KR20110047832A - Zinc oxide-based desulfurization sorbent prepared by spay-drying method and method for producting thereof - Google Patents

Abstract

PURPOSE: A zinc oxide-based desulfurizing agent and a method for manufacturing the same are provided to obtain the strength and the abrasion resistance of the agent using a spray-drying method. CONSTITUTION: A zinc oxide-based desulfurizing agent is obtained by forming a solid desulfurizing agent into slurry and undergoing a spray-drying method. The sold desulfurizing agent is composed of active component, support, regenerating agent, and inorganic binder. The active component is zinc oxide. The support is synthesized calcium silicate. The regenerating agent is nickel oxide. The inorganic binder includes one selected from pseudo boehmite, hydrotalcite, bentonite, and kaolin.

Description

Zinc-based desulfurization agent formed by spray drying method and manufacturing method thereof {ZINC OXIDE-BASED DESULFURIZATION SORBENT PREPARED BY SPAY-DRYING METHOD AND METHOD FOR PRODUCTING THEREOF}

The present invention relates to a zinc-based desulfurization agent, and more particularly, to a zinc-based desulfurization agent formed by a spray drying method to improve wear resistance.

In general, hot gas desulfurization produces gas by synthesizing fuels containing carbon such as solid fossil fuels such as coal, petroleum coke, and industrial wastes, and generating power generation, hydrogen production, It refers to the gas stream clean up of syngas at high temperature and high pressure before use in chemical raw material production, transportation fuel production, etc.

Desulfurization agent used in high temperature dry desulfurization process can also be used to remove sulfur components in other chemical industry processes such as fuel refinement of fuel cell, coal liquefaction process, and ultimately to generate sulfur oxides (SOx) which cause acid rain. Can be used to prevent

Conventionally, zinc-based desulfurization agents have been developed for the purpose of applying particles to a fixed bed or a moving bed desulfurization process by preparing particles after pasting by an extrusion molding method and a granulation method. In addition, a fluidized bed, in particular a high speed fluidized bed desulfurization process, has been proposed to improve the prior art. Fluidized bed process has the advantage of easy contact temperature control and continuous operation of the absorption and regeneration reaction due to excellent contact between the gas and the solid.

U.S. Patent No. 5,281,445 (January 25, 1994) assigned to Khare of Phillips Petroleum is a mixture of zinc oxide, diatomaceous earth, and alumina sol, extruded, and then fired to form a nickel oxide precursor. A desulfurization agent for applying to a fixed bed and a moving bed desulfurization process after supporting and firing is disclosed. U.S. Patent No. 5,439,867 (August 8, 1995), issued to Khare of Phillips Petroleum, describes the use of a granulator to apply a desulfurization agent with similar composition to the fluidized bed desulfurization process. A method is disclosed.

However, in order to apply the desulfurization agent prepared by the conventional method to the fluidized bed process, it is inexpensive because it has to go through the process of controlling the size of particles such as grinding and screening, and the desulfurization agent has an irregular shape by pulverization and is applicable to the fluidized bed desulfurization process. In this case, the wear loss is large and problems may occur with fluidization or solid circulation.

U.S. Patent No. 6,056,871 (May 2, 2000) granted to Khare et al. Is almost the same as U.S. Patent No. 5,439,867, but dry mixes the desulfurizing agent raw material, and thus nickel oxide (NiO) precursor. The present invention discloses a method of preparing a desulfurization agent with a granulator by supporting a desulfurizer dough. However, in order to repeatedly use the desulfurization agent in the absorption and regeneration reaction in the fluidized bed desulfurization process at high temperature and high pressure, it has not only high sulfur absorption capacity but also spherical shape, particle size, size distribution and packing density suitable for fluidization. Although the conventional techniques do not meet these requirements, there is a problem that is particularly unsuitable as a mass production technique.

