KR100426497B1 - Zinc Oxide-Based Sorbents Applicable to Fluidized-bed and/or Transport Desulfurization Processes from Coal Gas and/or other carbonaceous synthesis gas, Preparing Methods thereof and Slurrys for Preparing the Same - Google Patents

Abstract

The present invention relates to a desulfurization agent used for removing impurities of sulfur components in syngas such as coal gas generated in a gasifier in a high temperature and high pressure fluidized bed desulfurization process, a manufacturing method thereof, and a slurry for desulfurization agent manufacture.

Desulfurization agent of the present invention 40 to 60% by weight of zinc oxide as the desulfurization active ingredient; 4-10% by weight of a transition metal oxide as a regeneration accelerator; 15-50% by weight of diatomaceous earth as a support; And inorganic binders 5 to 41% by weight, wear index AI (Abrasion Index) is less than 90%,

The manufacturing method comprises the above step of providing a desulfurizing agent component; pH adjustment and wet grinding step; Slurrying step of dispersing by adding a dispersant, an organic binder and an antifoaming agent; Forming by spray drying to make the desulfurizer granules; And firing steps,

The slurry according to the present invention is composed of 0.5 to 4 parts by weight of dispersant, 1 to 8 parts by weight of organic binder, and 40 to 200 parts by weight of water as a dispersion medium, based on 100 parts by weight of the above desulfurizing agent component:

The slurry has a concentration of 30-50 wt%, a pH of 5-14, a viscosity of 300-1600 cps,

The desulfurizing agent of the present invention, which has ideal properties as a desulfurizing agent for fluidized bed according to the manufacturing method of the present invention, has a high density, is concentrated in a narrow range of particles, exhibits excellent performance in desulfurization ability, etc. It is expected that the economic effect of refilling desulfurization agent and the life of the desulfurization agent will be greatly increased, and physical damage during operation, unlike the case where regeneration enhancer is supported by the manufacture of desulfurization agent directly added with regeneration enhancer, is also expected. Degradation of the desulfurization agent due to the separation of the regeneration enhancer can be prevented in advance, and the desulfurization process and the regeneration reaction temperature are substantially the same since the desulfurization agent including the regeneration enhancer is manufactured, which simplifies the desulfurization process. There is the effect that cost is reduced,

In addition, the colloidal slurry according to the present invention is adjusted to pH with acid or base to prevent aggregation and coagulation occurring in the mixing process of the inorganic raw material, and also contains a dispersing agent, an organic binder, an antifoaming agent, etc. Solid raw materials are pulverized to an average of 1 μm or less, so that dispersibility and stability are improved, and thus characteristics such as density of final desulfurization agent, uniform distribution of raw material particles, wear resistance, and desulfurization ability can be improved when desulfurization agent is prepared by spray drying. Do.

Description

Zinc Oxide-Based Sorbents Applicable to Fluidized-bed and / or Transport Desulfurization Processes from Coal Gas and / or other carbonaceous synthesis gas, Preparing Methods Specification and Slurrys for Preparing the Same}

The present invention relates to a desulfurization agent that can be effectively used in a hot gas desulfuization process for a fluidized bed or a high-speed fluidized bed to remove sulfur from coal gas or syngas stream of high temperature and high pressure, and a method for producing the slurry and a slurry for the desulfurization agent production. In more detail, it is formed of a high-temperature dry molded sphere composed of a desulfurizing agent active ingredient, a regeneration enhancer for improving regeneration of the desulfurizing agent, a support and an inorganic binder, and greatly improves wear resistance and durability, thereby refilling the desulfurizing agent when applied to a fluidized bed desulfurization process. It is possible to considerably reduce the cost and include the regeneration enhancer, so the sulfidation and regeneration reaction temperature ranges are substantially the same, which simplifies the desulfurization process, thus reducing the operation and maintenance costs, and reducing the separation of the regeneration accelerators. Can greatly reduce the risk of performance degradation And fluid bed or high-speed fluidized bed high temperature dry zinc-based desulfurizing agent for having a variety of advantages, that relates to a production method and a desulfurizing agent for making the slurry.

In general, hot gas desulfuization technology refers to solid fossil fuels such as coal, refinery and industrial wastes (e.g., petroleum coke, bottom residues, waste tires, solids). High-temperature, high-pressure syngas from coal or synthetic gas produced by gasifying carbon-containing fuel, such as waste (RDF), prior to transportation fuel production processes such as power generation, hydrogen production, chemical raw material production, and gasoline. It refers to gas stream cleanup. This technology is used in coal gasification combined cycle among alternative energy technologies. The desulfurization agent used in the high temperature dry desulfurization process, which is one of the clean coal technology (CCT) technology, can be used to remove sulfur in fuel cell fuel purification and general chemical industry process. It is possible to remove the SO _x that is sourced. Desulfurizer production techniques can also be applied to the production of fluidized catalytic cracking catalysts (FCC catalysts) used in refinery processes.

Conventionally, zinc-based desulfurization agents have been developed for the purpose of application to laboratory scale apparatus, fixed bed and moving bed desulfurization processes which are manufactured by extrusion molding or granulator.

In addition, a fluidized bed, in particular a high-speed fluidized bed desulfurization process, has been proposed to improve the prior art, and the fluidized bed process has a high contact between gas and solid, and absorbent-solid gas interface between the absorption reaction process and the regeneration reaction process. However, by circulating a solid substance that adsorbs sorbate when gas molecules or solutes are adsorbed to a solid liquid interface, temperature control and continuous operation of each reactor are easy.

U.S. Patent No. 5,281,445 (1994.1.25.) Granted to Khare of Phillips Petroleum is a mixture of zinc oxide, diatomaceous earth and alumina sol, extruded, calcined and supported by a nickel oxide precursor. The desulfurization agent for firing again and applying mainly to a fixed bed and a moving-bed desulfurization process is proposed.

In addition, U.S. Patent No. 5,439,867 (August 8, 1995) issued to a curry of Philips Petroleum et al. Proposes a method of forming a desulfurization agent having a composition similar to the above by using a granulator to apply to a fluidized bed desulfurization process. In order to apply the desulfurization agent manufactured by one method to the fluidized bed desulfurization process, it is inexpensive because the particles have to be pulverized and screened, and the shape of the selected desulfurization agent is irregular rather than spherical. Problems can also occur with fluidization or solid circulation. Since the desulfurization agent supports Ni (NO ₃ ) ₂ precursor in a desulfurization agent having a small specific surface area and calcines in an air atmosphere, the NiO membrane is coated on the surface of the desulfurization agent, thereby weakening the bonding force between the desulfurization agent and NiO, and finally, fluidized bed desulfurization process. In the process in which the desulfurization agent is fluidized or circulated, there is a problem in that the coating film is easily separated by being peeled off by wear and friction or broken by cracking.

U.S. Patent No. 6,056,871 (2000.5.2.) Recently granted to Curry et al. Is almost the same as U.S. Patent No. 5,439,867, but dry mixes the desulfurizing agent raw material, and supports NiO precursor to desulfurization agent. It has been proposed a method of preparing a desulfurization agent with a granulator by making a paste.

However, in order to be used repeatedly through the absorption and regeneration of sulfur in the high-temperature, high-pressure fluidized bed desulfurization process, the desulfurization agent must possess high strength and high density with high sulfur absorption ability and fast reaction speed, as well as spherical proper particle size and narrow particle distribution. Nevertheless, the conventional techniques as described above do not satisfy these requirements, and there are problems that are not suitable as mass production techniques.

In particular, in order to facilitate the design and operation of the desulfurization process by keeping the temperature of the sulfidation process and the regeneration reaction process constant, the desulfurizer absorbing sulfur is regenerated while the regeneration reaction temperature range of the desulfurization agent is maintained within the sulfidation temperature range. It needs to be. However, most of the prior art has a significant difference in the temperature ranges of the sulfidation and regeneration reactions, and desulfurization agents in which the resulfurization agent can be added to the desulfurization agent directly so that the sulfiding and regeneration reaction can proceed smoothly in a substantially similar temperature range. And its preparation method is believed to have not been proposed to date.

In addition, U.S. Patent Nos. 5,714,431 (July 2, 1988) granted to Gupta and Gangwal of the Research Triangle Institute (RTI) and U.S. Patent No. 5,972,835 to Gupta (October 26, 1999) discloses a zinc titanate desulfurization agent for a fluidized bed which is formed by spray drying, but this desulfurization agent does not include a regeneration catalyst. Therefore, in order to overcome the problems caused by the absence of the regenerated catalyst, US Patent No. 5,914,288 (1999.6.22.) Granted to Gupta of RTI described above is separately prepared for the regeneration catalyst and separately put into the process. Although the method is proposed, the life of the above-mentioned regeneration catalyst is only 4-5 cycles, and there is a problem that it is not practically applicable to the industrial site due to the remarkable lack of practicality.

Therefore, the first object of the present invention, the synthesis gas (fuel gas or coal gas) produced by gasifying coal and other fossil fuels, biomass, waste and the like at high temperature and high pressure, in particular coal gas used in the coal gasification combined cycle, etc. It has a shape, particle size, and distribution suitable for application to a fluidized bed desulfurization process that removes sulfur impurities such as hydrogen sulfide, etc., contained in fuel gases of high temperature and high pressure, and has improved wear resistance and desulfurization ability (sulfur absorption and sulfur absorption rate). To provide a possible desulfurizing agent or absorbent (hereinafter referred to as 'desulfurizing agent').

The second object of the present invention is to prevent the performance degradation due to the separation of the regeneration enhancer added in addition to the first object described above, and the sulfidation reaction temperature and the regeneration reaction temperature range are substantially the same to simplify the desulfurization process. In addition, the present invention provides a desulfurization agent capable of reducing operating and maintenance costs.

It is a third object of the present invention to provide an efficient method for preparing a desulfurizing agent according to the first and second objects described above.

The fourth object of the present invention is a homogeneously dispersed stable colloidal slurry capable of smoothly mass-producing a desulfurization agent according to the first and second objects described above by applying to the manufacturing method according to the third object. It is to provide.

According to one preferred aspect of the present invention for achieving the above-mentioned first and second objects of the present invention, 40 to 60% by weight of the precursor which can be converted into zinc oxide and zinc oxide as the desulfurization active ingredient; 4 to 10% by weight of transition metal oxides, sulfides or precursors thereof which can be converted to the Group 4-12 periodic table as a regeneration accelerator; 15-50% by weight of diatomaceous earth as a support; And inorganic binder 5 ~ 41% by weight: high temperature dry zinc for fluidized bed with average particle size 70 ~ 120㎛, particle distribution 30 ~ 400㎛ and wear index AI (Air Jet Index) 90% or less Desulfurization agents are provided.

According to a preferred aspect of the present invention for achieving the third object of the present invention described above, (A) 40 to 60% by weight of the precursor which can be converted into zinc oxide and zinc oxide as the desulfurizing agent active ingredient; 4 to 10% by weight of transition metal oxides, sulfides or precursors thereof which can be converted to the Group 4-12 periodic table as a regeneration accelerator; 15-50% by weight of diatomaceous earth as a support; And 5 to 41 wt% of an inorganic binder; (B) wet grinding after adjusting the pH by adding acid or base to the above-described desulfurizing agent component; (C) slurrying by adding a dispersant, an organic binder and an antifoaming agent to the wet milling mixture; (D) spray drying the slurry to form a desulfurizer granule; (E) predrying and calcining the granules (densification or calcination); (F) Optional step, high temperature dry zinc system for fluidized bed consisting of evaluating the physicochemical properties of the desulfurizer granules A method for preparing a desulfurization agent is provided.

