CATALYST FOR DESULFURIZATION, METHOD OF PREPARING THE SAME, AND DESULFURIZATION METHOD USING THE SAME

Abstract

Disclosed is a catalyst for desulfurization, including (a) an oxide selected from among SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3, (b) a metal selected from among Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb, and (c) a liquid compound selected from among sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2). The catalyst of the invention has a 2:1 type layered structure in which one octahedral layer is interposed between two tetrahedral layers and which has a net negative charge due to occupation of only two of three positively charged sites in the octahedral layer, and the catalyst for desulfurization is provided in the form of a metal chelate compound through chelation with a metal ion, whereby sulfur oxide (SO.sub.x) can be adsorbed and removed at high efficiency upon combustion of a combustible substance.

Claims

1. A catalyst for desulfurization, comprising: (a) an oxide selected from the group consisting of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3; (b) a metal selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb; and (c) a liquid compound selected from the group consisting of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2).

2. The catalyst for desulfurization of claim 1, wherein the oxide includes 15 to 90 parts by weight of SiO.sub.2, 15 to 100 parts by weight of Al.sub.2O.sub.3, 10 to 50 parts by weight of Fe.sub.2O.sub.3, 5 to 15 parts by weight of TiO.sub.2, 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 Na.sub.2O, 20 to 50 parts by weight of K.sub.2O and 5 to 20 parts by weight of P.sub.2O.sub.3, and the metal includes 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.

3. The catalyst for desulfurization of claim 1, wherein the oxide and the metal have a particle size of 1 to 2 m and a specific gravity of 2.5 to 3.0.

4. The catalyst for desulfurization of claim 1, wherein the liquid compound includes 20 to 130 parts by weight of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), 15 to 120 parts by weight of sodium hydroxide (NaOH), 50 to 250 parts by weight of sodium silicate (Na.sub.2SiO.sub.3) and 10 to 50 parts by weight of hydrogen peroxide (H.sub.2O.sub.2).

5. The catalyst for desulfurization of claim 1, wherein, in the catalyst for desulfurization, the oxide, the metal and the liquid compound are formed into a metal chelate compound.

6. The catalyst for desulfurization of claim 1, wherein the catalyst for desulfurization activates an adsorption effect of sulfur oxide (SO.sub.x) at 600 to 900 C.

7. A method of preparing a catalyst for desulfurization, comprising: (a) mixing and pulverizing an oxide powder selected from the group consisting of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3; (b) mixing and pulverizing a metal powder selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb; and (c) mixing the oxide powder of step (a) and the metal powder of step (b) with a liquid compound selected from the group consisting of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2) to yield a catalyst for desulfurization.

8. The method of claim 7, wherein the oxide powder in step (a) includes 15 to 90 parts by weight of SiO.sub.2, 15 to 100 parts by weight of Al.sub.2O.sub.3, 10 to 50 parts by weight of Fe.sub.2O.sub.3, 5 to 15 parts by weight of TiO.sub.2, 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 Na.sub.2O, 20 to 50 parts by weight of K.sub.2O and 5 to 20 parts by weight of P.sub.2O.sub.3.

9. The method of claim 7, wherein the metal powder in step (b) includes 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.

10. The method of claim 7, wherein the oxide powder in step (a) and the metal powder in step (b) are pulverized to a particle size of 1 to 2 m.

11. The method of claim 7, wherein the liquid compound in step (c) includes 20 to 130 parts by weight of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), 15 to 120 parts by weight of sodium hydroxide (NaOH), 50 to 250 parts by weight of sodium silicate (Na.sub.2SiO.sub.3) and 10 to 50 parts by weight of hydrogen peroxide (H.sub.2O.sub.2).

12. The method of claim 7, wherein, in step (c), the oxide powder, the metal powder and the liquid compound are formed into a metal chelate compound.

13. The method of claim 7, wherein the catalyst for desulfurization formed in step (c) is used in a form of a powder catalyst for desulfurization obtained by subjecting the catalyst for desulfurization to precipitation, separation and drying; and a liquid catalyst for desulfurization, which remains after separation of the precipitated catalyst for desulfurization.