The present invention has been made in accordance with the above requirements, the object of the present invention is to use a spray drying technology, suitable for the fluidized bed or high speed fluidized bed desulfurization process (shape), particle size (size), To provide a solid regenerable sorbent having size distribution, mechanical strength or attrition resistance, reactivity and wear resistance

Another object of the present invention is to provide a zinc-based desulfurization agent comprising zinc oxide as an active ingredient as a substance capable of selectively reacting with hydrogen sulfide contained in syngas to efficiently clean-up hydrogen sulfide.

Another object of the present invention is to uniformly distribute the active ingredient in the desulfurization agent particles to increase the utility of the active ingredient, to provide a wide specific surface area required for the reaction and to be used in a fluidized bed or a fast fluidized bed desulfurization process. It is to provide a zinc-based desulfurizing agent comprising a support such as calcium silicate and hydrotalcite and inorganic binders to give the strength.

The zinc-based desulfurization agent formed by the spray drying method of the present invention is a zinc-based desulfurization agent which removes sulfur components from the synthesis gas generated by gasification of a fuel containing carbon, and the solid desulfurization agent is slurried and manufactured by spray drying. The solid desulfurizer raw material is composed of 30 to 60 wt% of active ingredient, 30 to 60 wt% of support, 5 to 15 wt% of regeneration enhancer, and 5 to 15 wt% of inorganic binder.

The active ingredient may be zinc oxide, the support may be synthetic calcium silicate, and the regenerative promoter may be nickel oxide.

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

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

The zinc-based desulfurizing agent, the average particle size is 70 to 150μm, the particle distribution is 30 to 300μm, the shape of the particles are spherical, the packing density is 0.7 g / cc, it is preferable that the wear index is molded to be 40% or less. Do.

The flame retardant desulfurization agent has a sulfur absorption capacity of 10g S / 100 g or more than 10 wt% compared to the solid desulfurizer raw material.

An organic additive comprising 0.5 to 10 wt% anionic dispersant, 0.1 to 1 wt% antifoaming agent, and 0.5 to 5 wt% organic binder of the weight of the solid desulfurization agent raw material may be added so as to slurry the solid desulfurizing agent raw material.

The organic binder includes at least one of polyvinyl alcohol-based, polyllycol-based, and methyl cellulose-based.

The method for preparing zinc-based desulfurizer formed by the spray drying method of the present invention comprises a) 30 to 60 wt% of active ingredient, 30 to 60 wt% of support, 5 to 15 wt% of regeneration enhancer, and 5 to 15 wt% of inorganic binder in solid desulfurizer raw material. Providing a constructed solid desulfurizer feedstock; b) a slurrying step of adding the solid desulfurizer raw material to water, mixing and wet grinding to prepare a slurry; And c) a spray drying step of forming the slurry by a spray drying method to prepare a desulfurization agent granulating agent.

Step b) includes mixing the organic additives including the dispersant and the organic binder into the slurry to disperse and homogenize the solid desulfurizer raw material contained in the slurry.

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

Since the zinc-based desulfurization agent of the present invention is manufactured by molding a slurry using a spray dryer and performing dry firing, the synthesis gas generated by gasifying fossil fuel is converted into coal gas combined cycle (IGCC), fuel cell synthesis gas, and compound raw material. For use, it may be used in a fluidized bed desulfurization process to remove sulfur components such as hydrogen sulfide contained in syngas under high temperature and high pressure conditions.

Zinc-based desulfurization agent of the present invention can operate in the 350 ~ 650 ℃ range can use the synthesis gas generated in the gasifier with a minimum heat loss and does not generate secondary environmental pollutants such as waste water, economically purifying the synthesis gas There is an advantage to this.

The desulfurization agent of the present invention is included in the synthesis gas and in the nature of free flow solid sorbent particles having a shape, particle size and particle distribution suitable for fluidized bed or high velocity fluidized bed processes. Desulfurization agents are prepared using spray drying techniques to produce solid desulfurization agents that react efficiently with hydrogen sulfide.