According to a preferred aspect of the present invention for achieving the fourth object of the present invention described above, 40 to 60% by weight of the precursor which can be converted into zinc oxide and zinc oxide as the desulfurizing agent active ingredient; 4 to 10% by weight of transition metal oxides, sulfides or precursors thereof which can be converted to the Group 4-12 periodic table as a regeneration accelerator; 15-50% by weight of diatomaceous earth as a support; And 0.5 to 4 parts by weight of a dispersant, 1 to 8 parts by weight of an organic binder, 0.05 to 1 part by weight of an antifoaming agent as an optional component, and 40 to 200 water as a dispersion medium, based on 100 parts by weight of the desulfurizing agent component composed of 5 to 41% by weight of an inorganic binder. Consisting of parts by weight: a flowable colloidal slurry with a concentration of 30-50% by weight, a pH of 5-14 and a viscosity of 300-1600 cps is provided.

1 to 8 show the desulfurizing agents A and B of Example 1, the desulfurizing agent C of Example 2, the desulfurizing agent D of Example 3, the desulfurizing agent E of Example 4, the desulfurizing agent F of Example 5, and the desulfurizing agent G of Example 6, respectively. And an electron scanning microscope (SEM) photograph of the desulfurization agent H of Example 7.

Hereinafter, the present invention will be described in more detail, and for the sake of convenience, the desulfurizing agent according to the present invention will be referred to together with the preparation method and the slurry.

The final inorganic component constituting the high temperature dry desulfurization agent of the present invention comprises an active ingredient, a regeneration enhancer, a support, and an inorganic binder. These inorganic desulfurizer composition components are each or premixed at a predetermined ratio, and then thoroughly mixed with water, acid or base, organic additives, etc. to regrind and disperse to prepare a stable and homogeneous fluid colloidal slurry. The colloidal slurry thus prepared is spray dried through a pressurized nozzle to form spherical desulfurizer granules, and the spherical desulfurizer granules are formed into final desulfurizer granules according to the present invention through predrying and firing. In addition, if necessary, the performance of the prepared desulfurization agent can be evaluated in various ways.

The selection of raw materials of the inorganic composition components that can be used in the present invention affects the dispersion of the slurry, the shape of the desulfurizing agent, the particle size and its size distribution, the uniform distribution of the raw material particles in the desulfurizing agent particles, the packing density and the strength of the desulfurizing agent.

The active ingredient in the desulfurizing agent of the present invention includes zinc oxide in all forms including zinc oxide (ZnO) and its precursor which can be converted into zinc oxide, and the present invention is not particularly limited thereto. Examples of zinc oxide that can be preferably used in the present invention include commercial ZnO (+ 99%, <1 μm, Honzo Chemical Co.) having a particle size of 1 μm or less and having a purity of 99% or more.

Regeneration enhancers in the desulfurizing agent of the present invention include all types of transition metals including transition metal oxides of Group 4-12 of the periodic table, sulfides thereof or precursors which can be converted into them, and the present invention has particular limitations thereon. There is no. However, examples which can be preferably used in the present invention include nickel oxide (NiO), and particularly preferred examples are commercial NiO (green, <99%, -325 mesh, Japanese Chemical industry Co, Ltd) and commercial NiO (green). , 77.3% Ni, <0.8 mu m, Seido Chemical Industry Co. Ltd., Japan).

The desulfurizer support in the desulfurization agent of the present invention includes all types of diatomaceous earth whose SiO ₂ is the main component, and as the diatomaceous earth which can be preferably used in the present invention, the average particle diameter of Celite Korea Ltd. is 70 μm. Commercial diatomaceous earth (Celite 535, pH = 10, 89.6% SiO ₂ , 4.0% Al ₂ O ₃ , 1.3% Fe ₂ O ₃ , 0.2% P ₂ O ₅ , 0.2% TiO ₂ , 0.8% CaO, 0.6% MgO Commercial diatomaceous earth (Filter Cel, pH = 8, 89.0% SiO ₂ , 3.3% Al ₂ O ₃ , 1.4% Fe ₂ O, with 3.3% Na ₂ O + K ₂ O, 0.2% Ignition loss) ₃ , 0.3% P ₂ O ₅ , 0.2% TiO ₂ , 0.8% CaO, 0.6% MgO, 1.0% Na ₂ O + k ₂ O, 0.2% Ignition loss). Diatomaceous earth as a support may be preferably pulverized with an air jet mill (particle size) of 10 ㎛ (average particle size: 4 ㎛).

In the desulfurization agent of the present invention, the inorganic binder is densely packed between the desulfurization constituents to prepare a high-density desulfurization agent, and also serves to improve the strength of the desulfurization agent by binding the active component and the support well.

Examples of the inorganic binder that can be applied to the desulfurization agent of the present invention include, but are not limited to, ceramic-based alumina, bentonite, kaolin, or any mixture thereof, which is a plastic binder in water.

Examples of preferred alumina binders in the present invention include 50 nm sized alumina sol or boehmite, aluminum oxyhydroxide, or AlOOH, which has properties similar to alumina sol in water, acidic and basic aqueous solutions. Various alumina sol or boehmite may be used as the alumina binder, and a preferred example is alumina sol (Nyacol Al20, 20 wt% solids, pH 4.0, 50 nm size) of PQ Corporation or Laboche Chemical. Pseudo-Boehmite (Versal 900, size 60-65 μm) from LaRoche Chemicals.

In the clay binder of the present invention, kaolin may be used in all types of kaolin, and there is no particular limitation thereto, and examples of which may be preferably used in the present invention include kaolin (ASP-200: manufactured by Engelhard). 38.5% Al ₂ O ₃ , 45.4% 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, ignition loss 13.6%) Can be mentioned.

In addition, bentonite among the clay binders of the present invention may use any commercial bentonite including natural sodium bentonite and synthetic sodium bentonite, and there is no particular limitation thereto. (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).

When the powders (ceramic particles) are mixed with a liquid in a developing manner, the powder particles are not dispersed by forming aggregates by self-cohesion. Furthermore, the pH in the aqueous solution of the inorganic component used in the present invention is ZnO (20 wt%), diatomaceous earth (14 wt%), alumina sol (20 wt%), boehmite (17 wt%), nickel oxide (13 wt%), bentonite For (10 wt%) and kaolin (10 wt%), 9, 10, 4, 5, 6-7, 8.3-9 and 3.5-5, respectively. Since they have different isoelectric points in the aqueous solution (that is, they have different charges), when the powders are mixed with water, they are agglomerate together rather than dispersed mainly due to the electrostatic attraction of the particles. . In the present invention, in order to disperse such agglomerates into primary particles, the pH of the aqueous solution is preferentially adjusted with an acid or a base, and a dispersant is added to the slurry so that the fluidity and homogeneity of the slurry can be improved with a high speed mixer and a stirred bead mill. Prepare a stable colloidal slurry.

Dispersion of the slurry leads to the improvement of the quality by preventing the aggregation of particles, the workability and economical efficiency by the production of high concentration slurry, the prevention of non-uniformity due to the dispersion stability and the productivity. In the present invention, in order to prevent agglomeration of the slurry to prepare a homogeneous and stable flowable colloidal slurry, the raw materials are mixed or wet-pulverized, respectively, so as to disperse the particles in an aqueous solution, and then wetted with an acid or a base as necessary. Can be adjusted. In mixing the pulverized raw materials with other raw materials, the slurry is maintained in a high concentration state using a dispersant and water. After adding an organic binder and an antifoaming agent, the colloid slurry is finally adjusted in concentration, viscosity and pH. The impurities are removed through a sieve and spray-dried to obtain a desulfurizer granule.

The present invention can be largely divided into three kinds of desulfurizing agent compositions according to the type of inorganic binder used.

In the case of the desulfurizer composition using only alumina sol as the inorganic binder, it is composed of 40-60 wt% ZnO, 4-10 wt% NiO, 30-50 wt% diatomaceous earth, and 5-16 wt% alumina sol.

In the case of the desulfurizer composition using alumina sol and bentonite as the inorganic binder, it is composed of 40-60 wt% ZnO, 4-10 wt% NiO, 25-45 wt% diatomaceous earth, 5-16 wt% alumina sol, and 2-10 wt% bentonite.

For desulfurizer compositions using boehmite, bentonite and kaolin as inorganic binders, 40-60 wt% ZnO, 4-10 wt% NiO, 15-40 wt% diatomaceous earth, 5-16 wt% boehmite, 2-10 wt% bentonite , 5-15 wt% kaolin.

In the present invention, when using alumina sol, or alumina sol and bentonite as an inorganic binder, the pH of the slurry is adjusted from acidic to neutral with inorganic or organic acids. As examples of the inorganic acid that can be used, various kinds of acids such as nitric acid, hydrochloric acid and sulfuric acid can be selected, but inorganic acids including phosphorus are excluded. As the organic acid, acetic acid, formic acid, citric acid and the like may be used, but it may be preferable to use dilute nitric acid.

When boehmite is used as the inorganic binder, the pH of the slurry is adjusted to basic using a base. Examples of the base that can be used include ammonia water (NH ₄ OH), urea, ethanolamine (or 2-aminoethanol), but any type of organic base may be used, and it may be preferable to use ammonia water. .

The addition of acid and base may be added at any stage prior to spray drying molding, but it may be desirable to add at the beginning of raw material mixing to prevent coagulation or aggregation during the mixing of the raw materials. That is, an appropriate amount of acid or base is added before using the dispersant. In addition, since acid and base can also be used as a viscosity increasing agent of the slurry, when the viscosity of the slurry is low, an appropriate amount of acid or base is added and mixed well to adjust the viscosity of the slurry or, if necessary, to adjust the viscosity of the slurry together with a dispersant. do.

In the present invention, an organic additive, ie, a dispersant, an organic binder and an antifoaming agent, may be used during the preparation of the colloidal slurry to control the concentration, viscosity, stability, fluidity, strength and density of the granules, and the like. In particular, what should be considered in the selection of organic additives (dispersants, organic binders and antifoaming agents) used in the present invention is that they must be water soluble and compatible.

The dispersant used in the present invention has a function of controlling the pH of the slurry, as well as controlling the particle surface charge, dispersion and aggregation, thereby increasing the concentration of the slurry. Spray-drying of poorly dispersed slurries results in crushed, donut-like, or tempura-like desulfurizer granules that adversely affect the final product.

Organic dispersants are mostly polymeric inorganic salts and are anionic dispersants. Examples of such dispersants include polycarboxylate anionic surfactants, naphthalene formalin condensed sulfonates, sodium silicates, fatty acid polyhydric alcohols, fluorosurfactants (Fluorosurfac tant), and the like. Preferred examples include the use of anionic polycarboxylates or the use of a small amount of fluorosurfactant.

Examples of anionic polycarboxylate dispersants include no ash and excellent dispersibility of ceramics at pH 4-11 of the slurry, making them suitable for the production of high-concentration slurries of 30 to 60 wt%, from Sanopco Korea Ltd. Cerasperse 5468-CF (40%, pH = 6.8, viscosity 85 cps, specific gravity 1.15, hereinafter referred to as 'SN5468 dispersant'). The dispersant may be used in an amount of 0.5 to 4 wt% of the weight of the desulfurizer solid, and preferably, 1.5 to 3 wt%. In the present invention, Zonyl TBS (DuPont) Zonyl TBS (specific gravity 1.2, 33%, 6 <pH <8, or less) is a fluorosurfactant known to have excellent dispersibility in acid and basic in a composition containing an alumina sol inorganic binder. 'TBS dispersant' may be used between pH 2-12 of the slurry. Since the TBS dispersant is used as a foaming agent (foaming agent), it is not preferable to use in excess, it is appropriate to use in an amount of 0.005-0.1wt% based on the weight of the desulfurizer solids. In addition, 0.01-0.08 wt% based on the weight of the desulfurizer solids may be used in part with the ammonium polycarboxylic acid dispersant. The SN5468 dispersant may be added during any of the mixing and dispersing of the raw materials but must be added prior to spray drying molding. When mixed with TBS dispersants, the TBS dispersants may be added as far as possible to the final slurry stage, i.e. all of the desulfurizer inorganic raw material, then added in the course of controlling the properties of the slurry and the viscosity of the increased slurry can be adjusted using the SN5468 dispersant. Should be That is, the TBS dispersant may also be used as a dispersion and viscosity increasing agent of the slurry.

