JP2013508527A - Zinc-based desulfurization agent molded by spray drying method and method for producing the same - Google Patents

Abstract

The zinc-based desulfurizing agent molded by the spray drying method of the present invention is a slurry in which a solid desulfurizing agent raw material is slurried as a zinc-based desulfurizing agent that removes sulfur components from synthesis gas produced by gasification of carbon-containing fuel. The solid desulfurization agent raw material is formed by a drying method, and the solid desulfurization agent raw material has an active ingredient of 30 to 60 wt%, a support of 30 to 60 wt%, a regeneration enhancer of 5 to 15 wt%, and an inorganic binder of 5 to 5%. It is composed of 15 wt%.
The zinc-based desulfurization agent of the present invention is produced by forming a slurry using a spray dryer and drying and calcining it, so fluidized bed desulfurization that removes sulfur components contained in synthesis gas under high temperature and high pressure conditions. Can be used in the process.

Description

  The present invention relates to a zinc-based desulfurizing agent, and more particularly to a zinc-based desulfurizing agent which is molded by a spray drying method and has improved wear resistance.

  In general, hot gas desulfurization technology gasifies a fuel containing carbon such as solid fossil fuel such as coal, petroleum coke, industrial waste, etc. to generate synthesis gas. In other words, the sulfur component contained in the synthesis gas is removed at high temperature and high pressure before being used for power production, hydrogen production, chemical raw material production, transportation fuel production, and the like.

  Desulfurization agents used in high-temperature dry desulfurization processes can be used to remove sulfur components in other chemical industry processes such as fuel cell fuel refining, coal liquefaction processes, and ultimately cause acid rain Can be used to basically prevent the generation of sulfur oxides (SOx).

  Conventionally, zinc-based desulfurization agents have been developed for the purpose of producing particles after being kneaded by an extrusion molding method and a granulation method, and applying them to a fixed bed or moving bed desulfurization process. In addition, in order to improve the above prior art, a fluidized bed, particularly a high speed fluidized bed desulfurization process has been proposed. The fluidized bed process has the advantages of excellent gas and solid contact, easy temperature control of the reactor during absorption and regeneration reactions, and continuous operation.

  Patent Document 1 granted to Phillips Petroleum's Khale is a mixture of zinc oxide, diatomaceous earth and alumina sol, extruded, and then supported by a firing process to support a nickel oxide precursor. In addition, a desulfurizing agent is disclosed for application to a fixed bed and moving bed desulfurization step after further firing. Patent Document 2 granted to Phillips Petroleum's Khale is a granulator for applying a desulfurization agent having a composition similar to the above to a fluidized bed desulfurization process. Discloses a method of molding.

  However, in order to apply the desulfurizing agent produced by the conventional method as described above to the fluidized bed process, it is necessary to proceed with a process of controlling the particle size such as grinding and sorting, which is uneconomical. When the desulfurization agent has an irregular shape by pulverization and is applied to a fluidized bed desulfurization process, wear loss is large, and problems may occur in fluidization and solid circulation.

  Patent Document 3 assigned to Khale and the like is also almost the same as Patent Document 2, but the desulfurizing agent raw material is dry-mixed (drymix), and a nickel oxide (NiO) precursor is supported on the desulfurizing agent. A method for producing a desulfurization agent by using a granulator by making a paste is disclosed. However, in order to repeatedly use the desulfurization agent in the absorption and regeneration reaction in the high-temperature and high-pressure fluidized bed desulfurization process, not only the high sulfur absorption capacity but also the spherical shape and the particle size suitable for fluidization (size). ), The distribution of size and packing density must be retained, but the conventional technology does not meet such requirements and is not particularly suitable for mass production technology. .

US Pat. No. 5,281,445 US Pat. No. 5,439,867 US Pat. No. 6,056,871

  The present invention has been made in accordance with the above-described requirements, and the object of the present invention is to use a spray drying technology to form a particle shape suitable for a fluidized bed or high-speed fluidized bed desulfurization process ( It provides a solid desulfurizer with shape, particle size, size distribution, mechanical strength or attrition resistance, reactivity and wear resistance.