Specifically, the present invention forms a desulfurizer having improved abrasion resistance by molding and drying and firing a slurry prepared by the composition of the solid desulfurizer raw material, the formulation of the solid desulfurizer raw material, and the homogenizing. The slurry is mixed with water by adding organic additives such as solid desulfurizer raw material, dispersant (solid raw material, particle dispersion and fluidity control), antifoaming agent (prevents the deformation of particles due to foam during spray drying molding process) and organic binder. Can be prepared.

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

The active ingredient may be metal oxides capable of efficiently removing the sulfur impurities contained in the synthesis gas by selectively reacting with hydrogen sulfide contained in the synthesis gas to generate metal sulfide. The active ingredient may be 30 to 60 wt% (weight percent by weight) of the total solid desulfurizer feedstock, preferably the active ingredient is 25 to 40 wt% in the total solid desulfurizer feedstock.

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

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

Solid desulfurizer raw material is to distribute the active ingredient well in the desulfurizer particles to increase the usefulness of the active ingredient, and to provide a large specific surface area required for the reaction, ceramics containing alumina and silica (ceramic) ), 30 to 60 wt% of natural or synthesized zeolite.

The support may be a synthetic calcium silicate series containing silicon dioxide (SiO ₂ ) as a main component. Synthetic calcium silicate may be 30 to 60 wt% of the total solid desulfurizer feed.

Synthetic calcium silicate that can be preferably used in the present invention, commercial synthetic calcium silicate Class C (Micro Cel-C, pH = 10, 50.0%, SiO _{2 with} an average particle diameter of 70 μm of Celite Corp.) , 1.8% Al ₂ O ₃ , 0.6% Fe ₂ O ₃ , 27.0% CaO, 0.5% MgO, 1.3% Na ₂ O + K ₂ O, 18.0% Ignition loss) or E grade (Micro Cel-E, pH = 8.4 , 47.0%, SiO ₂ , 2.5% Al ₂ O ₃ , 0.7% Fe ₂ O ₃ , 32.0% CaO, 0.6% MgO, 1.2% Na ₂ O + K ₂ O, 16.0% Ignition loss).

The inorganic binders are densely packed between the desulfurizer raw materials to prepare a high-density desulfurizer and serve to improve the strength of the desulfurizer by binding the active ingredient and the support well.

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

Examples of alumina binders include boehmite, aluminum oxyhydroxide, or ALOOH, which has properties similar to alumina sol in aqueous solutions. Preferred examples include pseudo-Boehmit (Versal 900, size 60-65 μm) from LaRoche Chemicals.

Hydrotalcite may be used as the ratio of magnesium oxide to calcium oxide 0.3 ~ 0.7, preferably, the ratio of magnesium oxide to calcium oxide is 0.5.

Kaolin, a clay binder, can use all types of kaolin, with no particular limitation. Kaolin that may be preferably used in the present invention is kaolin (ASP-200: 38.5% Al ₂ O ₃ , 45.4% SiO ₂ , 0.2% Na ₂ O, 1.6% TiO ₂ , 0.03% CaO, 0.5) from Engelhard. % Fe ₂ O ₃ , 0.02% MgO, 0.15% K ₂ O, 0.2% Ignition loss 13.6%).

Bentonite, a clay binder, may use any commercial bentonite, including natural sodium bentonite and synthetic sodium bentonite, without particular limitation. Bentonite that can be preferably used in the present invention is synthetic sodium bentonite (63.1% SiO2, 16.6% Al2O₃, 3.28% Fe2O₃, 3.07% CaO, 2.82% MgO, 3.06% Na2O, 8.11% moisture May be).

The regeneration enhancer may be a transition metal oxide of Group 4 to 12 of the periodic table, a sulfide thereof, or any type of transition metal that can be converted thereto, and there is no particular limitation thereto. Regeneration enhancers that may be preferably used in the present invention may be nickel oxide (NiO), and particularly preferred examples thereof include commercial nickel oxide (green, <99%, -325mesh, Japanese Chemical industry Co. Ltd) and commercial nickel oxide (green, 77.3% Ni, <0.8 μm, Seido Chemical Industry Co Ltd., Japan).