The zinc oxide, nickel oxide and diatomaceous earth used in the present invention are not plastic and cannot be formed by water alone. The addition of the inorganic binder used in the present invention is insufficient plasticity, and thus the spray-dried desulfurization granules (green body) Since the strength cannot be imparted to), it is necessary to use an organic binder capable of binding the particles. The organic binder is coated on each ceramic particle to serve as a lubricating oil in spray-drying molding to provide fluidity and impart strength to the granules. In addition, since the viscosity of the aqueous solution is different and the strength is also different according to the type of the organic binder, it is necessary to select the organic binder in consideration of the components of the ceramic, the molding method and the like. The organic binder may be classified according to the strength of the desulfurization agent granules before firing. When the low strength organic binder (Wax, Gum, etc.) is used, the granules are easily deformed and may be attached to a container or the like during handling. On the other hand, high-strength organic binders (Dextrine, Starches, Lignin, etc.) are strong and hard granules. Such granules are dimensionally stable and have good fluidity and good handleability. However, these organic binders need to use lubricant because of their low lubricity. Medium-strength organic binders are suitable for spray-drying and forming the desulfurizing agent, and examples thereof include polyvinyl alcohol (PVA), polyglycol (PEG), methylcellulose, or any mixture thereof. have. It is also important to increase the density by sintering granules when firing the spray-dried molded desulfurization agent, but it is necessary to bake at a low temperature in order to increase the strength, so it is used in a large amount compared to additives, especially other organic additives. The organic binder is preferably completely decomposed and removed at or below the firing temperature.

Since the viscosity of the final slurry suitable for spray-drying using the pressure nozzle in the present invention is about 1700 cps or less, the modified polystyrene glycol of low viscosity (Sannopco HS-BD-20A, 45%, viscosity 800 cps, pH 8 , Specific gravity 0.99, hereinafter referred to as 'PEG'), and the like. PEG has good plasticity and does not evaporate during spray drying and contains little ash. The organic binder may use 1-8 wt% based on the weight of the desulfurization agent solids, preferably about 1-2 wt%. The organic binder is added to the slurry through a high speed stirring process with a Fryma CoBall mill and then added before the spray drying. When the organic binder is added to the slurry and then mixed by stirring, the organic binder is mixed for a short time (about 5-10 minutes) at medium speed stirring (6000 rpm) or less, preferably stirred at 1000 rpm or less, and more preferably 30 at 300 rpm or less. It may be to stir for more than a minute.

If bubbles are generated during the preparation of the slurry, in particular during the mixing of the slurry after the addition of the organic binder, it not only interferes with spray drying molding but also affects the quality of the product. Bubble elimination and suppression are fundamentally important in the preparation of slurry and injecting the slurry into the pressurized nozzle of the spray dryer. The basic action of the antifoaming agent is to lower the interfacial tension of the bubbles to aggregate the fine bubbles to form large bubbles that are susceptible to flotation, to break off the surface of the slurry, and to lower the surface viscosity to prevent the entrained air from becoming a stable bubble.

When spray drying using a pressure nozzle atomizer (Atomizer), it is necessary to improve the continuous productivity and product quality by using an antifoaming agent that suppresses the occurrence of microbubbles and an excellent antifoaming agent of bubbles. When the compressed slurry delivered to the pump is sprayed through the nozzle, bubbles in the slurry burst and small lumps of slurry accumulate around the nozzle hole, which impedes uniform spraying of the slurry, which eventually blocks the nozzle hole. This will affect the shape of the desulfurization agent. Antifoaming agents for ceramics are largely divided into solution type and emulsion type, and the composition is based on chemical structure, such as silica silicon, silicon, metal soap, amido, polyether, polyester, polyglycol, organophosphate, Higher alcohols, lactic acid fats and oil-based polymers. The use of the antifoaming agent is not desirable to select only with the effect of the antifoaming agent, and should be selected after a full understanding of its shortcomings.

As the antifoaming agent used in the present invention, it is optimal to remove bubbles in the slurry to which the organic binder PEG is applied, and it is preferable to use an antifoaming agent for ceramics without ash, which has a strong anti-foaming property, and removes bubbles in the slurry. One preferred example is HS-Deformer 551 manufactured by Sanopco Co., Ltd., which is a polyether (hereinafter referred to as HS551 defoamer). The amount used is preferably 0.1% or less of the added weight of the organic binder, more preferably from 0.05 to 1wt% based on the weight of the desulfurizer solids. In addition, HS-Deformer 551 has a viscosity and specific gravity of 300 cps and 0.99, respectively, and has little effect on pH and good compatibility, so that little oil spot is formed. The addition of the antifoaming agent is preferably carried out together with the organic binder or before the spray drying molding after the addition of the organic binder. If necessary, a small amount may be added before the process of pulverizing and dispersing the raw material with the Prima cobalt mill or before the high speed stirring or the high speed stirring to increase the grinding and dispersion efficiency.

In the present invention, the first step in preparing a slurry is to prepare a colloidal slurry by grinding the average particle size of all the desulfurization materials to 1 μm or less. CoBall annular bead mill (CoBall annular bead mill: model MS-12, Fryma Mashinen AG, Switzerland: hereinafter referred to as 'Fryma CoBall mill') that can be preferably used in the present invention is a kind of stirred bead mill, wet grinding (wet It can be usefully used for grinding, homogenizing and dispersing slurry. Prima cobalt mill can adjust the degree of grinding in accordance with the operating conditions, the average particle size can be ground to less than 1㎛ by two grinding, the maximum size is about 5㎛ or less. In addition, colloidal slurry may be prepared by mixing and dispersing particles of 1 μm or less.

In the present invention, nickel oxide and diatomaceous earth having an average particle diameter of 1 μm or more, respectively, are mixed or wet-pulverized with a Prima cobalt mill to make an average particle size of 1 μm or less (maximum particle size 5 μm or less), or It can be used by mixing with other inorganic raw materials, regrinding, homogenizing and dispersing. In the present invention, when the pH of the mixture is not adjusted before mixing nickel oxide or diatomaceous earth with water and pulverizing the prima cobalt mill, the pH may be adjusted with an acid or a base in the next mixing process. In order to maintain the fluidity of the slurry during the mixing of the raw materials, it is preferable to adjust the pH to an acid or a base from the initial grinding of the raw materials. The pH of the mixture of nickel oxide in water is about 6.58 at 28 ° C. Agglomerates are formed by agglomeration of the wet milled mixture. The pH of the mixture of diatomaceous earth and water is about 10.4 at 28 ℃. If it is left for more than 5 hours with high speed stirring without adjusting the pH, the diatomaceous earth will sink. In particular, the diatomaceous earth in the bead mill solidifies during or after grinding with Prima cobalt mill without adjusting pH, so the equipment should be disassembled and washed immediately after use. Diatomaceous earth with an average particle diameter of 1 µm or less tends to aggregate easily compared to a diatomaceous earth mixture having a large particle size. In the present invention, in order to prevent aggregation and coagulation in the pulverization and mixing of the raw materials, the pH of the mixture is adjusted using an acid and a base so that the pH range is between 1.0-14. The acid is used to adjust the pH of the mixture and slurry to be between 1-7 when grinding or mixing the raw materials. When using a base to grind or mix the raw materials, the pH of the mixture and slurry is adjusted to be between 7-14.

The second step of the slurry preparation in the present invention relates to the mixing method and the order of the raw materials of the average particle size of the desulfurizer inorganic raw material is 1㎛ or less. In the present invention, any equipment or apparatus capable of producing a homogeneous slurry by mixing an inorganic raw material and an organic additive having a particle size of about 1 μm with water may be used. As an example, a Prima cobalt mill, a high-speed stirrer (4-liter Waring Blender, Cole Parmer), and a stirrer (mechanical stirrer, 1200 rpm or less) can be used. The high speed stirrer can be adjusted to about 6000 rpm, 15000 rpm, 18000 rpm, 20000 rpm. Subsequently, in the present invention, the stirring at about 6000 rpm is referred to as a shear mix, the stirring at 15000 rpm or more is referred to as a high shear mix, and the stirring of the slurry at 1200 rpm or less is classified as a low speed stirring. When the slurry is cooled in the process of homogenizing and dispersing the slurry using a Prima cobalt mill and a high speed stirring, an organic binder and an antifoaming agent are added to the almost completed slurry, and a slow stirring is mainly used when aging the slurry. In the present invention, the slow stirring of 300rpm or less is mainly used to measure the concentration, pH, viscosity and zeta potential of the final slurry.

In the present invention, the characteristics of the slurry change according to the mixing order and method of mixing the raw materials and the organic additives, but if the fluidity of the slurry is kept to a minimum during all mixing processes, the slurry according to the present invention may be prepared regardless of any mixing order and method. can do. In other words, when using Prima Cobalt mill it should be possible to transfer the raw material mixture or slurry by a feed pump (feed pump). In the process of mixing a mixture or slurry using a high speed stirrer, a dispersant or the like must be used to maintain a minimum fluidity so that raw materials and additives can be mixed. In the present invention, the mixture and the slurry maintain the minimum fluidity, so that the raw material and the organic additive are mixed, regrinded, homogenized, dispersed and redispersed in a prima cobalt mill and a high speed stirrer, and the characteristics of the final slurry are spray-dried. And the shaped desulfurizer is calcined and then the properties of the slurry are controlled so that the properties of the final desulphurizer have a performance suitable for the fluidized bed desulfurization process.

In the present invention, before the addition of zinc oxide, the pH of the mixture or slurry was adjusted to acid so as to be 1-7. In particular, during the initial grinding and mixing, the pH of the mixture or slurry is adjusted at 1 to 4 in consideration of the increase in the pH of the mixture or slurry as the particles become smaller or homogenized and dispersed during the Prima cobal milling process or the high speed stirring process.

In the present invention, it may be desirable to prepare a colloidal slurry by pulverizing diatomaceous earth and nickel oxide at a pH of 4 or less and mixing zinc oxide and alumina sol in the mixture. The dispersing agent may be added to reduce the fluidity of the slurry during mixing or to lower the viscosity of the well-dispersed homogenized slurry.

When referring to the concentration, pH and viscosity of the slurry according to the present invention to which all the raw materials of the inorganic desulfurization agent are added, the concentration is 30-50 wt%, the pH is 5-9, and the viscosity is 300-1600 cps. Can be adjusted. In addition, the concentration, pH and viscosity of the slurry according to the present invention in the state in which all the desulfurizer raw materials are added by adding the organic additive and the antifoaming agent can be adjusted to be 35-45 wt%, 6-8 and 350-1400 cps, respectively.

In the present invention, in order to adjust the pH of the mixture or slurry containing zinc oxide to 6 or less using nitric acid in the process of mixing zinc oxide in the mixture or slurry, zinc oxide is mixed with inorganic raw materials. It is advantageous to add it later in the process. The pH of the mixture or slurry of the process prior to adding zinc oxide can be adjusted to 10 or less using an acid, and in the present invention it may be desirable to adjust to 3-5. In addition, it is preferable not to adjust pH of the slurry in the state which added zinc oxide using a separate acid. The pH of these slurries is mainly between 6-8. In the present invention, to adjust the pH in the final slurry adjustment step, an acid is added to the slurry, followed by stirring the slurry for a sufficient time to maintain a constant pH of the slurry to prepare a stable slurry. After the addition of acid, the slurry should be left under stirring for at least 2 hours in order to have stable slurry properties. After the pH of the slurry is stabilized, in particular, the viscosity of the slurry is adjusted with a dispersant or the like as necessary.