14. A desulfurization method wherein the catalyst for desulfurization of claim 1, comprising adsorbing and removing sulfur oxide by mixing the catalyst for desulfurization with a combustible substance and combusting the combustible substance.

15. The desulfurization method of claim 14, wherein an amount of the catalyst for desulfurization that is mixed is adjusted depending on amounts of C, H, N and S in the combustible substance.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 shows the results of testing of average SO.sub.2 emission according to an embodiment of the present invention;

[0029] FIG. 2 shows SO.sub.2 emission reduction efficiency according to an embodiment of the present invention;

[0030] FIG. 3 shows the results of testing of average SO.sub.2 emission in individual excess oxygen ranges according to an embodiment of the present invention;

[0031] FIG. 4 shows SO.sub.2 emission reduction efficiency according to an embodiment of the present invention;

[0032] FIG. 5 shows average SO.sub.2 emission reduction efficiency in the entire excess oxygen range according to an embodiment of the present invention; and

[0033] FIG. 6 shows the proportion of unburned carbon emitted from exhaust gas according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0034] Specific structural and functional descriptions of embodiments of the present invention disclosed herein are only for the purpose of illustrating the embodiments of the present invention. The present invention may be embodied in many different forms without departing from the spirit and significant characteristics of the present invention. Therefore, the embodiments of the present invention are disclosed only for illustrative purposes, and should not be construed as limiting the present invention. Hereinafter, a detailed description will be given of the present invention with reference to the accompanying drawings.

[0035] The present invention pertains to a catalyst for desulfurization, comprising (a) at least one oxide selected from the group consisting of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3, (b) at least one metal selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb, and (c) at least one liquid compound selected from the group consisting of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2).

[0036] The catalyst for desulfurization according to the present invention may include at least one oxide selected from the group consisting of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3, and preferably includes all oxides of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3, as in the following embodiment.

[0037] When all of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3 are included, the typical chemical formula is represented by K.sub.0.8-0.9 (Al, Fe, Mg).sub.2(Si, Al).sub.4O.sub.10(OH).sub.2, which is a mineral called illite. Here, illite typically has a 2:1 structure, in which one octahedral layer is interposed between two tetrahedral layers and the octahedral layer has a dioctahedral structure due to occupation of only two of three positively charged sites in the binding configuration thereof with cations, thus representing a net negative charge due to the lack of cations. Thereby, when the combustible substance mixed with the catalyst for desulfurization is combusted, sulfur oxide (SO.sub.x) may be adsorbed.

[0038] The catalyst for desulfurization may include, as the oxides, to 90 parts by weight of SiO.sub.2, 15 to 100 parts by weight of Al.sub.2O.sub.3, to 50 parts by weight of Fe.sub.2O.sub.3, 5 to 15 parts by weight of TiO.sub.2, to 150 parts by weight of MgO, 10 to 20 parts by weight of MnO, to 200 parts by weight of CaO, 15 to 45 parts by weight of Na.sub.2O, to 50 parts by weight of K.sub.2O and 5 to 20 parts by weight of P.sub.2O.sub.3.

[0039] Also, the oxides may be mixed and pulverized to particles having a particle size of 1 to 2 m using a pulverizer before formation into the catalyst for desulfurization, and may be used in the form of a powder having color streaks and a silvery white color, with a specific gravity of 2.5 to 3.0.

[0040] The catalyst for desulfurization according to the present invention may include at least one metal selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb, and preferably includes all metals of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb, as in the following embodiment.

[0041] The catalyst for desulfurization may include, as the metals, 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.

[0042] As in the oxides, the metals may be mixed and pulverized to particles having a particle size of 1 to 2 m using a pulverizer, and may be used in the form of a powder having color streaks and a silvery white color, with a specific gravity of 2.5 to 3.0.

[0043] The catalyst for desulfurization according to the present invention may include at least one liquid compound selected from the group consisting of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2), and preferably includes all liquid compounds of sodium tetraborate, sodium hydroxide, sodium silicate and hydrogen peroxide, as in the following embodiment.

[0044] In the catalyst for desulfurization according to the present invention, the oxide and the liquid compound are mixed and react to thus function as a chelating agent, followed by chelation through coordinate bonding with the metal, thereby forming a metal chelate compound.