Organic additives may be used to homogenize the solid desulfurizer raw materials in the process of preparing the solid desulfurizer raw materials according to the present invention into a colloidal slurry. The organic additive may be composed of a slurry fluidity improver, an antifoaming agent, and an organic binder, which is a dispersant or a kind of dispersant. When only the solid desulfurizing agent raw material itself is mixed with water, there is a problem that it is difficult to prepare a mixing and colloidal slurry due to less plasticity and difficult to disperse. The organic additives solve this problem.

Dispersant is a high concentration of the slurry by adjusting the pH of the slurry, the charge, dispersion, and aggregation of the surface of the slurry, it is possible to use an anionic dispersant having a good compatibility and there is no particular limitation. The dispersant may be used in an amount of 0.1 to 10 wt% of the total weight of the solid desulfurization raw material, and preferably 0.5 to 10 wt%. The anionic dispersant may be an anionic polycarboxylate dispersant. Anionic polycarboxylate dispersants are, for example, ashless and have excellent dispersibility of ceramics at pH 4-11 of the slurry, making them suitable for the production of high concentration slurries of 25-40 wt%. Cerasperse 5468-CF (40%, pH = 6.8, viscosity 85 cps, specific gravity 1.15, hereinafter referred to as 'SN5468 dispersant').

The defoamer serves to remove bubbles generated in the slurry to which the dispersant and the organic binder are applied, and may be a metal soap-based and polyester-based nonionic surfactant. As a preferred example, the antifoaming agent may be HS-deformer 551 of Sanopco Co., Ltd. which is a polyether (hereinafter referred to as HS551 antifoaming agent). The amount used is preferably 0.1% or less of the weight of the added organic binder, more preferably in the range of 0.1 to 1 wt% based on the weight of the solid desulfurization agent raw material. In addition, the HS551 antifoaming agent 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 after the addition of the organic binder before the spray drying molding. If necessary, a small amount may be added before the process of pulverizing and dispersing the raw material in the cobal mill (high energy ball mill) of Primas, before the high-speed stirring or during the high-speed stirring to increase the grinding and dispersing efficiency.

The organic binder is a mixed organic binder composed of polyvinyl alcohol (PVA), poly glycol (PEG), methyl cellulose (methyl celluloses) or a combination thereof. As a preferred example, a low viscosity modified polystyrene glycol (Sannopco HS-BD-20A, 45%, viscosity 800 cps, pH 8, specific gravity 0.99, hereinafter referred to as 'PEG') can be used, based on 100 total solids. And 0.5 to 5 wt%. The organic binder added in the slurry preparation step imparts plasticity and fluidity of the slurry and ultimately gives strength to the desulfurizer particles granulated by spray-drying molding, thereby preventing the handling of the granules prior to predrying and firing. Make it easy.

The zinc-based desulfurizer production method according to the present invention includes a desulfurizer raw material providing step, a slurrying step, a spray drying step and a firing step.

The desulfurizer raw material providing step is to provide the solid desulfurizer raw material.

In the slurrying step, the solid desulfurizer raw material is added to water according to the composition and mixed, the organic additive is added and mixed (mixing process), and the particles of the mixed slurry are wet milled (comminution). (The grinding process) and homogenizing (dispersing) the particles of the slurry by dispersing.

The pulverization process is a process of pulverizing the solid desulfurizer raw material into particles of 1 μm or less. Grinding processes can be air-jet mills, roller mills, ball mills, attrition mills, vibratory mills, planetary mills, or beads Wet milling techniques can be used to mechanically grind the solid desulfurizer feedstock using a variety of grinding equipment such as a bead mill. Wet grinding technology has a high grinding effect and no blowing of particles generated during dry grinding.