In the present invention, it may be desirable to use a small amount of TBS dispersant in the preparation of the slurry. The dispersant may be preferable to be used together with an antifoaming agent because the dispersing force is strong but a lot of foam occurs during stirring. If the viscosity of the slurry is low during the final slurry preparation due to the strong dispersing force, the viscosity of the slurry is adjusted by adding it within the range of 0.005-0.1 wt% of the solid content of the desulfurization slurry to increase the viscosity of the slurry, and if necessary, SN The viscosity of the final slurry is readjusted with 5468 dispersant.

In the present invention, acids or bases are used to increase the viscosity of the final slurry. TBS dispersants may be used with acids or bases to increase slurry viscosity. Increasing the viscosity of the slurry with an acid and a base is preferred to stir the slurry for a sufficient time to stabilize the slurry's pH (at least about 2 hours) and then to control the slurry properties.

In the present invention, bentonite may be used as the inorganic binder together with the alumina sol. Bentonite, a clay inorganic binder, can be used as a binder and to facilitate mixing of other inorganic raw materials during the preparation of the mixture and slurry. Therefore, in the present invention, it may be preferable to add the bentonite addition process before the initial mixing of the raw materials, especially before adding zinc oxide.

In the present invention, from the process of adding the organic binder to the slurry, the slurry is stirred under medium speed stirring to control the properties of the slurry. In the present invention, the slurry is mainly prepared using a low speed stirrer. In the present invention, the slurry was prepared by mixing, homogenizing and dispersing the slurry to which the organic additive was added at high speed, but it was confirmed that there is no change in the characteristics of the slurry due to decomposition of the organic binder. However, polymer organic binders such as PEG may be preferable to prepare a slurry by low speed stirring because shear strength is relatively weak. When controlling the properties of the slurry using organic additives or acids and bases during low speed stirring, the homogenization and stability of the slurry should be maintained by stirring for at least 30 minutes.

In the present invention, nickel oxide having a thickness of about 40 μm or less may be wet pulverized two or more times, and mixed in any process during the preparation of the slurry, and the pH of the mixture may be adjusted by acid (pH = 1-7) or base (pH) during wet grinding. It may be desirable to grind and adjust between 7 and 7). Since the density of nickel oxide (6.670) is the largest among the raw materials used during the single wet or mixed wet milling with the Prima cobalt mill, it is separated during the grinding process. There may be discomfort to go through several grinding processes, and a negligible amount may remain in the hose of Prima Cobalt Mill. Therefore, it may be desirable to use commercial NiO (green, 77.3% Ni, <0.8 μm, Seido Chemical Industry Co. Ltd., Japan) with an average particle size of nickel oxide of about 1 μm. When using fine nickel oxide of 1㎛ size may be added at any stage of the mixing and slurry manufacturing process, it may be desirable to add to the slurry prior to the addition of the organic binder.

The present invention includes the process of preparing the final slurry by adjusting the pH of the mixture and the slurry to basic in the process of mixing the raw material and the slurry. In the preparation of the basic slurry, boehmite may be used instead of the acidic alumina sol. The size of boehmite solid particles is about 60㎛, but it is dispersed in water and has the same characteristics as alumina sol. Although it varies slightly depending on the crystallinity of the boehmite raw material, it has a large specific surface area at about 450-580 ℃ similar to alumina sol. Is converted to transition alumina. Boehmite, as a solid, has almost no limitations in addition method and addition step in the slurry preparation process, is advantageous in controlling slurry concentration, and unlike acidic alumina sol, it has the advantage of being well dispersed in both acid and basic aqueous solution. In the present invention, boehmite, bentonite and kaolin may be used as the inorganic binder in the process of preparing the basic slurry. Bentonite and kaolin, which are clay binders, are widely used as inorganic binders, and the plasticity of inorganic binders can be increased by using bentonite and kaolin together. In the present invention, the average particle size of the inorganic desulfurization agent raw material used in the preparation of the basic slurry is 5 μm or less, and thus, the raw material grinding may not be performed separately. Therefore, in the present invention, by sequentially mixing the raw materials constituting the inorganic binder and the support such as bentonite, kaolin, diatomaceous earth and boehmite with water to adjust the pH of the slurry between 7-14 with an inorganic or organic base such as ammonia water, a high-speed mixer The mixture was dispersed and dispersed in the furnace, and zinc oxide and nickel oxide were respectively added or mixed (dry mixed) to the slurry to prepare a slurry to which all the inorganic raw materials were added. This process is simple, unlike the process of adjusting the pH to acid when adding the desulfurizer raw material except zinc oxide, there is an advantage that the fluidity is well maintained during the slurry manufacturing process. In the process of preparing the basic slurry, the minimum dispersant necessary to maintain the fluidity of the slurry is added. The slurry thus prepared was cooled to prepare a colloidal slurry which was regrind, dispersed and homogenized one or more times with a prima cobalt mill. When grinding, dispersing and homogenizing with a Prima Cobalt mill one or more times, dispersants should be used to maintain the flowable slurry. In the present invention, the final pH of the basic colloidal slurry may be adjusted between 7-14, specifically 9-11, and more specifically 10 ± 0.5.

All colloidal slurry prepared according to the present invention is controlled by the characteristics of the slurry while stirring at high speed or low speed and sufficiently aged to remove the foreign matter by sieving, and then transferred to the slurry tank of the spray dryer for spray drying. The aging process is regarded as the time elapsed from the addition of all inorganic and organic additives of the desulfurization agent. If the mixing and slurry production process for a long time takes a long time, after adjusting the pH of the slurry can be regarded as the process of aging. Although the aging process varies depending on the stirring speed, at least 2 hours is suitable for low speed stirring, and the time can be shortened when controlling the characteristics of the slurry by high speed stirring. The process of removing impurities such as dried slurry agglomerates, dusts, etc. in the slurry may be carried out at any point in the previous stage in which all raw materials of the desulfurizing agent are added and the properties of the slurry are controlled to spray dry form the slurry. This process may also be carried out by installing a filtration device, such as a sieve, in the process of transferring the slurry to the nozzle of the sprayer with a feed pump in the spray drying molding process. That is, foreign matter should be removed by any conventional method prior to spray-drying molding so as not to interfere with the spray-drying molding process.

In the present invention, a stable, homogeneous, and well-dispersed flowable slurry is molded into a spray dryer to prepare spherical desulfurizer granules. Operation conditions of the spray dryer are selected so that the particle size distribution of the desulfurization agent is 30 ~ 300㎛. Factors affecting the shape, particle size and distribution of the desulfurizing agent particles, the structure of the desulfurizing agent include the concentration and viscosity of the slurry, the degree of dispersion, the injection pressure and amount of the slurry, the drying capacity and temperature of the spray dryer. These parameters may vary depending on the structure and nozzle type of the spray dryer.

The spray dryer used in the present invention is designed and manufactured by itself, and the size of the drying cylinder is 2m in height and 1m in diameter, and the dryer including the conical cylinder is 2.94m in length and dried by a heater. The spray dryer can be spray-dried co-currently using a rotary wheel atomizer or a pressure nozzle at the top, and is designed to be spray-dried counter-currently using a pressure nozzle installed at the bottom.

In the present invention, in order to manufacture an average particle diameter of about 70-120㎛ size in such a small spray dryer, a pressure nozzle (Centrifugal Pressure Nozzle, inner diameter 0.4 ~ 0.7) in the lower part of the spray dryer to increase the residence time of the particles sprayed inside the dryer. mm) was used for the Counter-Current Fountain Configuration spray method. Typical operating conditions for spray dryers are injection pressure 8-12 kg / cm ² , pressurized nozzle internal diameter 0.51 mm, spray dryer inlet temperature 260-280 ° C, spray dryer outlet temperature 90-150 ° C. The yield of the spray dryer is 70-80%.

In the present invention, a homogeneous, well dispersed, stable flowable slurry having a high concentration between 20 and 50 wt% can be prepared. The particle distribution of the desulfurization agent calcined by molding the colloidal slurry with a spray dryer is between 30 and 300 μm, and in order to prepare a spherical desulfurization agent having an average particle size of 70 to 120 μm, the concentration and viscosity of the slurry are 25 to 45 wt% and 100, respectively. Between -1400 cps is suitable, and the present invention is mainly adjusted so that the concentration and viscosity of the slurry are 30 ± 5 wt% and 500 ± 200 cps.

The granules of the desulfurization agent manufactured by spray drying molding are dried for 2 hours or more in a reflux dryer in an air atmosphere of 110 to 150 ° C. The dried granules are heated to 5 ° C./min in an air atmosphere and calcined for at least two hours at a temperature between 600-1000 ° C. to produce a final desulfurizing agent. In the present invention, it may be desirable to bake at least two hours, especially at temperatures between 650-850 ° C. In the present invention, in order to efficiently remove and remove the solvent and the organic additive by combustion, the temperature may be raised to 650-850 ° C. after maintaining the temperature at 200 ° C. and 500 ° C. for 1 to 2 hours, respectively.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, it should be understood that these examples are only for illustrating the present invention and not for limiting the present invention.

Example 1 Preparation of Desulfurizers A and B

This example shows a process of crushing nickel oxide, mixing it with diatomaceous earth, regrinding, and then mixing each raw material.

CoBall annular bead mill: model MS-12, Fryma Mashinen AG, Switzerland The wet pulverization was then performed three times with a 'Fryma CoBall mill' to give an average particle diameter of 1 탆 or less (nickel oxide pulverized and dispersed to form an aggregate after standing). A high-speed mixer (rpm 1600) containing 1.6 kg of diatomaceous earth (Celite 535, Celite Corp. USA) ground in a nickel oxide slurry and 2 kg of zinc oxide (Honzo Chemical Co. Jn) having an average particle diameter of 0.34 μm. The mixture was added sequentially to the mixture, cooled well with high speed stirring, and then re-crushed and dispersed twice with a Prima cobalt mill to prepare a homogeneous slurry. The slurry was divided into three parts by volume, divided into slurry A, B, and C, and then prepared into a slurry by the following procedure.

Slurry A was placed in a high speed mixer and the pH of the slurry was adjusted to 6.31 (32 ° C.) with 50 mL of 3M HNO ₃ while stirring. To the slurry at pH 6.31, 667 g of alumina sol (Alumina sol, 20 wt%, Nyacol AL20, The PQ Corp. USA) was added and stirred in small portions, and about 5 ml of SN5468 dispersant was added to make the slurry smoothly stirred. 40 mL was used in this process. After all the alumina sol was added, the mixture was stirred at a higher speed for 5 minutes, and then the slurry was transferred to a cooling vessel to cool the slurry while stirring at a slow speed with a mechanical stirrer. 37 g of PEG organic binder and 2 ml of HS551 antifoam were added to the cooled slurry, and the mixture was stirred at low speed for about 1 hour. At this time, the slurry had a pH of 7.98 (23 ° C.) and a viscosity of 162 cps (Brookfield viscometer model: RVD-1 +, spindle No3, 60 rpm). Since the viscosity was low, 10 ml of 6M HNO ₃ and 6 ml of dispersant were added, and the slurry was aged for about 15 hours with gentle stirring. The aged slurry had a pH of 7.38 at 21.3 占 폚 and a viscosity of 385 cps. 15 ml of 6M HNO ₃ and 18.2 ml of a dispersant were further added and stirred to adjust the concentration, pH and viscosity of the slurry A to 40 wt%, 7.22 (22 ° C.) and 605 cps (22 ° C.). The slurry thus prepared was filtered through a 120 mesh / 400mesh sieve to remove large foreign matters and agglomerates, and then transferred to a slurry tank of the spray dryer, sprayed through a pump, and sprayed into a spray dryer to form a desulfurizer granule. A counter-current spray configuration was used using a pressurized nozzle (inner diameter 0.51 mm). The hot air temperature of the spray dryer inlet was 270 ° C., the outlet temperature was 110-130 ° C., and the slurry spray pressure was about 10-15 kg / cm ² . The desulfurization agent granules (Green Body) thus prepared were dried at 120 ° C. for 2 hours or more in a dryer, and then fired at 750 ° C. in a firing furnace for 3 hours or longer. Before reaching the firing temperature, the solvent was kept at 200 ° C., 500 ° C. and 650 ° C. for 1 hour to remove the solvent and almost completely decompose the organics. The temperature increase rate was 5 degrees C / min. The desulfurization agent thus prepared was designated as desulfurization agent A.