  Another object of the present invention is a zinc-based material containing zinc oxide as an active ingredient as a substance that can selectively react with hydrogen sulfide contained in synthesis gas to efficiently purify hydrogen sulfide. It is to provide a desulfurization agent.

  Still another object of the present invention is to provide a wide specific surface area necessary for the reaction by increasing the utilization of the active ingredient by distributing the active ingredient well within the desulfurization agent particles (uniform distribution), Zinc-based including a support such as calcium silicate, hydrotalcite and inorganic binders to provide strength that can be used in fluidized bed or high speed fluidized bed desulfurization processes It is to provide a desulfurization agent.

  The zinc-based desulfurizing agent molded by the spray drying method of the present invention is a slurry in which a solid desulfurizing agent raw material is slurried as a zinc-based desulfurizing agent that removes sulfur components from synthesis gas produced by gasification of carbon-containing fuel. The solid desulfurizing agent raw material is molded and manufactured by a drying method, and the solid desulfurizing agent raw material is 30 to 60 wt% of active ingredient, 30 to 60 wt% of support, 5 to 15 wt% of regeneration enhancer, and inorganic binder 5 It is composed of ˜15 wt%.

  The active ingredient can be zinc oxide, the support can be synthetic calcium silicate, and the regeneration enhancer can be nickel oxide.

  The inorganic binder includes at least one selected from similar boehmite, hydrotalcite, bentonite and kaolin.

  The hydrotalcite preferably has a magnesium oxide to calcium oxide ratio of 0.3 to 0.7.

  The zinc-based desulfurization agent has an average particle size of 70 to 150 μm, a particle distribution of 30 to 300 μm, a spherical particle shape, a packing density of 0.7 g / cc, and a wear index of 40%. It is preferable to be molded into the following.

  The zinc-based desulfurizing agent preferably has a sulfur absorption capacity of 10 gS / 100 g or 10 wt% or more of the solid desulfurizing agent raw material.

  0.5 to 10 wt% of an anionic dispersant, 0.1 to 1 wt% of an antifoaming agent based on the weight of the solid desulfurization agent raw material, so that the solid desulfurization agent raw material is uniformly slurried; An organic additive composed of 5-5 wt% organic binder can be added.

  The organic binder includes at least one of polyvinyl alcohol, polyglycol and methylcellulose.

  The method for producing a zinc-based desulfurization agent molded by the spray drying method of the present invention includes: a) active ingredient 30 to 60 wt%, solid support 30 to 60 wt%, regeneration enhancer 5 to 15 wt%, and inorganic A step of preparing a solid desulfurizing agent raw material composed of 5 to 15 wt% of a binder, b) a slurrying step of adding the solid desulfurizing agent raw material to water, mixing, wet-grinding, and producing as a slurry; c And a spray-drying step in which the slurry is formed by a spray-drying method and produced as a desulfurizing agent granule.

  The step b) includes a step of mixing an organic additive containing a dispersant and an organic binder into the slurry, and dispersing and homogenizing the solid desulfurizing agent raw material contained in the slurry.

  In the step c), the slurry can be spray-dried countercurrently using a spray dryer provided with a pressure nozzle.

  Since the zinc-based desulfurization agent of the present invention is produced by forming a slurry using a spray dryer, and drying and calcining it, the synthesis gas generated by gasifying fossil fuel is converted into coal gasification combined power generation (IGCC). ), For use in fuel cell synthesis gas, compound raw materials, etc., it can be used in a fluidized bed desulfurization process for removing sulfur components such as hydrogen sulfide contained in synthesis gas under conditions of high temperature and high pressure.

  The zinc-based desulfurization agent of the present invention can be operated in the range of 350 to 650 ° C., can use the synthesis gas generated in the gasifier with minimum heat loss, and is a secondary environmental pollution such as waste water. Since no substance is generated, there is an advantage that the synthesis gas can be purified economically.

