Method for producing desulfurization catalyst, and desulfurization method using the same

Abstract

A method for manufacturing a solid pretreatment desulfurization catalyst according to one embodiment of the present invention comprises: (a) a step of manufacturing a liquid pretreatment desulfurization catalyst; (b) a step of crushing a support having a porous structure with pores to a certain size; (c) a step of immersing the support crushed to a certain size in step (b) into the liquid pretreatment desulfurization catalyst manufactured in step (a) for 10 to 60 minutes; and (d) a step of introducing the support into a dryer in a state where the liquid pretreatment desulfurization catalyst has penetrated into the pores of the support by the impregnation in step (c), and then drying at a temperature of 100°C or higher for a certain period of time.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a solid pretreatment desulfurization catalyst and a desulfurization method using the same. More specifically, the invention relates to a method for manufacturing a solid pretreatment desulfurization catalyst and a desulfurization method using the same, wherein the weight of the desulfurization catalyst is minimized by impregnating a liquid pretreatment desulfurization catalyst into a porous support and drying it to solidify it, thereby simplifying the manufacturing process equipment and improving storage stability and logistics costs. Background Technology

[0002] Sulfur oxides (SOx) and nitrogen oxides (NOx) are identified as sources of air pollution; in particular, sulfur oxides are contained in industrial flue gases emitted from the combustion of fossil fuels containing sulfur, posing problems such as causing various forms of environmental pollution, including acid rain.

[0003] Desulfurization methods to remove sulfur oxides from such industrial flue gases have been continuously researched, and factories or fossil fuel power plants have generally used flue gas desulfurization, a post-combustion treatment method.

[0004] Flue gas desulfurization refers to the process of desulfurizing flue gas after burning fossil fuels containing sulfur gas, and this flue gas desulfurization method can be divided into wet and dry methods. The wet method is a method of removing sulfur oxides by washing flue gas with ammonia water, sodium hydroxide solution, lime milk, etc., while the dry method is a method of removing sulfur oxides by bringing particles or powders such as activated carbon or carbonates into contact with flue gas to adsorb or react with sulfur dioxide.

[0005] However, using the flue gas desulfurization method requires constructing a separate desulfurization facility to treat flue gas, and it has the problem of requiring a large amount of manpower and costs to operate the facility, as well as a complex desulfurization process.

[0006] Therefore, in order to reduce sulfur oxide emissions associated with the combustion of fossil fuels, there is an urgent need for research on pretreatment desulfurization catalysts and desulfurization methods that enable simultaneous desulfurization during the combustion process by mixing the catalyst into the fuel before combustion.

[0007] An example of such a catalyst for pretreatment desulfurization is well illustrated in Patent Registration No. 1864999 (hereinafter referred to as the "previously filed patent"), previously filed by the applicant of the present invention.

[0008] According to the aforementioned previously filed patent, a liquid-phase pretreatment desulfurization catalyst that is simple, easy to apply, and has an excellent desulfurization effect during the combustion of fossil fuels, a method for manufacturing the desulfurization catalyst, and a desulfurization method using the desulfurization catalyst are disclosed.

[0009] However, the aforementioned liquid pretreatment desulfurization catalyst had the following problems.

[0010] First, conventional liquid pretreatment desulfurization catalysts are manufactured in a liquid state by mixing liquid raw materials and water, so the manufacturing process equipment is complex, storage safety is poor due to the characteristics of liquid chemical substances, and logistics and storage costs are increased because they must be transported in liquid form using tank trucks equipped with special containers.

[0011] Second, conventional liquid pretreatment desulfurization catalysts had the problem of increasing the cost burden of manufacturing process equipment because separate facilities were required for injection when mixed into combustion products, such as coal or petroleum, for pretreatment.

[0012] Third, when conventional liquid pretreatment desulfurization catalysts are added in large quantities to coal, for example, problems arise such as clogging of the coal inlet due to the gelation of the coal or flowing down in the form of slurry along with the coal on the conveyor belt transporting the coal.