Slurry B was slowly added to the high speed mixer while stirring, and 667 g of alumina sol was slowly added thereto, and the dispersant was added in necessary amounts so that the mixed slurry could be smoothly stirred at high speed. The slurry to which all the alumina sol was added was transferred to a cooling tube, and 37 g of PEG organic binder was added thereto and stirred. 50 ml of 6M HNO ₃ , a dispersant, and 2 ml of HS551 defoamer were added to the slurry, and the pH and viscosity of the slurry measured by stirring were 7.30 and 366 cps at 24.1 ° C. The dispersant added up to this point was 60.5 ml. When the slurry was added with 20 ml of 6M HNO ₃ and ₃ ml of TBS dispersant, the pH of the slurry was slightly lowered to 6.57 (21.7 ° C), but the viscosity was 1666 cps or more. In this state, the slurry was aged for about 15 hours with gentle stirring.

Slurry C was placed in a high speed mixer and 50 mL of 6 M HNO ₃ was added while stirring to lower the pH of the slurry (pH = 5.70, 45.6 ° C.), and 667 g of alumina sol was added at a time. In this process, only 5 ml of dispersant was required because of the fluidity of the slurry. The slurry was transferred to a cooling vessel, 37 g of PEG organic binder was added while stirring, and about 80 ml of a dispersant and 2 ml of HS551 antifoam were added while stirring. At this time, the slurry had a high pH of 1666 cps while the pH of the slurry was 6.66 at 32.3 ° C. In this state, the slurry was aged for about 15 hours with gentle stirring.

The adjusted slurry B and C were mixed in one cooling tank (concentration = 41.09 wt%), 20 ml of a dispersant and 164 ml of distilled water were added and stirred. The final slurry concentration was 40.26 wt% and the pH and viscosity were 6.74 and 1400 cps at 26 ° C., respectively. The slurry thus prepared was filtered through a 120mesh / 400 mesh sieve to remove large foreign matters and lumps, and then transferred to the slurry tank of the spray dryer, and sprayed with a spray dryer through a pump. The subsequent process was the same as the manufacturing process of the desulfurization agent A. The desulfurization agent thus prepared was designated as desulfurization agent B.

Example 2: Preparation of Antidetergent C

In this embodiment, a slurry is prepared by mixing, regrinding and dispersing diatomaceous earth and nickel oxide.

2 L of distilled water, 25 ml of 6M HNO ₃ and ₃₀₀ g of nickel oxide (Nihon Kagaku Sangyo Co. LTD, Jn, average particle diameter 30-40 µm) were added to the high speed mixer, and the mixture was stirred at a high speed for about 5 minutes. At this time, the pH of the mixture was 1.6 (29 ° C). The mixture was cooled and then wet milled twice with a Prima Cobalt mill (pH = 2.42, 42.4 ° C.). 2.5 L of distilled water and 1.6 kg of diatomaceous earth were added to a high speed mixer, and the mixture was cooled and stirred at high speed, and then pulverized once with a Prima cobalt mill (pH = 10.42, 28.4 ° C.). 30 mL of 6 M HNO ₃ was added to the diatomaceous earth slurry, and the pH of the slurry measured by stirring was 2.11 (31 ° C). Nickel oxide and diatomaceous earth slurry were put in one cooling chamber, stirred and cooled by a low speed stirrer (500 rpm or less), and then ground and dispersed once with a Prima cobal mill (pH = 3.32, 27 ° C). The slurry was divided into two high-speed stirrers in the same volume, and a small amount of dispersant was added to smooth the high-speed stirring while slowly adding 1 kg of zinc oxide to each stirrer while stirring at high speed. This process took about 15 minutes and the total amount of dispersant added was 22 ml. After addition of ZnO, the pH of each slurry was about 6.3 at 43 ° C. Further, 1 kg of alumina sol was added to the mixed slurry while stirring at high speed. 56 g of PEG organic binder and 10 ml of HS551 antifoam were added thereto, and the mixture was stirred at high speed for about 3 minutes to prepare a slurry. The slurries in both high speed stirrers were put together in a cooling vessel and stirred while adding 4 ml of HS551 antifoam. The pH and viscosity of the slurry were 6.90 and 1440 cps, respectively at 21.2 ° C. After the slurry was aged for about 12 hours, the pH and viscosity of the slurry were 6.77 and 1100 cps, respectively. The slurry was less plastic and found to aggregate around the vessel. 3.6 ml of acid-stable TBS dispersant was added to the slurry, and the viscosity of the slurry increased to 5300 cps. In addition, 3.8 ml was added. However, the viscosity was minimal and 107 ml of SN 5468 dispersant was added to readjust the viscosity, but spray-dried to 2550 cps. High viscosity was shown below. A slurry in which 75 g of bentonite was mixed with 600 ml of water and 20 ml of a SN 5468 dispersant was added to the slurry, and the mixture was stirred well to adjust the characteristics of the slurry. The pH and viscosity of the final slurry were 7.41 and 568 cps at 27 ° C, respectively. In addition, the concentration of the slurry was 38.7%. The slurry thus prepared was filtered through a 120 mesh / 400mesh sieve to remove large foreign matters and lumps, and then transferred to the slurry tank of the spray dryer, and sprayed with a spray dryer through a pump. After this process was carried out in the same manner as the spray drying molding method (slurry injection pressure 10 atm / kg ² ) of the desulfurization agent A, preliminary drying and firing method (but firing time 750 ℃ 6 hours). The desulfurization agent thus prepared was designated as desulfurization agent C.

Example 3: Preparation of Sulfur Dispersant D

In a high speed stirrer, a solution containing 2.3 L of distilled water and 27 ml of 3M HNO ₃ was added while stirring 1.6 kg of diatomaceous earth and 0.3 kg of nickel oxide, followed by cooling well (pH = 2.62, 30.2 ° C.). This mixture was regrind and dispersed twice with Prima Cobalt Mill. After one and two regrinds, the pH of the mixture increased to 7.14 (31.2 ° C) and 8.2 (38 ° C), respectively. 6 ml of 3 M HNO ₃ was added and stirred to adjust the pH of the mixture to 6.24 (27 ° C.). The mixture was transferred to a high speed stirrer, and 3.8 liters of distilled water and 40 ml of 6M HNO ₃ were added and stirred well. While stirring the mixture, 2 kg of zinc oxide, 200 g of bentonite, and 2 kg of alumina sol to which 3.6 ml of TBS dispersant was added were added in order and mixed. At this time, SN5468 dispersant was added in necessary amounts (153 ml required) to achieve smooth high speed stirring. The slurry was transferred to a cooling vessel and stirred at low speed to measure pH and viscosity, and the results were 7.9 and 620 cps at 26 ° C., respectively. 30 ml of 6M HNO ₃ was added, 25 ml of dispersant, 112 g of organic binder, and 6 ml of HS551 defoamer were added and stirred well. After the slurry was aged with stirring for at least 12 hours, the concentration of the slurry after removing this material with a sieve of 212 µm was 35 wt%, and the pH and concentration were 7.5 and 1210 cps at 27 ° C, respectively. The slurry thus prepared was transferred to the slurry tank of the spray dryer and sprayed into the spray dryer through a pump. Subsequently, desulfurizer D was prepared by spray drying, predrying, and firing in a similar manner to desulfurizer A.

Example 4 Preparation of Desulfurizer E

In a high speed stirrer, add 0.8 L of distilled water and 0.6 kg of nickel oxide while stirring (initial pH = 6.30, 26.3 ° C.), and add 4.3 ml of 3M HNO ₃ to adjust the pH to 3.01 (26.4 ° C.) and regrind twice with Prima cobalt mill. Dispersed. After grinding twice, the mixture had a pH of 6.7 (53 ° C). 2.8ℓ of distilled water and 3.2kg of diatomaceous earth were put into a high speed stirrer (initial pH = 10.02, 26 ℃), and 25.7ml of 3M HNO ₃ was added while stirring to adjust the pH to 7.2 (26.4 ℃) and pulverized once with Prima cobalt mill. Increased to 9.58 (36.6 ° C). The nickel oxide, which was pulverized twice, and the pulverized diatomaceous earth were mixed and stirred, and 55 ml of 6M HNO ₃ was added to adjust the pH to 4 (actual pH = 3.75, 29.6 ° C.), and regrind and dispersed in a prima cobal mill. In other words, nickel oxide was pulverized three times and diatomaceous earth was crushed and dispersed twice with a prima cobalt mill. The mixture was placed in a cooling vessel, and 3.8 L of distilled water and ZnO were added while stirring at low speed (pH = 6.68, 26.5 ° C). In addition, 20 ml of 6M HNO ₃ was added and stirred, and the pH was measured. As a result, it was hardly changed to 6.65 (24.3 ° C.) [In order to adjust the pH of the mixture to 4, 500 ml of the mixture was mixed with 100 ml of distilled water and stirred, and the mixture was stirred. 70 ml of ₃ was added in total of 10 ml. The pH was 5.75 (33.1 캜).

0.4 kg of bentonite and 4 kg of alumina sol were placed in a high speed stirrer and stirred (initial pH = 5.6, 25 ° C.) to 25 ml of 6M HNO ₃ to gradually bring the pH to about 4 (actual 4.16, 40.3 ° C.).

The above two slurries were put in a high speed stirrer, mixed, and then put in a cooling tube, and 416 ml of a dispersant (SN 5468), 224 g of PEG organic binder, and 4 ml of HS551 antifoam were aged and stirred for about one night (about 12 hours). The slurry from which foreign matters were removed by a sieve of 210 µm was transferred to a spray dryer slurry tank, and 4 ml of HS551 antifoam was added thereto, followed by stirring well. The pH and viscosity of the final slurry were 7.43 and 490 cps at 26 ° C., respectively, and the concentration was 43.1 wt%. The slurry thus prepared was transferred to the slurry tank of the spray dryer and sprayed into the spray dryer through a pump. Subsequently, desulfurizer E was prepared by spray drying, predrying, and firing in a similar manner to desulfurizer A.

Example 5: Preparation of Desulfurizer F

1.6 L of distilled water, 10 ml of 3M HNO ₃ and 1.2 kg of nickel oxide were added to a high speed stirrer, and the mixture was stirred and cooled, and then regrind and dispersed twice with a prima cobal mill (pH = 3.20, 26.6 ° C.) (Slurry 1).

In a high speed stirrer, 8 ml of distilled water, 68 ml of 6M HNO ₃ and 6.4 kg of diatomaceous earth (4.4 kg of filter cel and 2.0 kg of celite) were stirred and cooled (initial pH = 3.2, 20.4 ° C.), and then triturated and dispersed twice with Prima cobalt mill. . Additional distilled water required in this process was about 2 liters and the pH of the diatomaceous earth slurry was 4.25 at 19 ° C. (Slurry 2).

7 L of distilled water, 60 ml of 6M HNO ₃ and 0.8 kg of bentonite were added to a high speed stirrer, and 8 kg of alumina sol was added slowly with stirring (pH = 6.25, 30.5 ° C.). 180 ml of 6M HNO ₃ was further added to adjust the pH to about 4, and 200 ml of a dispersant was added and stirred, but the flowability of the slurry was not good (Slurry 3).

Slurry 2 was transferred to a vat, slurry 3 and 1 were added in order with stirring, and 350 ml of dispersant was added and stirred well. 8 kg of zinc oxide was slowly added thereto while stirring, and the required amount of SN5468 dispersant was added to facilitate stirring. The amount of dispersant consumed in the course of adding zinc oxide was 350 ml in total. The slurry was added to 3-4 L each in a high speed stirrer and redispersed by high speed stirring for about 10 minutes. 448 g of PEG organic binder and 20 ml of HS551 defoaming agent were added to the redispersed slurry in a vat while stirring to cool (Slurry 4).