In the present embodiment, the wet grinding equipment will be described by using a case of using a high energy bead mill. High energy bead mills have a gap between the rotor and the stator, which can be charged with 60-80 vol% of the volume of the grinding equipment vessel to achieve particle grinding and slurry homogenization. Preferably, the grinding media is filled to 65-75 vol% of the volume of the grinding equipment vessel. The grinding media use yttrium stabilized zirconia beads to prevent contamination of the desulfurizer feedstock by wear. The size of the ball is preferably a single size ball between 0.3 mm and 1.25 mm.

In the grinding process, two to three wet milling processes may be performed to make the particles of the solid raw material included in the slurry into particles of 1 μm or less. In a plurality of wet grinding processes, distilled water or a modifier (or dispersant) and an antifoaming agent may be added to control the concentration or fluidity of the slurry so that the slurry can be transported through a pump for the next grinding process.

Organic slurry is added to all the prepared slurries, and if necessary, dispersant and antifoaming agent are added or water is added to adjust the concentration of the slurry to adjust the properties of the slurry. Then, after removing the foreign matter through the aging (aging) process, the slurry from which the foreign matter is removed is transferred to a pump and transported to a spray dryer. Organic binders can be used a number of organic binders, but modified polyethylene glycol (polyethylene glycol, PEG) 0.5 ~ 5 vol% was used. There is no particular restriction on the flowability of the final slurry to be delivered to the spray dryer and any viscosity that can be pumped is possible. In this example, the viscosity of the slurry was 300 cP or more.

If the size of the used solid desulfurizing agent raw material particles are several micrometers or less in size, the grinding process may be omitted. Removal of foreign matter contained in the slurry may be performed by a vacuum sieve process. Foreign objects include dust, dried slurry mass, large particle raw materials, and the like.

The spray drying step is a step of forming a stable, homogeneous, dispersed flowable slurry through a spray dryer to form a spherical desulfurizer green body through a slurry drying step. Operation conditions of the spray dryer can be selected so that the particle size distribution of the desulfurization agent is 30 ~ 400㎛. Factors affecting the shape, size and size distribution of the desulfurizer particles, the morphology or texture of the desulfurizer, and the concentration and viscosity of the slurry, the degree of dispersion, Amount, drying capacity and temperature of the spray dryer. These parameters depend on the spray type (tomizer or nozzle) of the spray dryer.

Although there is no particular restriction on the spray dryer, the spray dryer used in the spray drying stage is designed by itself and dried by a heater having a drying chamber of 2m in height and 1m in diameter and including a conical barrel of 2.94m in length. Spray dryer. The spray dryer is designed to be spray dried in a counter-current fountain configuration using a centrifugal pressure nozzle installed at the bottom.

It is necessary to increase the residence time of the particles sprayed in the dryer in order to prepare the average particle of the desulfurizer granulator in the spray dryer to a size of about 70 to 150 μm. In order to increase the residence time of the sprayed particles, it is preferable to spray-dry in a counter-current fountain configuration using a centrifugal pressure nozzle installed under the spray dryer. The preferred operating conditions of the spray dryer are an injection pressure range of 6 to 15 kg / cm ² (10 kg / cm ² ), an internal diameter of 0.51 mm of the pressurized nozzle, a spray dryer inlet temperature of 260 to 300 ° C., and a spray dryer outlet temperature of 110 to 130 ° C.

The firing step is a step of drying the granules of the desulfurization agent formed in the spray drying step in a reflux dryer of 110 ~ 150 ℃ air atmosphere for 2 hours or more. The dried granules are calcined for two hours or more at a temperature between 350 ° C. and 1000 ° C. at an elevated temperature of 2 ° C./min in an air atmosphere to prepare a final desulfurization agent. Specifically, the firing step is heated to a final firing temperature between 350 ~ 850 ℃ firing for more than two hours. In order to efficiently remove the solvent and the organic additive in the firing process, it is preferable to maintain the temperature at 350 ° C to 850 ° C after maintaining the temperature at 200 ° C and 500 ° C for 1 to 2 hours, respectively.