[0013] For the reasons mentioned above, there is an urgent need to develop and distribute solid pretreatment desulfurization catalysts that not only minimize the weight of the catalyst by solidifying conventional liquid pretreatment desulfurization catalysts into a stable solid state, but also simplify manufacturing process equipment and improve storage stability and logistics costs. Prior art literature

[0014] delete

[65535] (Patent Document 0001) KR 1864999 B The problem to be solved

[0015] Accordingly, the present invention has been devised to resolve the above-mentioned problems and aims to provide a method for manufacturing a solid pretreatment desulfurization catalyst and a desulfurization method using the same, wherein the weight of the desulfurization catalyst is minimized by impregnating a liquid pretreatment desulfurization catalyst into a porous support and drying it to solidify it, thereby simplifying the manufacturing process equipment and improving storage stability and logistics costs. means of solving the problem

[0016] According to one embodiment, the method for manufacturing a solid pretreatment desulfurization catalyst of the present invention for achieving the above-mentioned purpose comprises: (a) a step of manufacturing a liquid pretreatment desulfurization catalyst; (b) a step of crushing a support having a porous structure with pores to a certain size; (c) a step of immersing the support crushed to a certain size in step (b) into the liquid pretreatment desulfurization catalyst manufactured in step (a) for 10 to 60 minutes; and (d) a step of introducing the support into a dryer in a state where the liquid pretreatment desulfurization catalyst has penetrated into the pores of the support through the impregnation in step (c), and then drying at a temperature of 100°C or higher for a certain period of time.

[0017] In addition, according to one embodiment, after step (d), the method further comprises the step of (e) grinding and pulverizing the dried support, in which a liquid pretreatment desulfurization catalyst has penetrated into the pores of the support.

[0018] Additionally, according to one embodiment, after step (e), (f) a step of feeding the solid powder produced through step (e) into an extruder to produce a pellet, or feeding the solid into a tablet press to produce a tablet.

[0019] In addition, according to one embodiment, the support of step (b) comprises at least one of vermiculite, perlite, diatomite, and activated carbon.

[0020] In addition, according to one embodiment, in step (c), the liquid phase pretreatment desulfurization catalyst and the support are mixed in a mass ratio of 5:1 to 20:1.

[0021] In addition, according to one embodiment, step (d) includes the step of introducing the support material infiltrated with the liquid pretreatment desulfurization catalyst into a dryer, then raising the temperature from room temperature to 230°C and drying for 5 to 6 hours.

[0022] In addition, according to one embodiment, step (d) comprises: (d-1) a step of first drying the carrier infiltrated with the liquid pretreatment desulfurization catalyst by raising the temperature from room temperature to 130°C and drying for 2 hours; and (d-2) a step of second drying the carrier dried in step (d-1) by raising the temperature to 230°C and drying for 2 to 3 hours.

[0023] In addition, according to one embodiment, the liquid-phase pretreatment desulfurization catalyst of step (a) comprises: one or more oxides selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3; one or more metals selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb; and one or more liquid-phase compositions selected from the group consisting of sodium tetraborate (Na2B4O7·10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), and hydrogen peroxide (H2O2).

[0024] Also, according to one embodiment, the oxide comprises 15 to 90 parts by weight of SiO2, 15 to 100 parts by weight of Al2O3, 10 to 50 parts by weight of Fe2O3, 5 to 15 parts by weight of TiO2, 20 to 150 parts by weight of MgO, 10 to 20 parts by weight of MnO, 20 to 200 parts by weight of CaO, 15 to 45 parts by weight of Na2O, 20 to 50 parts by weight of K2O, and 5 to 20 parts by weight of P2O3.

[0025] In addition, according to one embodiment, the metal comprises 0.0035 to 0.009 parts by weight of Li, 0.005 to 0.01 parts by weight of Cr, 0.001 to 0.005 parts by weight of Co, 0.006 to 0.015 parts by weight of Ni, 0.018 to 0.03 parts by weight of Cu, 0.035 to 0.05 parts by weight of Zn, 0.04 to 0.08 parts by weight of Ga, 0.02 to 0.05 parts by weight of Sr, 0.002 to 0.01 parts by weight of Cd, and 0.003 to 0.005 parts by weight of Pb.

[0026] Also, according to one embodiment, the liquid composition is sodium tetraborate (Na2B4O7 . It contains 20 to 130 parts by weight of 10H2O, 15 to 120 parts by weight of sodium hydroxide (NaOH), 50 to 250 parts by weight of sodium silicate (Na2SiO3), and 10 to 50 parts by weight of hydrogen peroxide (H2O2).

[0027] Meanwhile, the desulfurization method using the solid pretreatment desulfurization catalyst of the present invention is characterized by adsorbing and removing sulfur oxides by mixing the solid pretreatment desulfurization catalyst prepared as described above with combustion products and burning them.

[0028] In addition, according to one embodiment, the ratio of the solid pretreatment desulfurization catalyst mixed into the combustion product is controlled according to the ratio of the content of C, H, N, and S contained in the combustion product. Effects of the invention

[0029] As described above, the solid pretreatment desulfurization catalyst produced by the present invention minimizes the weight of the desulfurization catalyst by impregnating a porous support into a liquid pretreatment desulfurization catalyst, drying, and solidifying it; furthermore, it simplifies the manufacturing process equipment, improves storage stability against moisture and reduces logistics costs, and enhances the desulfurization effect by mixing it with combustion products as a pretreatment to adsorb and remove sulfur oxides (SOx) with high efficiency.

