present invention will be described in detail.

In the desulfurizing agent composition of the present invention, 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. For example, 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.

In the desulfurizing agent composition of the present invention, 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 (α-Al ₂ O ₃ ) or gamma phase (γ-Al ₂ O ₃ ) may be used, and the alumina of gamma phase (γ-Al ₂ O ₃ ) may be used. Preference is given to using alumina. In addition, 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. If the content is less than 5 parts by weight, the physical strength improvement effect according to the addition is insufficient, even if it exceeds 50 parts by weight may have a problem that the strength is lowered. In addition, 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.

In the present invention, the total content of the support is not particularly limited. For example, 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 may be lowered, thereby degrading 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.

In the present invention, the total content of the inorganic binder is not particularly limited. For example, 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.

On the other hand, 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.

In addition, 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.

On the other hand, in the present invention, 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. For example, nickel oxide (NiO) may be used. Examples of the nickel oxide (NiO) include, but are not limited to, commercial nickel oxide NiO (green, <99%, -325 mesh, Japanese Chemical industry Co, Ltd).

In the present invention, 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. Preferably, 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. Specific examples of 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. For example, one or more selected from the group consisting of polyvinyl alcohol (PVA), polyethylene glycol (PEG) and methyl cellulose can be used. 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.

In addition, step (A) may further comprise the step of adding a regeneration enhancer. Specifically, before the desulfurization agent composition according to the present invention is mixed with a solvent or after the slurry is prepared, 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. . At this time, the regeneration promoter may be used as the type and content of the above-mentioned regeneration accelerator.

In the present invention, 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.

Specifically 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 (μm) 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.

If necessary, 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. In addition, an organic binder may be added to maintain the particle shape during spray drying. On the other hand, if the raw material particles are several microns or less, the wet grinding process may be omitted.

In addition, the step (A) may further comprise the step of removing the foreign matter in the slurry after preparing the slurry. Through the above step, it is possible to remove the foreign matter or agglomerated raw materials that may cause the nozzle clogging during spray molding. Removal of the foreign matter can be carried out by filtering using a sieve.

In the present invention, 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.

At this time, 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. Specifically, 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.

In addition, the particle size distribution of the granules produced in the above step is preferably 30 ㎛ to 300 ㎛.

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 ℃, the dried granules may be raised to 350 to 850 ℃ at a rate of 1 to 5 ℃ / 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.

On the other hand, 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) is 40% or less, preferably 5 to 30%, more preferably 5 to 20, most preferably Preferably 5% to 15%.

At this time, if the wear index AI (Air jet Index) exceeds 40%, there is a problem that the amount of the desulfurization agent is lost when the particles are easily broken and scattered small particles when applied to the fluidized bed process.

In addition, 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 μm, and a particle distribution of 30 to 400 μm. When 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 μm or exceeds 180 μm, the solids in the fluidized bed process If the particle distribution is less than 30㎛, 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㎛ .

In addition, 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.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only for the understanding of the present invention, and the present invention is not limited thereto.

[Examples 1 to 3]

8 kg solid raw material was prepared by mixing to the composition as shown in the desulfurization agent composition of Table 1.

While adding the solid raw material prepared above to about 30 parts by weight relative to the distilled water, the anionic poly carboxylic acid dispersant and the antifoaming agent of the polyester nonionic surfactant in order to add the composition as shown in Table 1 The mixture slurry was prepared by mixing through an emulsion homogenizer.

The mixed slurry thus pulverized with a high energy bead mill for 2 times to prepare a homogenized colloidal slurry.

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. At this time, 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 content and slurry properties of the components used in the preparation of the high temperature dry desulfurization agent are shown in Table 1 below.

[Comparative Example 1 to Comparative Example 3]

In this Comparative Example, a desulfurization agent was prepared in the same manner as in the above Example with the composition shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Desulfurization Composition ZnO 50 50 50 46.5 44.4 46.5 Alumina 20 25 30 9.3 8.9 9.3 Kaolin - - - - - 9.3 Calcium silicate 10 10 10 - - - Celite - - - 37.2 35.6 23.2 Bentonite 5 5 5 - 4.4 4.7 Boehmite 10 10 - - - - Palgigorsky 5 - 5 - - - Nickel Oxide (NiO) - - - - - 7.0 Sum 100 100 100 100 100 100 Regenerative promoter Nickel Oxide (NiO) 7.5 7.5 7.5 7.0 6.7 - Organic additives Dispersant 2.2 2.7 2.6 1.91 2.25 1.03 TBS Dispersant - - - 0.1 - - Organic binder 2.5 2.5 2.5 1.16 1.17 1.16 Antifoam 0.03 0.03 0.03 0.18 0.18 0.12 Slurry properties Slurry Solids Content 27.3 27.7 27.8 38.7 39.65 39.88 Slurry pH 10.6 10.8 10.9 7.41 7.44 10.09 Slurry Viscosity (cPs) 1850 2510 2630 568 585-865 685 Unit: weight ratio of each compound based on 100 parts by weight of the total desulfurization agent composition.
Slurry Solids Content Unit: Weight ratio based on 100 parts by weight total slurry
Titanium oxide (NiO)-(green, <99%, -325 mesh, Japanese Chemical industry Co, Ltd)
Bentonite-Synthesis of Sodium Bentonite
Boehmite-like Boehmite from Labosch Chemicals (Versal 900, size 60-65 μm)

Test Example

The performance was tested in the following manner using the high temperature dry desulfurization agent for the fluidized bed prepared in Comparative Examples and Examples.