[0045] Also, the liquid compound may be adsorbed to ashes formed upon combustion of a combustible substance to thus react with sulfur oxide present in the ashes to remove sulfur oxide. NaBO.sub.2 is derived from sodium tetraborate Na.sub.2B.sub.4O.sub.7, and is then hydrogenated to produce NaBH.sub.4, after which the produced NaBH.sub.4 reacts with oxygen and sulfur oxide to give sodium sulfate (Na.sub.2SO.sub.4), thereby removing sulfur oxide. These reactions are represented in Schemes 1 and 2 below.

NaBH.sub.4+O.sub.3.fwdarw.Na.sub.2O.sub.2+H.sub.2O+B[Scheme 1]

1) Na.sub.2O.sub.2+SO.sub.3.fwdarw.Na.sub.2SO.sub.4+O

2) Na.sub.2O.sub.2+SO.sub.2.fwdarw.Na.sub.2SO.sub.4

3) Na.sub.2O.sub.2+SO.fwdarw.Na.sub.2SO.sub.3[Scheme 2]

[0046] Also, the catalyst for desulfurization may include, as the liquid compounds, 20 to 130 parts by weight of sodium tetraborate, to 120 parts by weight of sodium hydroxide, 50 to 250 parts by weight of sodium silicate and 10 to 50 parts by weight of hydrogen peroxide.

[0047] The catalyst for desulfurization according to the present invention is capable of activating the adsorption effect of sulfur oxide when the combustible substance is mixed therewith and combusted in the temperature range of 400 to 1200 C., but combustion in the temperature range of 600 to 900 C. may exhibit high efficiency.

[0048] In addition, the present invention pertains to a method of preparing the catalyst for desulfurization.

[0049] According to the present invention, the method of preparing the catalyst for desulfurization includes (a) mixing and pulverizing at least one oxide powder selected from the group consisting of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3; (b) mixing and pulverizing at least one metal powder selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb; and (c) mixing the oxide of step (a) and the metal of step (b) with at least one liquid compound selected from the group consisting of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2) to yield a catalyst for desulfurization.

[0050] In step (a), at least one oxide powder selected from the group consisting of SiO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, TiO.sub.2, MgO, MnO, CaO, Na.sub.2O, K.sub.2O and P.sub.2O.sub.3 is mixed and pulverized using a pulverizer.

[0051] In this step, the oxide powder may contain 15 to 90 parts by weight of SiO.sub.2, 15 to 100 parts by weight of Al.sub.2O.sub.3, 10 to 50 parts by weight of Fe.sub.2O.sub.3, 5 to 15 parts by weight of TiO.sub.2, 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 Na.sub.2O, 20 to 50 parts by weight of K.sub.2O and 5 to 20 parts by weight of P.sub.2O.sub.3.

[0052] Here, the pulverized oxide powder may be repetitively pulverized so as to have a particle size of 1 to 2 m.

[0053] In step (b), at least one metal powder selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb is mixed and pulverized using a pulverizer.

[0054] In this step, the metal powder may contain 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.

[0055] Here, the pulverized metal powder may be repetitively pulverized so as to have a particle size of 1 to 2 m.

[0056] In step (c), the oxide powder mixed and pulverized in step (a) and the metal powder mixed and pulverized in step (b) are mixed with at least one liquid compound selected from the group consisting of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), sodium hydroxide (NaOH), sodium silicate (Na.sub.2SiO.sub.3) and hydrogen peroxide (H.sub.2O.sub.2), thus affording a catalyst for desulfurization.

[0057] In this step, the liquid compound may contain 20 to 130 parts by weight of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O), 15 to 120 parts by weight of sodium hydroxide (NaOH), 50 to 250 parts by weight of sodium silicate (Na.sub.2SiO.sub.3) and 10 to 50 parts by weight of hydrogen peroxide (H.sub.2O.sub.2).

[0058] Here, when the liquid compound is mixed and reacted with the oxide powder mixed and pulverized in step (a) and the metal powder mixed and pulverized in step (b), the oxide powder and the liquid compound, functioning as a chelating agent, may be chelated with the metal powder, thereby forming a metal chelate compound.