The final desulfurization agent prepared through the desulfurization raw material providing step, the slurrying step, the spray drying step, and the firing step is a particle having a spherical shape, and the average particle size of the particles is 60 to 180 μm, more Specifically, it is 70-150 μm, the particle distribution is 30-400 μm, more specifically 30-300 μm, and the packing density is 0.7 g / cc or more, more specifically 0.8 g / cc.

Hereinafter, preferred embodiments and test examples of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. However, these are provided only for describing the present invention in detail, and the scope of the present invention is not limited thereto.

Example 1 Preparation of Desulfurization Agents A to D

In this example, 46.7% of zinc oxide (ZnO) was used as the active ingredient in a total of 2 kg of solid desulfurization agent, 23.3 ～ 32.6% of the synthetic calcium silicate of grade C (Microcel-C) and grade E (Microcel-E) as the support, and the inorganic binder. This is an example of manufacturing desulfurization agent with 14 ~ 23.3% and nickel oxide (NiO) as 6.7% as an enhancer.

Raw materials were added sequentially or at a time so that the slurry concentration was about 35%, and a dispersant and a defoamer were added and mixed at an amount of 10,000 to 25,000 rpm and mixed with an emulsifying homogenizer. . As a mixed slurry, a colloidal slurry was prepared using a high energy bead mill over a second stage.

About 1.16 wt% of polyethylene glycol (PEG; PolyEthylene Glycol) organic binder (SannopcoKorea, HS-BD-20A) was added to the colloidal slurry, and the mixture was stirred well, aged for at least 2 hours, and sieved to remove foreign substances. The concentration of the final slurry was adjusted to a range of about 26.5 ~ 34.7 wt% and the pH of the final slurry was adjusted using c-NH ₄ OH at a room temperature of 8.95 ~ 10.29.

Moreover, after adjusting the viscosity of the slurry to 520-1490 cP at room temperature, it spray-dried. The desulfurization agent granules thus manufactured were pre-dried at 120 ° C. for 2 hours or more in a dryer, and then calcined at 650 ° C. for 2 hours or more in a furnace to prepare a desulfurization agent. Before reaching the calcination temperature, the temperature was maintained at 200 ° C., 400 ° C. and 500 ° C. for about 1 hour, and the temperature increase rate was about 5 ° C./min. The desulfurization agents thus prepared are designated as desulfurization agents A, B, C and D according to the amount of the active ingredient.

Table 1 summarizes the composition of the desulfurization agent prepared in accordance with the present embodiment and the characteristics of the fluid-colloidal slurry to improve the wear resistance.

division Desulfurizer A Desulfurization agent B Desulfurizer C Desulfurizer D

Desulfurization

ZnO / wt% 46.7 46.7 46.7 46.7 Synthetic calcium silicate Class C / wt% 23.3 23.3 - 32.6 Synthetic Calcium Silicate Class E / wt% - - 32.6 - Pseudo-boehmite / wt% 9.3 - 9.3 9.3 Hydrotalcite / wt% - 9.3 - - kaoline 9.3 9.3 - - Bentonite / wt% 4.7 4.7 4.7 4.7 NiO / wt% 6.7 6.7 6.7 6.7 base c-NH4OH / (ml / kg solids) 15 135 37 33 Organic additives SN5468-CF / wt% 1.05 7.8 2.1 2.8 Organic binder / wt% 1.16 1.16 1.16 1.16 Antifoam / wt% 0.30 0.25 0.10 0.10
Slurry Characteristics
Solid content / wt% 29.2 26.5 30.4 34.7 Final pH 9.76 8.95 10.29 9.97 Final η / cPs 520 1490 680 560 Zeta potential ζ / mV - - -129 -32

Example 2 Physicochemical Properties of Desulfurization Agents A to D

In this example, the characteristics of the shape, size and distribution of the desulfurization agent, the packing density (ASTM D4164-88), BET, reactivity, etc. are measured without screening the prepared desulfurization agent. The initial reactivity and sulfur absorption capacity were simulated coal gas (10.4 vol% H2, 16.8 vol% CO, 6.1 vol% CO2, 10 vol% vapor, 3 vol% H2S, N2 Balance) at 500 ° C and atmospheric pressure. It is the result measured by STA-1500. The sample used for the test weighs 10 mg and the total flow rate is 50 ml per minute.