2 is a scanning electron micrograph of a zinc-based desulfurization agent manufactured according to an example of the present invention. 2 is a scanning electron micrograph of a zinc-based desulfurization agent manufactured according to an example of the present invention. 2 is a scanning electron micrograph of a zinc-based desulfurization agent manufactured according to an example of the present invention. 2 is a scanning electron micrograph of a zinc-based desulfurization agent manufactured according to an example of the present invention.

  The desulfurization agent of the present invention is a solid flowable solid sorbent particle having a shape, a particle size, and a particle distribution suitable for a fluidized bed or high-speed fluidized bed process. The desulfurization agent is produced using spray drying technology to produce a solid desulfurization agent that reacts efficiently with the characteristics of the particles and hydrogen sulfide contained in the synthesis gas.

  Specifically, in the present invention, a slurry manufactured through the composition of the solid desulfurizing agent raw material, the composition ratio of the solid desulfurizing agent raw material, and homogenizing is formed by a spray drying method, and dried and fired. Thus, a desulfurizing agent with improved wear resistance is produced. Slurry is a solid desulfurizing agent raw material, a dispersant (solid raw material, particle dispersion and fluidity control function), an antifoaming agent (preventing deformation of particles due to bubbles in the spray drying molding process), and an organic additive such as an organic binder. Can be added to water and mixed.

  The solid desulfurization agent raw material according to the present invention includes an active ingredient, a support, an inorganic binder, and a regeneration enhancer.

  The active component selectively reacts with hydrogen sulfide and the like contained in the synthesis gas to generate metal sulfide, thereby efficiently removing sulfur impurities contained in the synthesis gas. It can be a metal oxide. The active ingredient can be 30-60 wt% (weight percent by weight) of the total solid desulfurizing agent feedstock, preferably the active ingredient is 25-40 wt% of the total solid desulfurizing agent feedstock.

Metal oxides as active ingredients include zinc oxide (ZnO) and precursors that can be converted to zinc oxide. The active ingredient may be a synthetic raw material or a natural raw material, and preferably has a purity of 99% or more, but is not limited thereto.

  An active ingredient that can be preferably used in the present invention is, for example, zinc oxide (ZnO,> 99%, <1 μm, Honzo Chemical Co.) having a particle size of 1 μm or less and a purity of 99% or more. be able to.

  The solid desulfurizing agent raw material can improve the utilization of the active ingredient so that the active ingredient is well distributed in the desulfurizing agent particles, and can provide a wide specific surface area necessary for the reaction. 30 to 60 wt% of ceramics including silica and silica, natural or synthetic zeolite.

The support may be a synthetic calcium silicate system mainly composed of silicon dioxide (SiO ₂ ). Synthetic calcium silicate can be 30-60 wt% of the total solid desulfurization agent raw material.

The synthetic calcium silicate that can be preferably used in the present invention is Celite Corp. commercial synthetic calcium silicate C grade (Micro Cel-C, pH = 10, 50.0) having an average particle size of 70μ. %, SiO ₂ , 1.8% Al ₂ O ₃ , 0.6%
Fe ₂ O ₃ , 27.0% CaO, 0.5% MgO, 1.3% Na ₂ O + K ₂ O, 18.0%
Ignition loss) or E class (MicroCel-E, pH = 8.4,47.0 %, SiO 2, 2.5%
Al ₂ O ₃ , 0.7% Fe ₂ O ₃ , 32.0% CaO, 0.6% MgO, 1.2%
Na ₂ O + K ₂ O, 16.0% ignition loss).

  The inorganic binders are densely packed between the desulfurizing agent raw materials, and can produce a high-density desulfurizing agent, which provides a good bond between the active ingredient and the support, It serves to improve strength.

  The inorganic binder that can be preferably used in the present invention can be one or a mixture of one or more of alumina binder, hydrotalcite, bentonite, and kaolin. .

  Examples of alumina binders include boehmite (boehmite, aluminum oxyhydride, or ALOOH) that has properties similar to alumina sol in an aqueous solution. Preferable examples include similar boehmite (Pseudo-Boehmit: Versal 900, size 60-65 μm) of LaRoche Chemicals.

  As the hydrotalcite, one having a ratio of magnesium oxide to calcium oxide of 0.3 to 0.7 can be used. Preferably, the ratio of magnesium oxide to calcium oxide is preferably 0.5.