[0059] Also, the catalyst for desulfurization formed in this step may be precipitated for 24 to 72 hr and thus stabilized, and the precipitated catalyst for desulfurization is separated and naturally dried, and may thus be used as a powder catalyst for desulfurization. Further, a liquid composition, which remains after separation of the precipitated catalyst for desulfurization, may be used as a liquid catalyst for desulfurization.

[0060] In addition, the present invention pertains to a desulfurization method using the catalyst for desulfurization, in which a combustible substance is mixed with the catalyst for desulfurization and is combusted, thereby realizing desulfurization activity.

[0061] A conventional desulfurization method is performed in a manner in which sulfur oxide (SO.sub.x) is removed from exhaust gas generated after the combustion of a combustible substance, and is problematic because a desulfurizer therefor has to be used and extensive labor is required and high costs are incurred for operation of the desulfurizer. However, the desulfurization method using the catalyst for desulfurization according to the present invention is performed in a manner in which a combustible substance is mixed with the catalyst for desulfurization and then combusted, whereby the catalyst for desulfurization is capable of adsorbing and removing sulfur oxide generated upon combustion of the combustible substance, ultimately exhibiting desulfurization effects for reducing the emission of sulfur oxide.

[0062] Also, examples of the combustible substance to which the catalyst for desulfurization according to the present invention may be applied may include combustibles that generate heat through combustion, such as coal, oil, waste, biogas, and the like, with coal being particularly targeted.

[0063] As described above, the catalyst for desulfurization may include a powder catalyst for desulfurization and a liquid catalyst for desulfurization, which may be used separately or together depending on the amounts of C, H, N and S of a combustible substance to be combusted, whereby superior desulfurization effects may be exhibited in a simple and easy manner.

[0064] A better understanding will be given of the present invention through the following examples and test examples.

[0065] The examples and test examples are merely set forth to illustrate the present invention but are not to be construed as limiting the scope of the present invention.

Example 1

[0066] (1) Preparation of Catalyst for Desulfurization

[0067] As oxides, 150 kg of SiO.sub.2, 150 kg of Al.sub.2O.sub.3, 100 kg of Fe.sub.2O.sub.3, 50 kg of TiO.sub.2, 200 kg of MgO, 100 kg of MnO, 200 kg of CaO, 150 kg of Na.sub.2O, 200 kg of K.sub.2O, and 50 kg of P.sub.2O.sub.3 were mixed and pulverized using a pulverizer, thus forming an oxide powder.

[0068] As metals, 35 g of Li, 50 g of Cr, 10 g of Co, 60 g of Ni, 180 g of Cu, 350 g of Zn, 400 g of Ga, 200 g of Sr, 20 g of Cd, and 30 g of Pb were mixed and pulverized using a pulverizer, thus forming a metal powder.

[0069] The oxide powder and the metal powder were repetitively pulverized so as to have a particle size of 1 to 2 m.

[0070] 3000 kg of water was placed in a reactor, and 50 kg of sodium tetraborate (Na.sub.2B.sub.4O.sub.7.10H.sub.2O) was added thereto while the temperature was maintained at 50 to 60 C. After stirring for 30 min, 100 kg of sodium hydroxide (NaOH) was added thereto and stirred. After 10 min, the pulverized oxide powder was added at intervals of 5 min in an amount of 100 kg each time, and stirred for 2 hr or more. The temperature was increased to 60 to 80 C. with stirring, and 100 kg of sodium silicate (Na.sub.2SiO.sub.3) was added thereto. Stirring was performed for 30 min, after which the pulverized metal powder was added at intervals of 3 min in an amount of 20 g each time and stirred. Stirring was performed for 1 hr, after which 30 kg of hydrogen peroxide (H.sub.2O.sub.2) was added, followed by further stirring for 30 min and natural cooling for 1 hr.

[0071] The cooled product was stabilized for 48 hr, after which the liquid composition and the precipitated powder composition were separated from each other.

[0072] The precipitated powder composition was naturally dried, thereby yielding a powder catalyst for desulfurization (GTS-P).

[0073] Also, the liquid composition separated from the precipitated powder composition was transferred into an additional vessel, thereby yielding a liquid catalyst for desulfurization (GTS-W).