[0030] In addition, the solid pretreatment desulfurization catalyst produced by the present invention has an excellent effect of reducing the emission of sulfur oxides before the generation of flue gas by adsorbing to the ash generated from combustion particles during the combustion process of combustion products, activating porosity, and reacting with and removing sulfur oxides present in the ash.

[0031] Furthermore, unlike conventional methods for desulfurizing flue gas after fuel combustion, the solid pretreatment desulfurization catalyst produced by the present invention is mixed with the desulfurization catalyst and combusted before combustion, thereby eliminating the need for additional investment in desulfurization facilities and offering the excellent effect of being easily applicable regardless of the type of combustion product. Brief explanation of the drawing

[0032] FIG. 1 is a flowchart of the method for manufacturing a solid pretreatment desulfurization catalyst of the present invention. FIG. 2 is a step-by-step photographic image of a support and drying process using vermiculite as a support according to an embodiment of the present invention. FIG. 3a is a graph of the results of the first drying experiment of a carrier according to one embodiment of the present invention. FIG. 3b is a graph of the results of a secondary drying experiment of a carrier according to an embodiment of the present invention. FIG. 4a is a graph of the wetting test results of a solid catalyst using vermiculite as a support according to one embodiment of the present invention. Figure 4b is a photographic image showing the wetness state over time in Figure 4a. Specific details for implementing the invention

[0033] The terms used herein are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “comprising,” “having,” or “having” are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described herein, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0034] Unless otherwise defined in this specification, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains.

[0035] Terms such as those defined in commonly used dictionaries should be interpreted as having meanings consistent with their meanings in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this specification.

[0036] Hereinafter, a method for manufacturing a solid pretreatment desulfurization catalyst according to one embodiment of the present invention will be described in detail with reference to the attached drawings.

[0037] FIG. 1 is a flowchart of a method for manufacturing a solid pretreatment desulfurization catalyst according to the present invention, and FIG. 2 is a step-by-step photographic image of a supporting and drying process using vermiculite as a support according to one embodiment of the present invention.

[0038] First, referring to FIGS. 1 and 2, the configuration according to one embodiment of the present invention may be composed of the following steps according to one embodiment.

[0039] Step (a): Prepare a catalyst for liquid-phase pretreatment desulfurization. (S100)

[0040] A liquid-phase pretreatment desulfurization catalyst according to the present invention can be manufactured according to the following detailed steps in one embodiment.

[0041] Step (a-1): One or more oxide powders selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3 are mixed and finely ground.

[0042] Step (a-2): One or more metal powders selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb are mixed and finely ground.

[0043] Step (a-3): The oxide of Step (a-1) and the metal of Step (a-2) are combined with sodium tetraborate (Na2B4O7 . A desulfurization catalyst is formed by mixing with one or more liquid compositions selected from the group consisting of 10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), and hydrogen peroxide (H2O2).

[0044] Step (a-1) above is a step of mixing one or more oxide powders selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3 and pulverizing them through a pulverizer.

[0045] In this step, the oxide powder may comprise SiO215 to 90 parts by weight, Al2O315 to 100 parts by weight, Fe2O310 to 50 parts by weight, TiO25 to 15 parts by weight, MgO 20 to 150 parts by weight, MnO 10 to 20 parts by weight, CaO 20 to 200 parts by weight, Na2O 15 to 45 parts by weight, K2O 20 to 50 parts by weight, and P2O35 to 20 parts by weight.

[0046] In addition, the oxide powder finely divided in this step can be repeatedly divided so that the particle size is 1 to 2 μm.

[0047] Step (a-2) above is a step of mixing one or more metal powders selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb and pulverizing them through a pulverizer.

[0048] In this step, the metal powder may comprise 0.0035 to 0.009 parts by weight of Li, 0.005 to 0.01 parts by weight of Cr, 0.001 to 0.005 parts by weight of Co, 0.006 to 0.015 parts by weight of Ni, 0.018 to 0.03 parts by weight of Cu, 0.035 to 0.05 parts by weight of Zn, 0.04 to 0.08 parts by weight of Ga, 0.02 to 0.05 parts by weight of Sr, 0.002 to 0.01 parts by weight of Cd, and 0.003 to 0.005 parts by weight of Pb.