Kaolin, which is a clay binder, can use all types of kaolin, and there are no particular restrictions on this. The kaolin which can be preferably used in the present invention is kaolin (ASP-200: 38.5% Al ₂ O ₃ , 45.4%) manufactured by Engelhard.
_{SiO 2, 0.2% Na 2 O} , 1.6% TiO 2, 0.03% CaO, 0.5% Fe 2 O 3, 0.02%
MgO, 0.15% K ₂ O, 0.2% Ignition loss 13.6%).

As the bentonite which is a clay binder, all commercial bentonites including naturally-occurring sodium bentonite and synthetic sodium bentonite can be used, and there is no particular limitation on this. Bentonite that can be preferably used in the present invention is synthetic sodium bentonite (63.1% SiO ₂ , 16.6% Al ₂ O ₃ , 3.28%) manufactured by Tokai Chemical, Korea.
Fe ₂ O ₃ , 3.07% CaO, 2.82% MgO, 3.06% Na ₂ O, 8.11% moisture).

  The regeneration enhancer may be a transition metal oxide of Group 4 to 12 of the Periodic Table, a sulfide thereof, or any form of transition metal that can be converted to these, and there is no particular limitation thereto. . A regeneration enhancer that can be preferably used in the present invention can be nickel oxide (NiO), and particularly preferred examples include commercial nickel oxide (green, 99%, -325 mesh, Japan Chemical Industrial Co., Ltd.). Ltd.) and commercial nickel oxide (green, 77.3% Ni, 0.8um, Seido Chemical Industry Co Ltd., Japan).

  Organic additives may be used to homogenize the solid desulfurizing agent raw material in the process of preparing the solid desulfurizing agent raw material according to the present invention in a colloidal slurry. The organic additive can be composed of a dispersant or a slurry fluidity improver which is a kind of dispersant, an antifoaming agent and an organic binder. When only the solid desulfurizing agent raw material is mixed with water, there is a problem that mixing and colloidal slurry are difficult to produce because there is little calcination and it is difficult to disperse, but this problem is solved by the organic additive.

  The dispersant (dispersant) adjusts the pH of the slurry, the charge on the particle surface, dispersion, and aggregation, and increases the concentration of the slurry, and an anionic dispersant having good compatibility can be used. There are no special restrictions. The amount of the dispersant used may be 0.1 to 10 wt%, preferably 0.5 to 10 wt% of the total weight of the solid desulfurization raw material. The anionic dispersant can be an anionic polycarboxylate dispersant. Anionic polycarboxylate dispersants, for example, have no ash, are excellent in dispersibility of ceramics at a slurry pH of about 4-11, and are suitable for the production of high concentration slurry of 25 to 40 wt% in South Korea. KOREA LTD. Cerasperse 5468-CF (40%, pH = 6.8, viscosity 85 cps, specific gravity 1.15, hereinafter referred to as SN5468 dispersant).

  The defoamer functions to remove bubbles generated in the slurry to which the dispersant and the organic binder are applied, and can be a metal soap-based or polyester-based nonionic surfactant. As a preferred example, the antifoaming agent may be Sannoco HS-deformer 551 which is a polyether type (hereinafter referred to as HS551 antifoaming agent). The amount used is preferably 0.1% or less based on the weight of the added organic binder, and more preferably in the range of 0.1 to 1 wt% based on the weight of the solid desulfurizing agent raw material. Further, the HS551 antifoaming agent has a viscosity and specific gravity of 300 cps and 0.99, respectively, has little influence on pH, and has good compatibility, so that an oil spot (Oil Spot) is hardly formed. The antifoaming agent is preferably added together with the organic binder, or after the organic binder is added and before spray drying. If necessary, a small amount can be added before or during high-speed stirring before the process of pulverizing and dispersing the raw material in a Fuma Coball mill (high energy ball mill), thereby increasing the pulverization and dispersion efficiency.