Physical properties such as shape, average particle size and distribution, bulk density, specific surface area (BET), TGA sulfur absorption capacity, and Attrition Resistance of the high-temperature dry desulfurization agent for the fluidized bed prepared in this embodiment and the comparative example Measured.

(1) Measurement of shape, surface structure, particle size and distribution

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㎛) based on ASTM F-11. Calculated as arithmetic mean. Fill density was measured using AutoTap (Quantachrome) according to ASTM D 4164-88.

(2) Initial reactivity and sulfur absorption capacity measurement

Initial reactivity and sulfur absorption capacity were simulated coal gas (30 vol% H ₂ , 64 vol% CO, 3 vol% CO ₂ , 2 vol% H ₂ O, 1 vol% H ₂ S) and thermogravimetric at 500 ℃ and atmospheric pressure. Evaluation was performed using the Thermogravimetric analysis (TGA). The sample used for the test had a weight of 20 mg and a flow rate of 150 ml / min.

(3) Measurement of wear resistance (AI) and quartz wear resistance (CAI)

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.

The results measured by measuring physical properties, abrasion resistance, and the like of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 2 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 shape rectangle rectangle Dimple rectangle rectangle rectangle Average particle size (㎛) 115 114 135 91 114 100 Particle size distribution (㎛) 58-302 58-302 58-302 38-180 28-250 28-250 Fill density (g / cc) 0.92 0.91 0.83 1.0 0.89 1.03 Specific Surface Area BET (m ² / g) 51.4 - 52.2 20.0 21.3 18 Wear resistance (AI /%) 11.2 24.7 10.9 41 58 63 Modified wear resistance (CAI /%) 10.2 22.3 10.1 26 38 38

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. Particularly, the particle size distribution (38 ~ 180㎛) 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.

In particular, referring to Tables 1 and 2 above, 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. Compared with Comparative Examples 1 to 3 using abrasion resistance (AI) and modified wear resistance (CAI) values were found to be very low.

Moreover, 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.

Claims (23)

Desulfurization active ingredient;
A support containing alumina and calcium silicate; And
A desulfurizer composition comprising an inorganic binder containing at least one of bentonite, boehmite, or palgalisky.
The method of claim 1,
The active ingredient is at least one desulfurizing agent composition selected from the group consisting of zinc oxide, zinc sulfite, zinc sulfate, zinc hydroxide, zinc carbonate, zinc acetate and zinc nitrate.
The method of claim 1,
The support, desulfurizing agent composition comprising 5 to 50 parts by weight of alumina and 1 to 30 parts by weight of calcium silicate.
The method of claim 1,
The inorganic binder, desulfurization composition comprising 1 to 10 parts by weight of bentonite, 2 to 20 parts by weight of boehmite or 1 to 10 parts by weight of palgalskyite.
The method of claim 1,
30 to 70 parts by weight of the desulfurization active ingredient;
20 to 60 parts by weight of the support; And
Desulfurizer composition comprising 5 to 20 parts by weight of the inorganic binder.
Slurry composition comprising the desulfurizing agent composition according to claim 1 and a solvent as a solid raw material.
The method of claim 6,
Slurry composition having a content of a solid raw material of 15 to 50 parts by weight.
The method of claim 6,
The solid raw material slurry composition further comprises a regeneration enhancer.
The method of claim 8,
The regeneration promoter comprises a slurry composition comprising at least one selected from the group consisting of oxides or sulfides of the transition metals of Groups 4 to 12 of the periodic table and precursors that can be converted thereto.
The method of claim 6,
Slurry composition further comprising at least one organic additive selected from the group consisting of dispersants, defoamers and organic binders.
. The method of claim 10,
The dispersant is an anionic surfactant or a nonionic surfactant slurry composition.
The method of claim 10,
The antifoaming agent is at least one slurry composition selected from the group consisting of silicone, metal soap, amide, polyether, polyester, polyglycol, organophosphate and alcohol.
The method of claim 10,
Wherein said organic binder is at least one selected from the group consisting of polyvinyl alcohols, polyethylene glycols, and methylcelluloses.
(A) mixing a solid raw material comprising the desulfurizing agent composition according to claim 1 with a solvent to prepare a homogenized slurry;
(B) molding the slurry into granules; And
(C) a method for producing a desulfurization agent comprising the step of drying and firing the granules.
The method of claim 14,
Step (A) of preparing the slurry further comprises the step of adding a regeneration enhancer.
The method of claim 14,
Step (A) of preparing the slurry further comprises the step of adding at least one or more selected from the group consisting of a dispersant, an antifoaming agent and an organic binder.
The method of claim 14,
Step (A) of preparing the slurry further comprises the step of grinding the particles in the slurry.
The method of claim 14,
Step (A) of preparing the slurry further comprises the step of preparing a slurry, followed by removing foreign matter in the slurry.
The method of claim 14,
In the drying and calcining step (C), the drying temperature is 110 to 130 ℃ and drying time is 2 to 24 hours the manufacturing method of the desulfurization agent.
The method of claim 14,
In the drying and firing step (C), firing is carried out for 2 to 10 hours after raising the dried granules to 350 to 850 ℃ at a rate of 1 to 5 ℃ / min.
Desulfurization agent prepared by the manufacturing method according to claim 14, the wear index AI (Air jet Index) 40% or less.
The method of claim 21,
The desulfurizing agent has a packing density of 0.7 to 2.0 g / cc, an average particle size of 60 to 180 μm, and a particle distribution of 30 to 400 μm.
In a dry fluidized bed desulfurization method of removing sulfur by fluidizing a gas fuel and a desulfurization absorbent,
The desulfurization absorbent comprises a desulfurization agent according to claim 21.

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