[0049] In addition, the finely divided metal powder in this step can be repeatedly divided so that the particle size is reduced to 1 to 2 μm.

[0050] In step (a-3), the oxide powder and metal powder mixed and finely ground in steps (a-1) and (a-2) are mixed with sodium tetraborate (Na2B4O7 . A liquid-phase pretreatment desulfurization catalyst is formed by mixing with one or more liquid-phase compositions selected from the group consisting of 10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), and hydrogen peroxide (H2O2).

[0051] In this step, the liquid composition is sodium tetraborate (Na2B4O7 . It may contain 20 to 130 parts by weight of 10H2O, 15 to 120 parts by weight of sodium hydroxide (NaOH), 50 to 250 parts by weight of sodium silicate (Na2SiO3), and 10 to 50 parts by weight of hydrogen peroxide (H2O2).

[0052] In addition, when the oxide powder and metal powder mixed and finely ground in steps (a-1) and (a-2) are mixed and reacted in this step, the oxide powder and liquid composition can act as chelating agents to chelate with the metal powder and form a metal chelate compound.

[0053] In addition, the liquid pretreatment desulfurization catalyst formed in this step can be stabilized by precipitating for 24 to 72 hours, and the precipitated desulfurization catalyst can be separated and naturally dried to be used as a powder desulfurization catalyst, and the liquid composition remaining after separating the precipitated desulfurization catalyst can be used as the liquid pretreatment desulfurization catalyst of the present invention.

[0054] Here, the precipitate of the above-mentioned liquid desulfurization catalyst is air-dried and named as a powder catalyst for desulfurization (GTS-P), and the liquid composition from which the precipitated powder composition has been separated is transferred to a separate container and named as a liquid pretreatment desulfurization catalyst (GTS).

[0055] For reference, as previously described, the above-mentioned powder catalyst for desulfurization (GTS-P) can be solidified by naturally drying the precipitate of the liquid-phase pretreatment desulfurization catalyst (GTS); however, in this case, various problems as described below occurred.

[0056] First, due to the high viscosity of GTS-P, not only is the drying speed very slow, but difficulties also arose in internal drying caused by the solidification of the outer layer. Consequently, when the drying temperature was increased to dry GTS in an aqueous solution, the high solubility in water resulted in the substance existing as a high-viscosity liquid, leading to complexity in the manufacturing process.

[0057] Secondly, corrosion occurred in the metal equipment after drying, and problems arose regarding the formation of GTS deposits on the walls of the equipment. Furthermore, storage safety was poor due to moisture absorption when stored under normal atmospheric conditions, and the powdered solid of GTS-P resulting from simple drying absorbed moisture from the air and rapidly liquefied when dispersed in coal, thereby causing complexity in the addition method and equipment. For the reasons mentioned above, the desulfurization powder catalyst (GTS-P) was unsuitable for use as the solid pretreatment desulfurization catalyst of the present invention.

[0058] Accordingly, the liquid pretreatment desulfurization catalyst (GTS), which is one of the main materials of the present invention, is manufactured and prepared by the steps (a-1) to (a-3) described above.

[0060] Step (b): A porous support with pores is crushed to a certain size. (S200)

[0061] According to one embodiment, the carrier used was a porous material such as expanded vermiculite, pearlite, diatomite, or activated carbon. The carrier used had an apparent specific gravity of 0.1 to 0.5, an absorption rate of 60 to 300 cc / 100g, and a particle size of 10 to 2,000 μm.

[0062] The above-mentioned support is preferably a material having a porous structure, and the numerous pores within the support possess moisture retention capabilities, allowing it to appropriately contain components that perform desulfurization in a solid state. Additionally, it has permeability, which generates sodium sulfate (Na2SO4) through a reaction with sulfur oxides, and particularly due to its thermal insulation properties, it inhibits decomposition reactions in high-temperature regions. Typically, at temperatures above 1200°C, sodium sulfate decomposes into sulfur oxides and exits into flue gas, which can lead to a decrease in desulfurization performance. Furthermore, the presence of desulfurization components with strong alkaline properties within the porous material acts as a three-dimensional barrier that minimizes the adhesion of strong alkaline components to the inner wall of the combustion furnace, thereby avoiding high-temperature corrosion caused by alkali adhesion to the inner wall of the combustion furnace. In particular, expanded vermiculite with a plate-like structure has a faster moisture absorption rate, which offers the advantage of being favorable for solid-liquid impregnation.