During the preparation of the above-mentioned desulfurization agent CD, 2.841 kg of small desulfurization agent (mainly 40 μm or less) granules collected from the spray dryer cyclone, 4.622 L of distilled water and 70 mL of the dispersant were rapidly stirred and cooled, and regrind once with a Prima cobalt mill. Dispersed. 10 ml of HS551 defoamer and 78.4 g of PEG organic binder were added and stirred (Slurry 5).

Slurry 5 was added to slurry 4, stirred, and transferred to a high speed stirrer by 3-4 liters and stirred at about 6000 rpm for 5 minutes (required 6 ml of SN5468 dispersant). The mixed redispersed slurry was transferred to a cooling tank, 4 ml of HS551 defoaming agent was added to the mixture, stirred, and cooled to remove foreign substances with two sieves of 125 µm / 63 µm. To increase the viscosity (275 cps) of the slurry, 30 ml of 6M HNO ₃ was added thereto, and the slurry was aged for about 12 hours while stirring (viscosity 810 cps, 28 ° C). About 6 ml of SN5468 dispersant and 3 ml of HS551 defoaming agent were added, and the final slurry cooled by medium stirring (6000 rpm) was cooled to 7.44 and 585-865 cps at 26.4 ° C., and the concentration was 39.7 wt%. The slurry was transferred to the slurry tank of the spray dryer and sprayed through the pump to the spray dryer. Subsequently, desulfurization agent F was prepared by spray drying, predrying and firing in a similar manner to desulfurization agent A.

Example 6: Preparation of Desulfurizer G

This example shows a scale-up process using 34.4 kg of solid desulfurizer feedstock.

About 23 L of distilled water, 70 ml of 6M HNO ₃ and 11.02 kg of diatomaceous earth were mixed, and 1.6 kg of bentonite was added thereto, followed by high speed stirring. 120 ml of 6 M HNO ₃ was further added to the slurry to adjust the pH to 3.99 (28 ° C.), and once ground and dispersed with a Prima Cobal mill. After one grinding the pH of the slurry was 4.63 (38 ° C.) but increased over time to 7.53-7.86. Further 110 ml of 6M HNO ₃ was added to adjust the pH to 3.15 at 28.1 ° C. (Slurry 1).

2.4 kg of NiO was stirred and mixed with a solution of about 4 L of distilled water and 20 ml of 3M HNO ₃ (pH = 3.20, 26.6 ° C.). This mixture was regrind and dispersed three times with a Prima Cobalt mill. At this time, the pH of this NiO slurry increased from 26.4 ° C to 6.62, and the pH was adjusted to 30 ml of 3M HNO _{3, which} was 3.86 at 26.5 ° C (Slurry 2).

16 kg of ZnO was stirred at low speed by mixing ₂₃ l of distilled water and 420 ml of 6M HNO ₃ (pH = 6.47, 26.4 ° C.) (Slurry 3). Further addition of acid resulted in a slight change in pH.

Slurry 1 was placed in a vat and 16 kg of alumina sol was added slowly with stirring, slurries 2 and 3 were added sequentially, and SN5468 dispersant was added in 10-100 ml whenever necessary for smooth stirring. There was no solidification or agglomeration of the slurry in this mixing process, and the amount of dispersant required was 1344 ml. The roughly mixed slurry was put in a 3-4 L high speed stirrer, mixed and dispersed at high speed for 10 minutes, and a dispersant was administered as necessary. 40 ml of dispersant was required to disperse with a high speed stirrer. The dispersed slurry was cooled and aged for about 12 hours while stirring at low speed by adding 896 g of PEG organic binder and 40 ml of HS551 antifoaming agent. The concentration of the slurry was about 38 wt% and the pH and viscosity were 7.4 and 1260-1410 cps at about 30 ° C. 56 ml of SN5468 dispersant was further added to the mixture, stirred, and placed in a high speed stirrer for 3-4 liters. An additional 30 ml of HS551 antifoam was added and stirred with cooling. The concentration of the slurry measured after removing the foreign matter with a sieve of 125 μm / 45 μm was 38 wt%, and the pH and viscosity of the slurry were 7.60 and 670-680 cps at 26.4 ° C., respectively. The slurry thus prepared was transferred to the slurry tank of the spray dryer and sprayed into the spray dryer through a pump. Subsequently, desulfurization agent G was prepared by spray drying, predrying and firing in a similar manner to desulfurization agent A.

Example 7: Preparation of Desulfurizer H

This example shows the process of preparing a basic slurry from the mixing process using bentonite, kaolin and boehmite as inorganic binders. This process is simpler and more convenient than adjusting the mixture or slurry with acid.

2 liters of distilled water and 30 ml of c-NH ₄ OH were added to a high speed stirrer, and 200 g of kaolin, 100 g of bentonite, and 500 g of diatomaceous earth were sequentially added and mixed well for about 10 minutes (pH = 9.76, 36.7 ° C) (Slurry 1).

1 L of distilled water and 200 g of boehmite were added to another high speed stirrer, and the pH of the mixture measured by stirring was 4.96 at 16.1 ° C. 22 ml of c-NH ₄ OH was added to the mixture and mixed for about 10 minutes to adjust the pH of the mixture to about 10 (actual pH = 9.8, 28 ° C.) (Slurry 2).

Slurry 2 was placed in slurry 1 and mixed and dispersed by high speed stirring for about 5 minutes. While drying the slurry at high speed, 1 kg of dry mixed ZnO and 150 g of NiO were slowly added (within 35 minutes of time required). As the ZnO and NiO mixtures were added, the dispersant was added in an amount necessary to facilitate high speed stirring, and the SN5468 dispersant required in the process was 30 ml. After both ZnO and NiO mixtures were added, the mixture was stirred at a high speed for another 5 minutes, and the slurry was transferred to a cooling vessel, and about 10 mL of SN5468 dispersant was added and cooled with low stirring (pH = 9.97, 19.7 ° C). The cooled slurry was regrind and dispersed twice in a Prima Cobalt mill. The pH of the slurry milled and dispersed twice was 9.87 (17.8 ° C.). 56 g of PEG organic binder, 8 ml of SN5468 dispersant, 2 ml of HS551 defoamer, and 10 ml of c-NH ₄ OH were added while stirring the slurry in a cooling vessel. The pH and viscosity of the slurry were 9.92 (21.5 ° C) and 930 cps (20.5 ° C), respectively. The slurry was aged with stirring overnight (about 12 hours). The concentration, pH, viscosity and zeta potential of the aged slurry were 46.3 wt%, 9.98 (15 ° C.), 1020 cps (15 ° C.) and -25 mV, respectively. To adjust the slurry concentration to 40wt%, add about 300ml of distilled water and stir for more than 30 minutes.The concentration, pH, viscosity, and zeta potential of the slurry were 39.88wt%, 9.92 (15 ℃), 590cps (15 ℃) and- 25 mV. The slurry was filtered through a 125 μm / 45 μm sieve to remove this material and transferred to the slurry tank of the spray dryer to control the properties of the final slurry. In other words, 0.5 ml of HS551 defoamer and 10 ml of c-NH ₄ OH were added and stirred. The concentration, pH, viscosity, and zeta potential were 39.88 wt%, 10.1 (16.5 ° C.), 680 cps (16.5 ° C.), and -90 to 167, respectively. mV. The slurry thus prepared was transferred to the slurry tank of the spray dryer and sprayed into the spray dryer through a pump. Subsequently, desulfurization agent H was prepared by spray-drying molding, predrying and firing in a similar manner to desulfurization agent A.

Test Example 1 Composition and Slurry Characteristics of Desulfurization Agents A to H

Desulfurization agents prepared in Examples 1 to 7 are spherical in density 0.8-1.1 g / cc, average particle size is 90 ~ 120㎛, particle distribution is 40 ~ 300㎛, BET is 15 ~ 25m ² / g It was suitable for fluid bed desulfurization.

Table 1 below summarizes the composition of the desulfurization agents of Examples 1-7 and the properties of the colloidal slurry prepared above. The used nitric acid was summarized in terms of the amount of 6M HNO ₃ used. The measured slurry concentration, pH and viscosity may be measured using any moisture meter, pH meter and viscometer.In this case, the concentration and pH of the slurry can be measured using an infrared humidity analyzer (IR-200, Denver Instrument). ) And a benchtop pH meter (59003-05, Cole-Parmer) were used. The viscosity of the slurry was from a Brookfield Digital Viscometer (RDV-I +, Brookfield Engineering Laboratory, Inc.) with spindle # 3 at 60 rpm.

Desulfurization Agent Composition and Characteristics of Aqueous-colloidal Slurries : division Group 1 Group 2 Group3 Desulfurizer A Desulfurization agent B Desulfurizer C Desulfurizer D Desulfurizer E Desulfurizer F Desulfurizer G Desulfurization H Desulfurization ZnO / wt% 46.5 46.5 46.5 44.4 44.4 44.4 44.4 46.5 Celite / wt% 37.2 37.2 37.2 35.6 35.6 35.6 35.6 23.2 Kaolin / wt% 9.3 Bentonite / wt% 4.4 4.4 4.4 4.4 4.7 Alumina / wt% 9.3 9.3 9.3 8.9 8.9 8.9 8.9 9.3 NiO / wt% 7.0 7.0 7.0 6.7 6.7 6.7 6.7 7.0 Acid or base 6M HNO ₃ / (ml / kg solids) 34.88 41.86 14.77 20.12 21.51 17.11 21.66 - c-NH ₄ OH / (ml / kg solids) - - - - - - - 33.49 Organic additives SN 5468-CF / wt% 2.06 2.58 1.91 1.82 2.23 2.25 1.93 1.03 TBS / wt% 0.08 0.1 0.03 Organic binder / wt% 1.15 1.15 1.16 1.16 1.16 1.17 1.16 1.16 Antifoam / wt% 0.14 0.14 0.18 0.14 0.09 0.18 0.20 0.12 Slurry properties Solid content / wt% 39.8 40.26 38.7 35 43.1 39.65 37.5 39.88 Final pH 7.22 6.74 7.41 7.49 7.43 7.44 7.61 10.09 Final η / cps 605 1400 568 1210 490 585-865 635 685

Test Example 2 Measurement of Physical Properties of Desulfurization Agent

In this test example, physical properties such as the shape, particle size and distribution, bulk density, specific surface area (BET) and abrasion resistance of the desulfurization agent in Examples 1 to 7 were measured.

The shape and surface structure were examined by SEM-EDS (JSM 6400, Joel), and the particle size and distribution were 10g sample using MEINZER-II Shaker and 13 standard (38-355㎛) based on ASTM F-11. Was classified for 30 minutes and calculated as an arithmetic mean. Fill density was measured using AutoTap (Quantachrome) according to ASTM D 4164-88.

In the present invention, using the gravimetric analyzer (STA 1500, Rheometric), the sulfidation and regeneration of the desulfurization agent was measured at atmospheric pressure. The reaction gas composition used for the sulfidation reaction was 9.7vol% H ₂ , 17.5vol% CO, 6.1vol% CO ₂ , 0.4vol% CH ₄ , 3vol% H ₂ S and 63.3vol% N ₂ . Regeneration reaction gas was used as air. The sample amount used for the reaction was 10 mg and the flow rate was 50 ml / min. Sulfur capacity was measured at 500 ° C, and regenerability was measured at 100% on the basis that 100% of the sample was completely regenerated while absorbing sulfur at 650 ° C.