Table 2 summarizes the initial physicochemical properties of the desulfurizers that meet the physical conditions, and FIGS. 1 to 4 are scanning electron microscope (SEM) images of the desulfurizers A, B, C and D, respectively. It can be seen that the shape, particle size, and distribution of the desulfurization agent manufactured as shown in FIGS. 1 to 4 of the present embodiment satisfy the conditions required for a commercial fluidized bed desulfurization process.

division Desulfurizer A Desulfurizer B Desulfurizer C Desulfurizer D shape rectangle rectangle rectangle rectangle Average particle size / μm 112 86 111 92 Particle Size Distribution / μm 38-250 38-150 38-250 38-150 Fill density (g / cc) 1.03 1.18 0.80 0.84 BET / (m ² / g) 15 6 39.3 10.4 TGA Sulfur Absorption / (wt%), Primary 15.5 11 19.6 13 TGA sulfur absorption capacity / (wt%), 2nd 15.7 11 16 12 Regeneration /%, 650 ℃ 100 100 82 92

Example 3 Wear Resistance Properties of Desulfurization Agents A to D

In this example, attrition resistance of the desulfurization agent formed by spray drying was measured. Wear resistance is one of the most important indicators required in fluidized or fast fluidized bed desulfurization processes. The wear resistance of the prepared desulfurization agent was measured in accordance with the test method and sequence proposed in the specification by using a 3-hole attrition tester manufactured according to the American Society for Testing Materials (ASTM) D5757-95. Measured accordingly.

The calculation method shows the modified wear index (CAI) calculated by excluding the 5-hour wear index (AI) suggested by ASTM and the fine powder collected during the first hour of the fine powder collected for 5 hours. In addition, the wear rate (AR) divided by the amount of fine powder worn over 5 hours (AR) and the corrected wear rate were also presented. The results of measuring wear resistance of 50 g of desulfurizing agent for 5 hours at a flow rate of 10 liters per minute are summarized in Table 3.

division Desulfurizer A Desulfurizer B Desulfurizer C Desulfurizer D Wear resistance, AI /% rectangle rectangle rectangle rectangle Average particle size / μm 112 86 111 92 Particle Size Distribution / μm 38-250 38-150 38-250 38-150 Fill density (g / cc) 1.03 1.18 0.80 0.84

In the present invention, it has been shown that a high-strength desulfurization agent suitable for a fluidized bed process capable of removing sulfur components contained in syngas using spray drying techniques. This manufacturing method is a competitive technique because of easy mass production and relatively low cost.

As shown in Table 2, desulfurization agents A to D have physical and chemical characteristics suitable for fluidized bed or high speed fluidized bed desulfurization processes. In particular, the wear resistance is greatly improved, so that the loss of desulfurization agent due to abrasion due to fast solid circulation in the fluidized bed process can be reduced, so that the desulfurization agent can be reduced. It is economical because it can be compact.

When designing a fluidized bed or a high-speed fluidized bed process, it is designed based on volume rather than weight of desulfurization agent. Therefore, the higher the packing density of the desulfurization agent, the greater the mass flow rate of the desulfurization agent, which makes it easier to control the reaction temperature in the process. Can be reduced.

In addition, the present invention can significantly reduce the environmental pollution caused by the use of fossil fuels and contribute to the improvement of generation efficiency (45-69%) of the coal gasification combined cycle power generation by supplying the desulfurization agent necessary for purification for coal gasification combined cycle (IGCC) in the future. have. It can also provide dry refining technology for the production of synthetic oil through fuel cell fuel and coal liquefaction.