  Organic binders are mixed organic binders composed of polyvinyl alcohol (PVA), polyglycol (PEG) or methylcelluloses or combinations thereof. As a preferred example, low-viscosity modified polyethylene glycol (Sanopco HS-BD-20A, 45%, viscosity 800 cps, pH 8, specific gravity 0.99, hereinafter referred to as PEG) can be used, and the total solid raw material 100 is used as a reference. 0.5 to 5 wt%. The organic binder added in the slurry production stage provides the slurry with plasticity and fluidity, and, ultimately, provides strength to the desulfurization agent particles (green body) granulated by spray drying. This facilitates the handling of the granulate prior to pre-drying and firing.

  The method for producing a zinc-based desulfurizing agent according to the present invention includes a desulfurizing agent raw material providing step, a slurrying step, a spray drying step, and a firing step.

  The step of providing the desulfurizing agent raw material is a step of preparing the solid desulfurizing agent raw material.

  In the slurrying step, the prepared solid desulfurizing agent raw material is added to water according to the composition and mixed, the organic additive is added and mixed (mixing process), and the particles of the mixed slurry are wet-milled (wetmilling). Then, the particles are comminuted (pulverization process), and the particles of the slurry are dispersed and homogenized (dispersion process).

  The pulverization process is a process of pulverizing the solid desulfurizing agent raw material into particles of 1 μm or less. The grinding process can be an air-jet mill, a roll mill, a ball mill, an attrition mill, a vibration mill, a planetary mill, or a bead mill (bead mill). Various milling equipment such as bead mill) can be used to wet milling technique that mechanically mills the solid desulfurization agent raw material. The wet pulverization technique has a large pulverization effect, and there is no skipping of particles generated during dry pulverization.

  In the present embodiment, the wet pulverization equipment will be described by exemplifying the case of using a bead mill. In the energy bead mill, there is a gap between a rotor and a stator, and this is filled with 60-80 vol% of the grinding equipment container volume to perform grinding of the particles and homogenization of the slurry. be able to. Preferably, the grinding medium is filled with 65 to 75 vol% of the grinding equipment container volume. As the grinding medium, yttrium-stabilized zirconia beads stabilized with yttrium are used in order to prevent contamination of the desulfurizing agent raw material due to wear. The size of the ball is preferably a single size ball having a size of 0.3 mm to 1.25 mm.

  In order to make the particles of the solid raw material contained in the slurry in the grinding process into particles having a size of 1 μm or less, the wet milling process may be performed 2-3 times. Add distilled water or improver (or dispersant) and anti-foaming agent to adjust slurry concentration or fluidity so that slurry can be transported through pump for subsequent grinding process in multiple wet grinding processes Can do.

  An organic binder is added to all the produced slurries, and if necessary, a dispersant and an antifoaming agent are added, or water is added to adjust the concentration of the slurry, thereby adjusting the properties of the slurry. And after removing a foreign material through an aging process, the slurry from which the foreign material has been removed is transferred through a pump and transported to a spray dryer. Various organic binders can be used as the organic binder, but modified polyethylene glycol (PEG) is used in an amount of 0.5 to 5 vol%. There is no particular restriction on the flowability of the final slurry that is transported to the spray dryer, and any viscosity that can be transferred via a pump is possible. In this example, the viscosity of the slurry was 300 cP or more.

  If the size of the solid desulfurizing agent raw material particles used is several micrometers or less, the pulverization process can be omitted. Removal of foreign substances contained in the slurry can be performed by a vacuum filtration process. The foreign material includes dust, a dried slurry mass, a raw material having large particles, and the like.

  The spray-drying step is a step in which a stable, homogeneous and dispersed fluid slurry is formed in a spray dryer to produce a spherical desulfurization agent granule (green body). The operating conditions of the spray dryer can be selected so that the particle size distribution of the desulfurizing agent is 30 to 400 μm. Factors affecting the shape of desulfurizing agent particles (Shape), particle size (Size) and particle distribution (Size Distribution), and the structure of desulfurizing agent (morphology or texture) include the concentration and viscosity of the slurry, the degree of dispersion, and the slurry. Injection pressure and amount, drying capacity and temperature of spray dryer. Such variables vary depending on the spray form (atomizer or nozzle) of the spray dryer.