[0064] Step (c): The support material ground to a certain size in Step (b) in Step (b) is immersed in the liquid pretreatment desulfurization catalyst prepared in Step (a) and impregnated for 10 to 60 minutes. (S300)

[0065] According to one embodiment, the mass ratio of the liquid pretreatment desulfurization catalyst (GTS) and the vermiculite support can be mixed in the range of 5:1 to 20:1, and more preferably mixed to have a mass ratio of 10:1.

[0066] The time for impregnating the above liquid pretreatment desulfurization catalyst (GTS) into the vermiculite support is at least 1 hour so that the liquid pretreatment desulfurization catalyst can be sufficiently impregnated between the pores of the vermiculite support.

[0068] Step (d): After the liquid pretreatment desulfurization catalyst has penetrated into the pores of the support through the impregnation of Step (c), the support is placed in a dryer and dried at a temperature of 100°C or higher for a certain period of time. (S400)

[0069] Here, after the support material infiltrated with the liquid pretreatment desulfurization catalyst is introduced into a dryer, the internal temperature of the dryer is raised from room temperature to 230°C and dried for 5 to 6 hours.

[0070] Additionally, the above step (d) may be composed of the following detailed steps according to one embodiment.

[0071] Step (d-1): After placing the support material infiltrated with the liquid pretreatment desulfurization catalyst into a dryer, the temperature inside the dryer is raised from room temperature to 130°C and then first dried for 2 hours.

[0072] Step (d-2): The carrier that was dried first in Step (d-1) is heated to 230°C and dried secondly for 2 to 3 hours.

[0073] As described above, by performing multi-stage drying for a sufficient drying time through a first drying step of heating from room temperature to 130°C followed by drying, and a second drying step of heating from 130°C to 230°C followed by drying, it was confirmed that heat penetrated evenly into the interior of the porous structure, resulting in uniform drying. Furthermore, in the drying experiment described below, it was confirmed that the moisture content of the support material infiltrated with the liquid pretreatment desulfurization catalyst reached less than 5% in the product after completing the second drying step. (Refer to Figures 3a and 3b)

[0074] Meanwhile, according to another embodiment, a moisture content of less than 5% can be reached by performing only the secondary drying of step (d-2) for 160 minutes, without sequentially undergoing the primary and secondary drying processes of steps (d-1) and (d-2) as in the above-described embodiment. (Refer to the bottom table in FIG. 3b)

[0075] In addition, in the above-described embodiment and other embodiments, when a drum-type powder dryer is used, the drying time can be further shortened because the support material is dried while rolling within the drum-type drying tank, which provides a more advantageous benefit for the continuous production of the solid pretreatment desulfurization catalyst of the present invention.

[0077] Step (e): After drying the support material with the liquid pretreatment desulfurization catalyst infiltrated into its pores, the support material is placed in a grinder and ground to a certain size. (S500)

[0078] The grinding size can be adjusted so that the solid material is ground to a particle size of 10 mesh (1.9 mm) or less using a grinder, but it can be ground to an appropriate size depending on the type of combustion material and the mixing method. Therefore, the solid material prepared in powder form as described above can be used directly as the solid pretreatment desulfurization catalyst (first form) of the present invention.

[0080] Step (f): The solid powder prepared through Step (e) is fed into an extruder to produce pellets (second form), or the solid is fed into a tablet press to produce tablets (third form). (S600)

[0081] As described above, the solid pretreatment desulfurization catalyst of the present invention (hereinafter referred to as 'GTS-S'), processed into a powder (first form), pellet (second form), or tablet (third form) by the steps (a) to (f) described above, is finally manufactured.

[0082] That is, various forms of GTS-S products can be manufactured, such as shipping the dried product made of powder as a GTS-S product, processing it into a pellet form using an extruder, or grinding the solid component to a particle size of 10 mesh (1.9 mm) or less using a grinder and then processing it into a tablet using a tablet press. At this time, according to one embodiment, the size of the pellet or tablet manufactured as described above can be manufactured with a diameter of 2 mm to 50 mm and a length of within 1 relative to the diameter (L / D).

[0084] <Experimental Example 1> Drying Experiment of Vermiculite-Supported Solid Pretreatment Desulfurization Catalyst (GTS-S)

[0085] Hereinafter, the present invention will be explained in more detail with reference to FIGS. 3a and 3b regarding the results of drying experiments on a vermiculite support. However, the presented experimental results are merely specific examples of the present invention and are not intended to limit the scope of the present invention.

[0086] FIG. 3a is a graph of the results of a first drying experiment of a solid pretreatment desulfurization catalyst according to one embodiment of the present invention.

[0087] GTS-S 1st Drying Test Results @130℃

[0088] After placing GTS-S into a dryer, the temperature was raised from room temperature to 130°C, and the moisture content was measured at regular intervals while drying.