Attrition Resistance of the prepared desulfurizer is used as the most important indicator when applying desulfurizer to fluidized bed desulfurization process. The wear resistance of the prepared desulfurization agent was measured by self-fabricating equipment according to ASTM D5757-95. The test method is almost identical to that described in ASTM D5757-95. However, in the standard condition (273.15K, 1bar), a standard flowmeter was installed at the rear of the wear gauge to adjust the injection air volume so that the discharge flow rate of the wear gauge was 10.00 ℓ / min ± 0.05, and the reverse pressure was installed at the front of the pressure gauge. There is a difference depending on the method (for example, a check valve), etc., it is maintained at 2.20 ~ 2.6kg / cm ² and there is a difference from 130 ~ 180kPa prescribed by ASTM. 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. The wear index (CAI) is also presented. 50 g of desulfurization agent was measured for 5 hours at 10 slm flow rate.

Physical and chemical properties of the desulfurization agents prepared in the present invention are summarized in Table 2 below.

Physical and chemical properties of desulfurization agents : division Desulfurizer A Desulfurizer B Desulfurizer C Desulfurizer D Desulfurizer E Desulfurizer F Desulfurizer G Desulfurization H shape rectangle rectangle rectangle rectangle rectangle rectangle rectangle rectangle Average particle size / ㎛ 96 96 91 98 112 114 102 100 Particle Distribution / ㎛ 38-180 38-180 38-180 38-180 38-250 38-250 38-180 38-250 Fill density / (g / cc) 0.9 0.85 0.89 1.0 0.98 0.89 1.03 1.03 BET / (m ² / g) 25.4 22.1 18.7 20.0 20.13 21.3 19.13 18 1st TGA ^* Yellow Loading Amount / (wt%) 17.27 15.92 17.52 15.66 15.51 15.24 17.26 18 2nd TGA yellow loading / (wt%) 14.0 13.68 13.71 15.84 16.62 15.44 15.90 16.8 Regeneration /%, 650 ℃ 74 75 75 91 86 90 86 93 AI /% 49 61 41 89 47 58 63 63 CAI * /% 32 48.5 26 83 32 38 44 38 AR /% 6.1 6.1 6.1 8.9 4.7 6.0 6.3 6.3 CAR /% 4.4 4.6 4.5 6.8 3.1 3.5 3.7 2.9

^* Thermogravimetric Analysis

As can be seen from the accompanying Figures 1 to 8, the shape, particle size, and distribution of the prepared desulfurization agent satisfy all of the conditions required for commercial fluidized bed desulfurization, and in particular, the particle size distribution (40-250 μm) is quite significant. It is narrow and has a high density of 0.85-1.05g / cc, which allows good fluidization and solid circulation in the fluidized bed desulfurization process, and has an effect of controlling excess heat due to exothermic reaction during the regeneration process. In addition, the initial sulfur absorption capacity is also excellent in reactivity at 75% or more of the theoretical value (21wt%), and despite the change of the inorganic binder, the sulfur absorption capacity was found to be generally similar to 13.5-17wt%. Desulfurizer groups using alumina sol (desulfurizers A, B, C), alumina sol and bentonite (D, E, F, G), alumina, bentonite and kaolin (desulfurizer H) as inorganic binders were 75%, 86 at 650 ° C, respectively. The regeneration of -90% and 93% showed better regeneration of the desulfurization agent using the mixed inorganic binder.

The wear index (AI) and modified wear index (CAI) of Akzo Fluidized Catalytic Cracking (FCC) catalysts used by oil companies in accordance with ASTM method are 23 and 17%, respectively, except AI desulfurization agent D prepared in the present invention. And CAI were 40-60% and 25-48%. The refinery's FCC process has a spatial velocity of 3.05-5.55 m / s, whereas a fluidized bed desulfurization process has a space flow rate of about 0.1 m / s. In the case of a fast fluidized bed desulfurization process similar to the FCC process, since the solid circulation density is considerably smaller than that of the FCC, the desulfurization agent according to the present invention has a relatively small loss of desulfurization agent due to friction and abrasion between desulfurization agents in the solid circulation process. Of course, it can be applied to the high-speed fluidized bed desulfurization process.

Test Example 3 Determination of Reaction Capacity of Desulfurization Agent

In this embodiment, the reaction ability of the desulfurization agent which can be repeatedly reused by regenerating sulfur desulfurization agent absorbed sulfur by hydrogen sulfide removal reaction in a fluidized bed desulfurization process was tested in a high-temperature, high-pressure fixed bed reactor.

The sulfidation and regeneration cycles were repeated in a high temperature, high pressure fluidized bed reactor (9.7 cm ID) at 500 ° C and 5 atm. The fluidization rate in the reactor was 0.05 m / s and the flow rate was 39 slpm. The simulated coal gas composition (Volume%) is 1% H ₂ S, 11.7% H ₂ , 19.0% CO, 6.8% CO ₂ , 0.4% CH ₄ , 10% H ₂ O, balance N ₂ . The regeneration reaction gas was air. The time until the 100 ppm hydrogen sulfide concentration leaked (breakthrough time) was 5-6 hours, and the sulfur absorption power up to this time was 11.3 wt%. Breakthrough time and sulfur uptake were maintained during the four cycle test. In addition, the sulfidation and regeneration reaction temperatures were carried out at 500 ° C. by the direct addition of regeneration enhancers. At 500 ° C., the regeneration reactions were smooth and complete.

As described above, the desulfurization agent according to the present invention has a high density, is concentrated in a narrow range of particles, exhibits excellent performance in desulfurization ability, etc., and also greatly improves abrasion resistance and durability, and thus refilling cost and lifetime of the desulfurization agent. It is expected that the economic effect of the extension of the desulfurization agent will be considerably great.In particular, the desulfurization agent due to separation of the regeneration accelerator due to physical damage during operation, unlike the case where the regeneration enhancer is supported by the preparation of the desulfurization agent to which the regeneration enhancer is added directly. The desulfurization process can be prevented in advance, and the desulfurization process and the regeneration reaction temperature are substantially the same since the desulfurization agent including the regeneration accelerator is manufactured, thereby simplifying the desulfurization process, thereby reducing the operation and maintenance costs.

In addition, the production method of the present invention is well dispersed by mixing, pulverizing and dispersing various kinds of desulfurizer solid raw materials with water and an organic additive, to prepare a homogeneous and stable flowable colloidal slurry, and then spray-drying molding to desulfurizer granules. By forming and then firing, it is possible to retain ideal properties as a desulfurization agent for fluidized beds.

In addition, the colloidal slurry according to the present invention is adjusted to pH with acid or base to prevent aggregation and coagulation occurring in the mixing process of the inorganic raw material, and also contains a dispersing agent, an organic binder, an antifoaming agent, etc. Solid raw materials are pulverized to an average of 1 μm or less, so that dispersibility and stability are improved, and thus, characteristics such as density of final desulfurization agent, uniform distribution of raw material particles, wear resistance, and desulfurization ability can be improved when desulfurization agent is manufactured by spray drying. .

Ultimately, the present invention is for regeneration when removing sulfides in various fuel gases or syngas produced by gasifying fossil fuel or other fuel such as coal in gasification combined cycle power generation and clean fuel of fuel cell. It can be effectively used as an absorbent or a catalyst. For example, high temperature refining technology is essential for IGCC, which produces electricity by gasifying inexpensive coal, to be competitive with other power generation methods. And the fuel cell), the present invention is expected because the market should be pioneered and led by high efficiency, low pollution (no pollution) and price down. In addition, since the desulfurization agent, which is a consumable product, will continue to be consumed even after the high-temperature purification technology is commercialized and commercialized, it is expected to have a great impact on the accompanying costs such as desulfurization supply and gasification combined cycle operation and management.

Therefore, the present invention not only contributes to the improvement of power generation efficiency (45% to 60%) by supplying desulfurization agents necessary for the purification of fuel or raw materials applied to new technologies such as footwear, and also reduces the environmental pollution caused by the use of fossil fuels. In addition, it is expected to have a great effect on the protection of catalysts and equipment used in the process of commercializing clean materials in other chemical processes, and to activate other catalyst manufacturing industries such as dry flue gas desulfurization catalysts.

Claims (80)