  Although there are no particular restrictions on the spray dryer, the spray dryer used in the spray drying stage has a drying chamber size of 2 m in height and 1 m in diameter, and the length including the conical chamber is 2 It is a spray dryer designed and manufactured by itself to dry with a .94m electric heater. The spray dryer was designed so that it could be spray-dried in a counter-current fountain configuration using a pressure nozzle installed at the bottom.

In order to produce the average particle size of the desulfurizing agent granule in the spray dryer to a size of about 70 to 150 μm, it is necessary to increase the residence time of the particles sprayed inside the dryer. In order to increase the residence time of the sprayed particles, it is preferable to spray-dry in counter-current (Counter-Current Fountain Configuration) using a pressurized nozzle (Centrifugal Pressure Nozzle) installed at the bottom of the spray dryer. . Preferred operating conditions of the spray dryer, the injection pressure ranges ^{6~15kg / cm 2 (10kg / cm} 2), the inside diameter of the pressure nozzle 0.51 mm, inlet temperature 260 to 300 ° C. of the spray dryer, the outlet of the spray drier The temperature is 110-130 ° C.

  The firing step is a step of drying the desulfurization agent granule formed and manufactured in the spray drying step for 2 hours or more in a reflux dryer in an air atmosphere of 110 to 150 ° C. The dried granulated body is fired at a temperature rise rate of 2 ° C./min for 2 hours or more in an air atmosphere to produce a final desulfurizing agent. Specifically, in the firing step, the temperature is raised to a final firing temperature of 350 to 850 ° C. and fired for 2 hours or more. In order to efficiently remove the solvent and the organic additive in the firing process, it is preferable to raise the temperature to 350 to 850 ° C. after maintaining at 200 ° C. and 500 ° C. for about 1 to 2 hours, respectively.

  The desulfurization agent finally produced through the desulfurization agent raw material preparation step, the slurrying step, the spray drying step, and the calcination step is a particle having a spherical shape and has an average particle size. Is 60 to 180 μm, more specifically 70 to 150 μm, the particle distribution is 30 to 400 μm, more specifically 30 to 300 μm, and the packing density is 0.7 g / cc or more, more specifically 0. 0.8 g / cc.

<Example>
Hereinafter, preferred embodiments and test examples of the present invention will be described in detail so that a person having ordinary knowledge in the technical field to which the present invention belongs can easily carry out. However, these are provided only for explaining the present invention in detail, and the scope of the present invention is not limited thereto.

<Example 1> Production of desulfurizing agents A to D In this example, zinc oxide (ZnO) 46.7% as an active component out of 2 kg of solid desulfurizing agent raw material as a whole, Class C (Microcel-C) as a support, and Desulfurizing agent with a composition ratio of 23.3 to 32.6% as a class E (Microcel-E) synthetic calcium silicate, 14 to 23.3% as an inorganic binder, and 6.7% of nickel oxide (NiO) as an enhancer It is an example regarding manufacture.

  Raw materials are added to water sequentially or at a time so that the slurry concentration is about 35%, a dispersant and a defoamer are added, and the mixture is adjusted to 10,000 to 25,000 rpm and stirred. It was mixed with an emulsifier (homogenizer). The mixed slurry was a colloidal slurry using a high energy bead mill over the secondary.

About 1.16 wt% of polyethylene glycol (PEG; Poly binder Glycol) organic binder (organic binder [Sanopco Korea, HS-BD-20A]) is added to the colloidal slurry, and the mixture is aged for 2 hours or more and filtered. The foreign matter was removed. The concentration of the final slurry is adjusted to a range of about 26.5 to 34.7 wt%, and the pH of the final slurry is adjusted using c-NH ₄ OH to be in the range of 8.95 to 10.29 at room temperature. did.

  The viscosity of the slurry was adjusted to 520 to 1490 cP at room temperature and then spray-dried. The desulfurization agent granulated body (green body) thus molded is preliminarily dried at 120 ° C. for 2 hours or more in a drier and then calcined at 650 ° C. for 2 hours or more in a furnace to produce a desulfurization agent. did. Before reaching the firing temperature, it stayed at 200 ° C., 400 ° C. and 500 ° C. for about 1 hour, and the rate of temperature increase was about 5 ° C./min. The desulfurizing agent thus produced is represented by desulfurizing agents A, B, C and D depending on the amount of the active ingredient.