[0089] As a result of measuring moisture content at 40-minute intervals after heating from room temperature to 130℃, it was confirmed that the moisture content of all samples 1 to 6 (Shinsung 1, 2, 3, SV1 1, 2, 3) was less than 50% starting from the 120-minute mark, meeting the target value for the first drying. (Refer to the moisture content table at the bottom of Fig. 3a)

[0090] Specifically, the change in moisture content due to weight loss was measured using a TGA (thermogravimetric analyzer, model name: TGA Q500) under conditions of 40~150℃ (10℃ / min)_N2.

[0091] Here, in the graph of Figure 3a above, Shinseong 1 to 3 are samples using Shinseong Mineral's No. 2 vermiculite, and SV1 1 to 3 are samples using Gwangwoo's SV1 vermiculite.

[0092] That is, although Shinsung 1, 2, 3 and SV1 1, 2, 3 differ in origin and thus have some differences in composition and absorption rate, to verify reproducibility as they are all samples with the same mass, three identical samples from each company were prepared and the weight change was measured.

[0094] FIG. 3b is a graph of the results of a secondary drying experiment of a solid pretreatment desulfurization catalyst according to one embodiment of the present invention.

[0095] GTS-S 2nd Drying Test Results @230℃

[0096] The second drying was carried out by accelerated drying (rapid drying) at 230°C, which is higher than the temperature of the first drying shown in Fig. 3a above.

[0097] After raising the temperature from room temperature to 230℃ and measuring the moisture content at 20-minute intervals, it was confirmed that the moisture content of all samples 1 to 6 (Shinsung 1, 2, 3, SV1 1, 2, 3) was less than 5% starting from the point where 160 minutes had elapsed, thus meeting the final moisture content target value (less than 5%) of the drying process.

[0098] Specifically, the change in moisture content due to weight loss was measured using a TGA (thermogravimetric analyzer, model name: TGA Q500) under conditions of 40~150℃ (10℃ / min)_N2.

[0100] In other words, during the aforementioned second drying, the moisture content reached the target value of 50% from the first drying after 60 minutes, and after 160 minutes, it reached the final target value of less than 5%; thus, it was confirmed that an additional approximately 100 minutes were required from the point when the first drying was completed to the point when the second drying was finally completed. (Refer to the moisture content table at the bottom of Fig. 3b)

[0101] Here, in the graph of Figure 3b above, Shinseong 1 to 3 are samples using Shinseong Mineral's No. 2 vermiculite, and SV1 1 to 3 are samples using Gwangwoo's SV1 vermiculite.

[0102] In addition, to verify reproducibility with samples of the same mass as shown in Figure 3a above, three identical samples from each company were prepared and the weight change was measured.

[0104] <Experimental Example 2> Wetting Test of Vermiculite-Supported Solid Pretreatment Desulfurization Catalyst (GTS-S)

[0105] Hereinafter, the present invention will be described in more detail with reference to FIGS. 4a and 4b regarding the results of a wetting test of a vermiculite carrier. However, the presented test results are merely specific examples of the present invention and are not intended to limit the scope of the present invention.

[0106] FIG. 4a is a graph showing the results of a wet test of a solid catalyst using vermiculite as a support according to one embodiment of the present invention, and FIG. 4b is a photographic image showing the wet state according to the elapsed time of FIG. 4a.

[0107] Referring to Fig. 4a, the weight percentage (%) increase of absorbed moisture was measured at regular intervals after leaving the finished GTS-S product manufactured according to the present invention in the atmosphere.

[0108] The sample of the example used in the test was 1.01 g of a solid pretreatment desulfurization catalyst (GTS-S) using a vermiculite support prepared according to the present invention, and the sample of the comparative example was 0.35 g of a powder catalyst (GTS-P) without a support.

[0109] The weight percentage (%) of moisture per sample, i.e., the amount of moisture absorbed, can be calculated as follows.

[0110] Moisture absorption amount (%) = (Weight of GTS-S finished product after exposure to air - Weight of GTS-S finished product) / (Weight of GTS-S finished product) * 100 %

[0112] As a result of the measurement, the weight percentage of moisture (amount of moisture absorbed) in both the sample of the example and the comparative example increased rapidly from 400 minutes to a certain point between 400 and 500 minutes.

[0113] In particular, the sample of the comparative example increased by more than three times compared to the sample of the example. Referring to Fig. 4b, several problems were found in the dry solid of the powder catalyst without a support (GTS-P) of the comparative example, such as wall adhesion, clumping, and conversion into an aqueous solution form, due to the rapid increase in moisture after (b) 411 minutes and (c) 1420 minutes.