Although the detailed description of the present invention described above has been described with reference to a preferred embodiment of the present invention, a person skilled in the art without departing from the spirit and scope of the present invention described in the claims to be described later It will be understood that various modifications and variations can be made in the present invention. Therefore, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification but should be defined by the claims.

1 to 4 is a scanning electron micrograph of the zinc-based desulfurization agent prepared according to an embodiment of the present invention.

Claims (13)

A zinc-based desulfurization agent that removes sulfur from the synthesis gas produced by gasification of a fuel containing carbon, which is prepared by slurrying a solid desulfurizer raw material and forming it by a spray drying method. The solid desulfurization agent raw material is a zinc-based desulfurization agent formed by a spray drying method consisting of 30 ~ 60wt% of the active ingredient, 30 ~ 60wt% of the support, 5 ~ 15wt% of the regeneration enhancer, and 5 ~ 15wt% of the inorganic binder. The method of claim 1, The active ingredient is zinc oxide, the support is a synthetic calcium silicate, the regenerator is nickel oxide zinc-based desulfurization agent molded by a spray drying method. The method of claim 1, wherein the inorganic binder, Zinc-based desulfurization agent formed by a spray drying method comprising at least one selected from pseudo-boehmite, hydrotalcite, bentonite and kaolin. The method of claim 3, wherein the hydrotalcite, A zinc-based desulfurization agent formed by the spray drying method having a calcium oxide to magnesium oxide ratio of 0.3 to 0.7. The method of claim 1, wherein the zinc-based desulfurization agent, A zinc-based desulfurization agent molded by the spray drying method, wherein the average particle size is 70 to 150 μm and the particle distribution is 30 to 300 μm. The method of claim 1, wherein the zinc-based desulfurization agent, A zinc-based desulfurization agent formed by a spray drying method in which the particles have a spherical shape and a packing density of 0.7 g / cc. The method of claim 1, wherein the zinc-based desulfurization agent, Zinc-based desulfurization agent formed by spray drying method which is formed with a wear index of 40% or less. The method of claim 1, wherein the zinc-based desulfurization agent, Zinc-based desulfurization agent formed by the spray drying method having a sulfur absorption capacity of 10g S / 100 g or more than 10 wt% compared to the solid desulfurization raw material. The method of claim 1, Molded by a spray drying method in which an organic additive consisting of 0.5 ~ 10wt% anionic dispersant, 0.1 ~ 1wt% defoamer, 0.5 ~ 5wt% organic binder of the weight of the solid desulfurizer raw material is added to slurry the solid desulfurizer raw material to be homogenized. Zinc Desulfurization Agent. The method of claim 9, wherein the organic binder, Zinc-based desulfurization agent molded by a spray drying method comprising at least one of polyvinyl alcohol-based, polyl- lycol-based and methyl cellulose-based. a) providing a solid desulfurizer raw material composed of 30 to 60 wt% of active ingredient, 30 to 60 wt% of support, 5 to 15 wt% of regeneration enhancer, and 5 to 15 wt% of inorganic binder; b) a slurrying step of adding the solid desulfurizer raw material to water, mixing and wet grinding to prepare a slurry; And c) a method of preparing a zinc-based desulfurizing agent by a spray drying method comprising spray drying the slurry by forming the slurry by a spray drying method to produce a desulfurizing agent granulating agent. The method of claim 11, wherein b), Mixing an organic additive comprising a dispersant and an organic binder in the slurry to disperse and homogenize the solid desulfurizer raw material contained in the slurry method of producing a zinc-based desulfurization agent by a spray drying method. The method of claim 11, wherein step c) A method of producing a zinc-based desulfurization agent by a spray drying method for spray drying the slurry in a countercurrent manner using a spray dryer equipped with a pressure nozzle.

Images