  Table 1 summarizes the composition of the desulfurization agent produced by this example to improve the wear resistance and the characteristics of the flowable colloidal slurry.

<Example 2> Physicochemical characteristics of desulfurization agents A to D In this example, the produced desulfurization agent was not selected, and the shape, size and distribution of desulfurization agent, packing density (ASTM D4164-88), BET, It is the result of measuring characteristics such as reactivity. Initial reactivity and sulfur uptake are simulated coal gas (10.4 vol% H ₂ , 16.8 vol% CO, 6.1 vol%).
_{CO 2, 10vol% vapor, 3vol} % H 2 S, N 2 Balance) at 500 ° C., the result measured by the weight weight analyzer at normal pressure (Rheometrics STA-1500). The sample used for the test weighs 10 mg and the total flow rate is 50 ml per minute.

  Table 2 summarizes the initial physicochemical properties of the desulfurizing agent satisfying the physical conditions, and FIGS. 1 to 4 are scanning electron microscope (SEM) photographs of the desulfurizing agents A, B, C, and D, respectively. . It can be seen that the shape, particle size, and distribution of the desulfurizing agent produced as shown in FIGS.

Example 3 Abrasion Resistance Characteristics of Desulfurizing Agents A to D In this example, the abrasion resistance (Attrition Resistance) of a desulfurizing agent formed by a spray drying method was measured. Abrasion resistance is one of the most important indicators required in a fluidized bed or high speed fluidized bed desulfurization process. The abrasion resistance of the manufactured desulfurizing agent is standardized using an abrasion resistance measuring device (3-hole attrition tester) manufactured according to American Society for Testing Materials (ASTM) D5757-95. Measured by the test method and procedure presented in.

  The calculation method presents the 5-hour wear index (AI) presented by ASTM and the corrected wear index (CAI) calculated by removing the fine powder collected for the first hour from the fine powder collected for 5 hours. In addition, the wear rate (AR) obtained by dividing the amount of fine powder worn for 5 hours by time and the corrected wear rate were also presented. Table 3 summarizes the results of measuring the abrasion resistance of 50 g of desulfurizing agent at a flow rate of 10 liters per minute for 5 hours.

  In the present invention, it has been shown that a high-strength desulfurization agent in a form suitable for a fluidized bed process capable of removing a sulfur component contained in synthesis gas by using a spray drying technique can be produced. Such a manufacturing method is a competitive technology because it is easy to mass-produce and generates relatively little expense.

  As can be seen from Table 2, the desulfurizing agents A to D have physical and chemical characteristics suitable for a fluidized bed or high-speed fluidized bed desulfurization process. In particular, wear resistance is greatly improved, loss of desulfurization agent due to wear due to fast solid circulation in the fluidized bed process is reduced, depletion of desulfurization agent can be reduced, sulfur absorption capacity is high, desulfurization agent Can be used in relatively small amounts, which is economical because the process can be compacted.

  In addition, since the design is based on the volume rather than the weight of the desulfurizing agent when designing the fluidized bed or high-speed fluidized bed process, the higher the density of the desulfurizing agent, the greater the mass flow rate of the desulfurizing agent. The reaction temperature can be easily controlled, and the investment cost and operation cost can be reduced.

  Further, the present invention is attributed to the contribution of improving the power generation efficiency (45 to 69%) of coal gasification combined power generation and the use of fossil fuels by supplying the desulfurization agent necessary for refining for coal gasification combined power generation (IGCC). Environmental pollution can be greatly reduced. Further, it is possible to provide a dry refining technology necessary for the production of synthetic petroleum using fuel cell fuel and coal liquefaction.

  The detailed description of the present invention described above has been made with reference to preferred embodiments of the present invention. However, those of ordinary skill in the art will understand the concept of the present invention described in the claims below. It can be understood that various modifications and changes can be made to the present invention without departing from the technical scope. Therefore, the technical scope of the present invention is not limited to the contents described in the detailed description of the specification, but must be defined by the claims.