[0074] (2) Preparation of Example 1 (GTS-P 3)

[0075] 3 kg of the powder catalyst for desulfurization (GTS-P) obtained in (1) above was mixed with 97 kg of Russian coal, thereby producing Example 1 (GTS-P 3) containing 3 wt % of the catalyst.

Example 2

[0076] (1) Preparation of Catalyst for Desulfurization

[0077] A powder catalyst for desulfurization (GTS-P) was prepared in the same manner as in (1) of Example 1.

[0078] (2) Preparation of Example 2 (GTS-P 5)

[0079] 5 kg of the powder catalyst for desulfurization (GTS-P) obtained in (1) above was mixed with 95 kg of Russian coal, thereby producing Example 2 (GTS-P 5) containing 5 wt % of the catalyst.

Example 3

[0080] (1) Preparation of Catalyst for Desulfurization

[0081] A liquid catalyst for desulfurization (GTS-W) was prepared in the same manner as in (1) of Example 1.

[0082] (2) Preparation of Example 3 (GTS-W 0.3)

[0083] 0.3 kg of the liquid catalyst for desulfurization (GTS-W) obtained in (1) above was mixed with 99.7 kg of Russian coal, thereby producing Example 3 (GTS-W 0.3) containing 0.3 wt % of the catalyst.

Example 4

[0084] (1) Preparation of Catalyst for Desulfurization

[0085] A liquid catalyst for desulfurization (GTS-W) was prepared in the same manner as in (1) of Example 1.

[0086] (2) Preparation of Example 4 (GTS-W 0.5)

[0087] 0.5 kg of the liquid catalyst for desulfurization (GTS-W) obtained in (1) above was mixed with 99.5 kg of Russian coal, thereby producing Example 4 (GTS-W 0.5) containing 0.5 wt % of the catalyst.

Comparative Example

[0088] 100 kg of Russian coal, not mixed with the catalyst for desulfurization, was used.

<Test Example 1> Test of SO.SUB.2 .Emission Reduction Efficiency in DTF

[0089] (1) Test Conditions

[0090] In order to verify the desulfurization efficiency of the prepared catalyst for desulfurization, the desulfurization efficiency test for analyzing and comparing exhaust gas after combustion of Comparative Example using Russian coal applied in Russian coal-fired power plants and Examples 1 to 4 using mixtures of Russian coal and the catalyst for desulfurization was performed in a DTF (Drop Tube Furnace) for evaluating the combustion characteristics of coal.

[0091] As Russian coal used in Comparative Example and Examples 1 to 4, coal from Russia was used as samples, and in order to analyze the basic characteristics of Russian coal, industrial analysis and elemental analysis were carried out by means of an industrial analyzer (TGA-701, Leco) and an elemental analyzer (Micro-Truspec CHNS, Leco). The results are shown in Table 1 below.

TABLE-US-00001 TABLE 1 as received Ultimate analysis Proximate analysis [wt %] [wt %] as received as daf Moisture 20.53 C 72.98 Volatile matter 31.36 H 7.22 Fixed carbon 33.71 O 14.81 Ash 14.40 N 0.65 HHV.sup.1) (kcal/kg) 5,109 S 4.43 .sup.1)HHV = 8100 * C * 0.01 + 34200 * (H * 0.01 O * 0.01/8) + 2500 * S * 0.01 based as received

[0092] Table 1 shows the results of industrial analysis and elemental analysis of Russian coal.

[0093] Russian coal was used in the form of being pulverized to 75 m based on 200 mesh, which is the particle size used in a coal-fired power plant.

[0094] The desulfurization efficiency test of Comparative Example and Examples 1 to 4 was carried out using a 2-zone DTF, and sufficient combustion residence time was ensured under low excess oxygen conditions.

[0095] DTF operating conditions were set taking into consideration the operating conditions of the Russian coal-fired power plant. The conditions for the desulfurization efficiency test of DTF are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Parameter Unit Value Excess O.sub.2 % about 7 Furnace temperature C. 1,050 Coal feed rate g/min 0.01 Mixing ratio GTS-P % wt 3, 5 GTS-W % wt 0.3, 0.5

[0096] Table 2 shows the DTF desulfurization efficiency test conditions.