[0114] Therefore, it was confirmed that the sample of the example had superior moisture stability in absorbing moisture over time compared to the sample of the comparative example.

[0116] <Experimental Example 3> Results of Desulfurization Performance Test of Vermiculite-Supported Solid Pretreatment Desulfurization Catalyst (GTS-S) Using a Sulfur Analyzer

[0117] No Sample name Loading drainage (GTS / weight ratio of vermiculite) S Detected Amount (%) S Reduction Amount (%) S Reduction Rate (%) 1 Comparative Example (GTS-P) - 0.02 0.24 92.31 2 Example 1 (GTS-S) 10.8 0.02 0.24 92.31 3 Example 2 (GTS-S) 14.6 0.03 0.23 88.46 4 Example 3 (GTS-S) 19.8 0.03 0.23 88.46 5 Example 4 (GTS-S) 19.8 0.05 0.21 80.77 6 Example 5 (GTS-S) 9.7 0.02 0.24 92.31

[0118] As can be seen from the desulfurization performance test results table in Table 1 above, it was confirmed that the solid pretreatment desulfurization catalysts of Examples 1 to 5 of the present invention, which exhibit wet stability compared to the powder desulfurization catalyst without a support of the comparative example, showed equal or equivalent performance in terms of S (sulfur) detection amount, S reduction amount, and S reduction rate.

[0120] Specifically, for this desulfurization performance test, a sulfur analyzer CKiC (model name '5E-AS3200B') was used to mix 1 to 3 g of liquid pretreatment desulfurization catalyst (GTS) with 10 g of finely ground coal and dry it, then weighed 45 to 45 mg of the coal sample into a crucible and measured the desulfurization performance at 1150°C for about 5 minutes.

[0121] In particular, Example 5 was found to be the most advantageous in terms of cost-effectiveness, as it showed the same desulfurization performance as the comparative example while having the smallest amount of liquid pretreatment desulfurization catalyst (GTS).

[0123] Meanwhile, the desulfurization method using the solid pretreatment desulfurization catalyst of the present invention is characterized by adsorbing and removing sulfur oxides as a pretreatment during the combustion process by mixing the solid pretreatment desulfurization catalyst prepared as described above with the combustion product in advance and then combusting it.

[0124] In addition, according to one embodiment, the mixing ratio of the solid pretreatment desulfurization catalyst mixed into the combustion product can be adjusted according to the ratio of C, H, N, and S content contained in the combustion product. For example, if the combustion product is Vietnam Uong Bi 3 coal, the sulfur content is high, so it is necessary to increase the amount of the solid pretreatment desulfurization catalyst (GTS-S) of the present invention and mix it more than with ordinary coal.

[0126] <Calculation Method for Adding Solidified GTS-S (Gs) to Coal>

[0127] The following is a formula for calculating the input amount of the solid pretreatment desulfurization catalyst (GTS-S) according to the present invention.

[0128] f(factor) = Gl / Gs ...........(Equation 1)

[0129] (where f is the mass ratio of the liquid catalyst GTS solution contained in the solid catalyst GTS-S, Gl is the mass of the liquid catalyst GTS, and Gs is the mass of the solid catalyst GTS-S.)

[0130] If the dry weight of GS is 35g when 100g of Gl is contained,

[0131] f=100g / 35g = 2.85

[0132] From the above (Equation 1), Gs = Gl / f was derived.

[0133] Therefore, if you need to add 12g by converting GTS-S to GTS,

[0134] Gs = Gl / f = 12g / 2.85 = 4.21g

[0135] Therefore, since the solid pretreatment desulfurization catalyst (GTS-S) of the present invention only requires 4.21g (35%) by weight, it is possible to achieve a 65% weight reduction effect compared to the conventional liquid pretreatment desulfurization catalyst (GTS) of 12g that had to be added to obtain the same desulfurization effect.

[0136] In addition, the desulfurization method using the desulfurization catalyst according to the present invention allows sulfur oxides in the flue gas to be removed in advance by mixing the solid pretreatment desulfurization catalyst with the combustion product before combustion and burning it, thereby activating the desulfurization function during the combustion process.

[0137] In other words, conventional flue gas desulfurization methods remove sulfur oxides (SOx) contained in the generated flue gas after burning only the combustion products; however, they had the disadvantage of requiring desulfurization equipment to perform this process, as well as significant manpower and costs for operation. However, the desulfurization method using a solid pretreatment desulfurization catalyst according to the present invention can exhibit an excellent desulfurization effect that ultimately reduces sulfur oxide emissions in flue gas by mixing the desulfurization catalyst with the combustion products before combustion and burning them together, thereby allowing the desulfurization catalyst to adsorb and remove sulfur oxides generated along with the combustion of the products during the combustion process.