  The zinc-based desulfurization agent of the present invention is used under conditions of high temperature and high pressure in order to use synthesis gas produced by gasifying fossil fuel for coal gasification combined power generation (IGCC), synthesis gas for fuel cells, compound raw materials, etc. Can be used in a fluidized bed desulfurization process for removing sulfur components such as hydrogen sulfide contained in the synthesis gas.

Claims (13)

A solid desulfurization agent raw material is slurried as a zinc-based desulfurization agent that removes sulfur components from the synthesis gas produced by gasification of fuel containing carbon, and is manufactured by being molded by a spray drying method.
The solid desulfurization agent raw material is composed of 30 to 60 wt% of the active ingredient, 30 to 60 wt% of the support, 5 to 15 wt% of the regeneration enhancing agent, and 5 to 15 wt% of the inorganic binder among the solid desulfurization agent raw material. Zinc-based desulfurizing agent formed by the method.   The zinc formed by the spray-drying method according to claim 1, wherein the active ingredient is zinc oxide, the support is a synthetic calcium silicate, and the regeneration enhancer is nickel oxide. Desulfurization agent. The inorganic binder is
The zinc-based desulfurization agent formed by the spray drying method according to claim 1, comprising at least one selected from similar boehmite, hydrotalcite, bentonite and kaolin. The hydrotalcite is
The ratio of magnesium oxide to calcium oxide is 0.3 to 0.7, and the zinc-based desulfurizing agent formed by the spray drying method according to claim 3. The zinc-based desulfurization agent is
The zinc-based desulfurization agent molded by the spray drying method according to claim 1, wherein the zinc-based desulfurization agent is molded into an average particle size of 70 to 150 µm and a particle distribution of 30 to 300 µm. The zinc-based desulfurization agent is
The zinc-based desulfurization agent formed by the spray drying method according to claim 1, wherein the particles are formed into a spherical shape and a packing density is 0.7 g / cc. The zinc-based desulfurization agent is
The zinc-based desulfurization agent formed by the spray-drying method according to claim 1, wherein the zinc-based desulfurization agent is formed into a wear index of 40% or less.   The zinc-based desulfurization agent formed by the spray-drying method according to claim 1, wherein the sulfur absorption capacity is 10 g S / 100 g or 10 wt% or more of the solid desulfurization agent raw material.   0.5 to 10 wt% of an anionic dispersant, 0.1 to 1 wt% of an antifoaming agent, and 0.5 to the solid desulfurization agent raw material weight so that the solid desulfurization agent raw material is uniformly slurried. The zinc-based desulfurization agent formed by the spray drying method according to claim 1, wherein an organic additive composed of ˜5 wt% organic binder is added. The organic binder is
The zinc-based desulfurization agent formed by the spray-drying method according to claim 9, comprising at least one selected from the group consisting of polyvinyl alcohol, polyglycol, and methylcellulose. a) A step of preparing a solid desulfurization agent raw material composed of 30 to 60 wt% of the active ingredient, 30 to 60 wt% of the support, 5 to 15 wt% of the regeneration enhancer, and 5 to 15 wt% of the inorganic binder among the solid desulfurization agent raw material When,
b) a slurrying step in which the solid desulfurizing agent raw material is added to water, mixed, wet pulverized, and manufactured as a slurry;
c) A method of producing a zinc-based desulfurization agent by a spray drying method, comprising: a spray drying step of forming the slurry by a spray drying method and producing the slurry as a desulfurization agent granule. The step b)
The spray according to claim 11, further comprising a step of mixing an organic additive containing a dispersant and an organic binder into the slurry, and dispersing and homogenizing the solid desulfurizing agent raw material contained in the slurry. A method of producing a zinc-based desulfurization agent by a drying method. Step c)
The method for producing a zinc-based desulfurization agent by the spray drying method according to claim 11, wherein the slurry is spray-dried in a countercurrent manner using a spray dryer provided with a pressure nozzle.

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