40-60 wt% of the precursor which can be converted into zinc oxide and zinc oxide as a desulfurization active ingredient; 4 to 10% by weight of transition metal oxides, sulfides or precursors thereof which can be converted to the Group 4-12 periodic table as a regeneration accelerator; 15-50% by weight of diatomaceous earth as a support; And Consists of 5 to 41% by weight of inorganic binder: Wear index of 90% or less High Temperature Dry Zinc System for Fluidized Bed Desulfurizer. The hot dry zinc system for a fluidized bed according to claim 1, wherein the desulfurization agent has an average particle size of 70 to 120 µm and a particle distribution of 30 to 400 µm. Desulfurizer. 3. The hot dry zinc system for fluidized bed according to claim 2, wherein the desulfurization agent is spherical substantially free of blow-holes and has a packing density of at least 0.80 g / cc. Desulfurizer. 3. The hot dry zinc system for a fluidized bed according to claim 2, wherein the desulfurization agent has an average particle size of about 100 mu m and a particle distribution of 40 mu m to 300 mu m. Desulfurizer. The hot dry zinc system for fluidized bed according to any one of claims 1 to 3, wherein the desulfurization agent has a desulfurization capacity of at least 10 g S / 100 desulfurization agent (ie, 10 wt%). Desulfurizer. The high temperature dry zinc system for fluidized bed according to any one of claims 1 to 3, wherein the wear index of the desulfurization agent is 60 or less. Desulfurizer. The hot dry zinc system for fluidized bed according to any one of claims 1 to 3, wherein the TGA regeneration at 650 ° C. of the desulfurization agent is 70% to 95%. Desulfurizer. The hot dry zinc system for fluidized bed according to claim 1, wherein the desulfurization component is zinc oxide (ZnO) and the regeneration enhancer is nickel oxide (NiO). Desulfurizer. The high-temperature dry zinc system for fluidized bed according to claim 1 or 8, wherein the zinc oxide (ZnO) has a particle size of 1 µm or less and a purity of 99% or more. Desulfurizer. The group of claim 1, wherein the transition metal compound is composed of vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, tin oxide, molybdenum oxide, sulfides thereof, and precursors thereof. High-temperature dry zinc-based fluid bed for at least one compound selected from Desulfurizer. The high temperature dry zinc-based desulfurization agent for fluidized bed according to claim 8, wherein the nickel oxide (NiO) has an average particle size of 1 µm or less. The high-temperature dry zinc-based desulfurization agent for fluidized bed according to claim 1, wherein the inorganic binder is at least one inorganic material selected from the group consisting of alumina sol, boehmite, bentonite, and kaolin. The high-temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 1 or 12, wherein the inorganic binder is composed of 5 to 15% by weight of alumina sol. The high-temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 1 or 12, wherein the inorganic binder is composed of 5 to 15% by weight of alumina sol and 2 to 10% by weight of bentonite. 13. The hot dry zinc-based desulfurization agent for a fluidized bed according to claim 1 or 12, wherein the inorganic binder comprises 5-15 wt% of boehmite, 2-10 wt% of bentonite, and 5-16 wt% of kaolin. High-temperature dry zinc system for fluidized bed consisting of the following steps Desulfurization Method: (A) 40 to 60% by weight of the precursor which can be converted to zinc oxide and zinc oxide as the desulfurization active ingredient, transition metal oxides of Groups 4-12 of the periodic table as regenerators, sulfides thereof or precursors that can be converted to them Providing a desulfurizing agent component comprised of 10% by weight, 15-50% by weight of diatomaceous earth as a support, and 5-41% by weight of an inorganic binder; (B) wet grinding after adjusting the pH by adding acid or base to the above-described desulfurizing agent component; (C) slurrying by adding a dispersant, an organic binder and an antifoaming agent to the wet milling mixture; (D) spray drying the slurry to form a desulfurizer granule; And (E) calcining the granules. 17. The hot dry zinc system for fluidized bed according to claim 16, further comprising the step (E) and (F) further measuring and evaluating the physicochemical properties of the desulfurizer granules. Method for preparing a desulfurization agent. 17. The hot dry zinc system for fluidized bed according to claim 16, wherein water is used for wet grinding in the step (B). Method for preparing a desulfurization agent. 19. The hot dry zinc system for fluidized bed according to claim 18, wherein the water is pure water of at least primary distilled water. Method for preparing a desulfurization agent. 17. The hot dry zinc system for fluidized bed according to claim 16, wherein the desulfurization component is zinc oxide (ZnO) and the regeneration enhancer is nickel oxide (NiO). Method for preparing a desulfurization agent. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16 or 20, wherein the zinc oxide (ZnO) has a particle size of 1 µm or less and the nickel oxide (NiO) has a particle size of 1 µm or less. The group according to claim 16, wherein the transition metal compound is composed of vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, tin oxide, molybdenum oxide, sulfides thereof and precursors thereof. High-temperature dry zinc-based fluid bed for at least one compound selected from Method for preparing a desulfurization agent. The method of claim 16, wherein the inorganic binder is at least one inorganic material selected from the group consisting of alumina sol, boehmite, bentonite, and kaolin. 24. The method for producing a high-temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16 or 23, wherein the inorganic binder is composed of 5 to 15% by weight of alumina sol. 24. The method of claim 16 or 23, wherein the inorganic binder comprises 5 to 15 wt% of alumina sol and 2 to 10 wt% of bentonite. 24. The method of claim 16 or 23, wherein the inorganic binder comprises 5-15 wt% of boehmite, 2-10 wt% of bentonite, and 5-16 wt% of kaolin. . 17. The compound according to claim 16, wherein said dispersant is at least one compound selected from the group consisting of polycarboxylate anionic surfactants, naphthalene formalin condensed sulfonates, sodium silicates, fatty acid polyhydric alcohols and fluorosurfactants. Method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed using. The method for producing a high-temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 27, wherein an anionic polycarboxylate and a fluorosurfactant are used as a dispersant. 29. The method for producing a high-temperature dry zinc-based desulfurization agent for fluidized bed according to claim 16, 27 or 28, wherein the amount of the dispersant used is 0.5 to 4 wt% based on the weight of the desulfurization agent solids. 29. The method for producing a high-temperature dry zinc-based desulfurization agent for fluidized bed according to claim 28, wherein the anionic polycarboxylate 1.5-3 wt% and the fluorosurfactant are used in an amount of 0.005-0.1 wt% based on the weight of the desulfurizing agent solids. . 17. The method of claim 16, wherein the organic binder comprises wax, gum, dextrin, starches, lignin, polyvinyl alcohol (PVA), polyglycol (PEG) and methyl cellulose. A method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed, which is at least one compound selected from the group. 32. The method of claim 31, wherein the organic binder is used in an amount of 1-8 wt% based on the weight of solids of the desulfurization agent. 33. The preparation of a high-temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, 31 or 32, wherein the organic binder is polyethylene glycol, and the amount of the organic binder is 1-2 wt% based on the solids weight of the desulfurization agent. Way. 17. The antifoaming agent according to claim 16, wherein the antifoaming agent is silica silicone, silicone, metal soap, amido, polyether, polyester, polyglycol, organophosphoric acid, higher alcohol, lactic acid fatty acid and oil-based polymer. A method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed, which is at least one compound selected from the group consisting of systems. 35. The method of claim 16 or 34, wherein the antifoaming agent is used in an amount of 0.05 to 1 wt% based on the weight of the desulfurizing agent solids. 36. The method for producing a high temperature dry zinc desulfurization agent for a fluidized bed according to claim 16, 34 or 35, wherein the antifoaming agent is a polyether antifoaming agent. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the acid for pH adjustment is an inorganic acid of nitric acid, hydrochloric acid or sulfuric acid, and the inorganic acid containing phosphorus is excluded. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the acid for pH adjustment is an organic acid of acetic acid, formic acid, oxalic acid or citric acid. The method of claim 16, wherein the pH adjusting base is ammonia water (NH ₄ OH), urea, or ethanolamine. 41. The method for producing a high temperature dry zinc-based desulfurization agent for fluidized bed according to claim 37, wherein the pH adjusting acid is nitric acid and the pH adjusting base is ammonia water. 17. The method of claim 16, wherein the wet-grinding step (B) of the high-temperature dry zinc-based desulfurization agent for a fluidized bed for grinding the average particle size of all inorganic raw materials to less than 1㎛ before and after mixing or during the slurrying step (C). Manufacturing method. 17. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the pH adjustment is adjusted to pH 1-7 when the pH adjustment is performed by addition of an acid. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the pH adjustment is adjusted to pH 7-14 when the pH adjustment is performed by addition of a base. 17. The method of claim 16, wherein the slurrying step (C) is formed into a fluid colloidal slurry through regrinding, mixing and dispersing of the desulfurizing agent component, redispersion, homogenization and stabilization. . 45. The method for preparing a hot dry zinc-based desulfurization agent for a fluidized bed according to claim 44, wherein the addition of the organic binder in the slurrying step (C) is followed by slow stirring (up to 1200 rpm). The method of claim 16, wherein the wet grinding step (B) is added to the water so that the solid concentration of the final slurry in the slurrying step (C) is 30 to 50% by weight, the water evaporated during the grinding and dispersion process is a slurry Method for producing a high-temperature dry zinc-based desulfurization agent for a fluidized bed supplemented in the step (C). 17. The method of claim 16, wherein the concentration of the slurry is adjusted before aging of the slurry in mixing and dispersing all the solid raw materials and adding the organic binder and the antifoaming agent to control the properties of the final slurry. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the pH of the mixture or slurry is adjusted to 10 or less. 17. The method of claim 16, wherein the pH is adjusted to between 1-7 at the beginning of milling and mixing. The method of claim 16, wherein the pH of the mixture or slurry before addition of zinc oxide is adjusted to 3-4 using an acid. 51. The method of any of claims 48 to 50, wherein the pH is adjusted to between 6-8 when zinc oxide is initially mixed. 51. The method of any of claims 48-50, wherein the pH is adjusted to between 3-5 in the state prior to addition and mixing of the alumina sol. 53. The method of claim 52, wherein the zinc oxide is mixed and dispersed to slurry before adding the alumina sol, and the pH of the slurry is adjusted to 9 or less. 51. The hot dry zinc system for fluidized bed according to any one of claims 48 to 50, wherein bentonite is used in an amount of 2 to 10% by weight to improve mixing and dispersibility in the (B) wet grinding step and (C) slurrying step. Method for preparing a desulfurization agent. The method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the viscosity of the slurry is adjusted in the slurrying step (C) using water, an acid, or a base, a dispersant alone, or any combination thereof. The method of claim 16, wherein in the slurrying step (C), an organic binder and an antifoaming agent are added to the fluidized slurry in which all the desulfurizing agent components are mixed, dispersed, and homogenized. The method of claim 16, wherein the concentration of the slurry in the slurrying step (C) is adjusted to 30-50 wt%, the pH is 5-9, and the viscosity is 300-1600 cps. The method of claim 16, wherein the concentration of the slurry in the slurrying step (C) is adjusted to 30-50 wt%, pH 7-14, and the viscosity is 300-1600 cps. 59. The process of claim 57 or 58, wherein the slurry concentration is adjusted to 35-45 wt%, pH 6-8, viscosity 350-900 cps. 59. The slurry of claim 57 or 58, wherein water is added to lower the slurry's concentration or viscosity when the slurry's concentration or viscosity is high, and when the slurry is low, acid or base is added to increase the viscosity of the slurry and The final viscosity of the method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed is readjusted using a dispersant. 61. The method of claim 60, wherein when an acid or base is added to the slurry in the final stage to increase the viscosity of the slurry, the slurry is added in the pre-aging stage of the slurry. 59. The process of claim 57 or 58, wherein the increase in viscosity of the slurry is carried out simultaneously using 0.005-0.1 wt% of a TBS dispersant and an acid or base. The method of claim 16, wherein in the slurrying step (C), a pH of the mixture or slurry is adjusted to a base of 7-14 to form a final slurry to form a hot slurry zinc-based desulfurization agent for a fluidized bed. 66. The method of claim 63, wherein the inorganic binder and the support are mixed with water so that the slurry concentration is 30-50 wt%, and the pH of the mixture is adjusted to 9-12 with a base, followed by addition of dry mixed zinc oxide and nickel oxide. Method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed to form a slurry. The slurry of claim 16, wherein the slurry is uniformly stabilized by performing an aging process of the slurry, which is left for at least 2 hours while stirring the slurry before and after finally controlling the properties of the slurry in the slurrying step (C). Method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed. The method for producing a hot-drying zinc-based desulfurization agent for a fluidized bed according to claim 16, wherein the foreign matter or the aggregated impurities in the slurry are sieved and removed during or after the slurrying step (C). 67. The method according to claim 66, wherein the impurities are sieved and removed before and after the slurry aging process before spray drying the slurry. The regeneration step of the granules according to claim 16, wherein the granules having the irregular shape, the aggregate shape, or the small particle size determined as defective before the firing step (D) are selected and returned to the slurrying step (C). Also a method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed comprising. The method of claim 16, wherein the firing step (E) is performed at a temperature of 600-1000 ° C. for at least 2 hours at a temperature increase rate of 5 ° C./min in an air atmosphere. The preliminary drying step according to claim 69, wherein, prior to the firing step (E), the granules as the desulfurizing agent prepared in the spray drying molding step (D) are dried in a reflux dryer in an air atmosphere of 110 to 150 ° C. In addition, a method for producing a high temperature dry zinc-based desulfurization agent for a fluidized bed. 71. The process of claim 69 or 70, wherein the calcining step is carried out at a temperature between 650-850 ° C. 72. The method for preparing a high temperature dry zinc-based desulfurization agent for a fluidized bed according to claim 71, comprising the step of removing and maintaining a certain time at a specific temperature between 180 and 650 ° C. to remove organic matter in the slurry. 40 to 60% by weight of zinc oxide as a desulfurization active ingredient and its precursor which can be converted into zinc oxide, 4 to 10% by weight of transition metal oxides of the periodic table Group 4-12 as regenerators, sulfides or precursors to be converted into them With respect to 100 parts by weight of a desulfurizing agent component composed of 15 to 50% by weight of diatomaceous earth as a support and 5 to 41% by weight of an inorganic binder, 0.5 to 4 parts by weight of dispersant, 1 to 8 parts by weight of organic binder, and 40 to 200 parts by weight of water as a dispersant. The slurry has a concentration of 30-50 wt%, a pH of 5-14, and a viscosity of 300-1600 cps. Flowable colloidal slurry for producing hot dry zinc-based desulfurization agent for fluidized bed. 74. The flowable colloidal slurry according to claim 73, wherein said slurry further comprises 0.05 to 1 part by weight of an antifoaming agent. 75. The flowable colloidal slurry according to claim 73 or 74, wherein the slurry has a concentration of 35 to 45% by weight and a viscosity of 350 to 950 cps. 76. The flowable colloidal slurry of claim 75 wherein the slurry has a pH of 5-9. 76. The flowable colloidal slurry of claim 75 wherein the slurry has a pH of 9-12. Wear index 20% or less of AI (Air Jet Index), average particle size 70 ~ 120㎛, particle distribution 30 ~ 400㎛, filling density 0.85 ~ 1.05g / cc, 13.5 ~ 17 g S / (100g desulfurization agent) Hot-drying zinc-based fluidized bed prepared by the process according to claim 16 having a TGA reproducibility of 70% to 95% at 650 ° C. Desulfurizer. High temperature dry zinc system for fluidized bed prepared from the slurry according to claim 73 Desulfurizer. Zinc-based according to claim 1 applied to the fixed bed, moving bed, fluidized bed or high-speed fluidized bed desulfurization process Desulfurizer.