[0138] In addition, the desulfurization catalyst of the present invention can be applied to combustible materials that generate heat through combustion, such as coal, petroleum, waste, and biogas, but preferably to coal.

[0139] In addition, the above-described solid pretreatment desulfurization catalyst is mixed in at a certain ratio before combustion of the combustion product and then combusted together with the combustion product; at this time, an excellent desulfurization effect can be maintained by adjusting the amount of the solid pretreatment desulfurization catalyst mixed in according to the content of C, H, N, and S contained in the combustion product.

[0140] Furthermore, the present invention is not limited solely to the embodiment described above. Since the same effect can be achieved even when the detailed configuration, number, or arrangement structure of the device is changed, it is hereby specified that those skilled in the art can add, delete, or modify various configurations within the scope of the technical concept of the present invention.

Claims

Claim 1 (a) one or more oxides selected from the group consisting of SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O, and P2O3; one or more metals selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd, and Pb; (a) a step of preparing a liquid pretreatment desulfurization catalyst comprising one or more liquid compositions selected from the group consisting of sodium tetraborate (Na2B4O7·10H2O), sodium hydroxide (NaOH), sodium silicate (Na2SiO3), and hydrogen peroxide (H2O2); (b) a step of grinding a support having a porous structure with pores to a predetermined size; (c) a step of immersing the support ground to a predetermined size in step (b) into the liquid pretreatment desulfurization catalyst prepared in step (a) for 10 to 60 minutes; (d) a step of introducing the support into a dryer in a state where the liquid pretreatment desulfurization catalyst has penetrated into the pores of the support by the impregnation in step (c), and drying at a temperature of 100°C or higher for a predetermined time; (e) a step of grinding the dried support, in which the liquid pretreatment desulfurization catalyst has penetrated into the pores of the support, into powder; (f) the step (e) comprising the step of using the solid produced as a powder through (e) as a catalyst for solid pretreatment desulfurization, feeding the solid into an extruder to produce pellets, or feeding the solid into a tablet press to produce tablets; wherein the support in step (b) is vermiculite, and in step (c), the ratio of the liquid pretreatment desulfurization catalyst to the support is 9.7:1 to 10.A method for manufacturing a solid pretreatment desulfurization catalyst, comprising mixing in a mass ratio of 8:1, and step (d) comprising: (d-1) a step of first drying the support infiltrated with the liquid pretreatment desulfurization catalyst for 2 hours after placing it in a dryer and raising the temperature from room temperature to 130°C; and (d-2) a step of adjusting the moisture content of the support infiltrated with the liquid pretreatment desulfurization catalyst to 5% or less by raising the temperature of the support dried first in step (d-1) to 230°C and second drying for 2 to 3 hours. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 delete Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 A method for preparing a solid pretreatment desulfurization catalyst according to claim 1, wherein the oxide comprises 15 to 90 parts by weight of SiO2, 15 to 100 parts by weight of Al2O3, 10 to 50 parts by weight of Fe2O3, 5 to 15 parts by weight of TiO2, 20 to 150 parts by weight of MgO, 10 to 20 parts by weight of MnO, 20 to 200 parts by weight of CaO, 15 to 45 parts by weight of Na2O, 20 to 50 parts by weight of K2O, and 5 to 20 parts by weight of P2O3. Claim 10 A method for manufacturing a solid pretreatment desulfurization catalyst according to claim 1, wherein the metal comprises 0.0035 to 0.009 parts by weight of Li, 0.005 to 0.01 parts by weight of Cr, 0.001 to 0.005 parts by weight of Co, 0.006 to 0.015 parts by weight of Ni, 0.018 to 0.03 parts by weight of Cu, 0.035 to 0.05 parts by weight of Zn, 0.04 to 0.08 parts by weight of Ga, 0.02 to 0.05 parts by weight of Sr, 0.002 to 0.01 parts by weight of Cd, and 0.003 to 0.005 parts by weight of Pb. Claim 11 In claim 1, the liquid composition is sodium tetraborate (Na2B4O7 . A method for preparing a solid pretreatment desulfurization catalyst comprising 20 to 130 parts by weight of 10H2O, 15 to 120 parts by weight of sodium hydroxide (NaOH), 50 to 250 parts by weight of sodium silicate (Na2SiO3), and 10 to 50 parts by weight of hydrogen peroxide (H2O2). Claim 12 delete Claim 13 delete

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