[0097] The DTF test conditions were as follows: an excess oxygen of 7%, a combustion chamber temperature of 1,050 C. and a coal feed rate of 0.01 g/min. The results of desulfurization efficiency of Comparative Example and Examples 1 to 4 were compared.

[0098] Also, in order to evaluate the effect of the catalyst for desulfurization, a continuous combustion gas analyzer was disposed downstream of the DTF, thereby analyzing gases emitted upon combustion, such as excess O.sub.2, CO, NO, SO.sub.2, NO.sub.2, CO.sub.2, etc.

[0099] (2) Results of Measurement of Average SO.sub.2 Emission

[0100] FIG. 1 shows the test results of average SO.sub.2 emission of Comparative Example and Examples 1 to 4, measured under test conditions of (1) above.

[0101] Average SO.sub.2 emission means that the total amount of SO.sub.2 emitted during the combustion of Comparative Example and Examples 1 to 4 supplied to the DTF was compared and analyzed; that is, the total amount of SO.sub.2 emitted from the initial stage of the test when SO.sub.2 emission is stabilized to the end stage when the coal supply is terminated, was averaged, compared and analyzed.

[0102] As shown in FIG. 1, the average SO.sub.2 emission was 743 ppm in Comparative Example (Raw coal), 403 ppm in Example 1 (GTS-P 3), 271 ppm in Example 2 (GTS-P 5), 538 ppm in Example 3 (GTS-W 0.3), and 435 ppm in Example 4 (GTS-W 0.5).

[0103] The average SO.sub.2 emission of Examples 1 to 4 was decreased overall compared to the average SO.sub.2 emission of Comparative Example.

[0104] In particular, as the amount of the catalyst for desulfurization that was mixed was increased, the SO.sub.2 emission reduction efficiency was increased. Depending on the type of catalyst, the SO.sub.2 emission reduction efficiency of Examples 1 and 2 containing the powder catalyst for desulfurization was significant. However, since the mixing ratio of Examples 1 and 2 is at least 10 times as high as that of Examples 3 and 4 containing the liquid catalyst for desulfurization, the SO.sub.2 emission reduction efficiency of Examples 3 and 4 containing the liquid catalyst for desulfurization is regarded as superior in consideration of the reduction efficiency based on the mixing ratio.

[0105] FIG. 2 shows the results of SO.sub.2 emission reduction efficiency relative to Comparative Example in the average SO.sub.2 emission of FIG. 1, in which the SO.sub.2 emission reduction efficiency was 46% in Example 1 (GTS-P 3), 64% in Example 2 (GTS-P 5), 28% in Example 3 (GTS-W 0.3), and 41% in Example 4 (GTS-W 0.5).

[0106] As shown in FIG. 2, although the coal-to-catalyst mixing ratio of Examples 3 and 4 containing the liquid catalyst for desulfurization is approximately one tenth of that of Examples 1 and 2 containing the powder catalyst for desulfurization, relatively high reduction efficiency can be found to result.

<Test Example 2> Test of Average SO.SUB.2 .Emission in Excess Oxygen Ranges

[0107] FIG. 3 shows the test results of average SO.sub.2 emission in individual excess oxygen ranges of Comparative Example and Examples 1 to 4.

[0108] The average SO.sub.2 emission test in individual excess oxygen ranges is conducted taking into account excess oxygen conditions in an actual Russian coal-fired boiler, and means that the excess oxygen during the test in DTF is divided into predetermined ranges and the average values of SO.sub.2 emission in the predetermined ranges are compared to analyze reduction efficiency. As such, analysis was carried out, except for cases of SO.sub.2 emission in the presence of CO.sub.x of 100 ppm or more due to incomplete combustion or excess fuel and in the presence of NO.sub.x of 50 ppm or less due to incomplete combustion.

[0109] The minimum amount of oxygen theoretically required to completely combust a combustible substance is called the theoretical oxygen amount, and a greater amount of oxygen than the theoretical amount is supplied to the actual combustion device, and the amount of oxygen thus supplied is called the actual oxygen amount. The excess oxygen indicates the ratio of the actual oxygen amount relative to the theoretical oxygen amount.

[0110] As shown in FIG. 3, the excess oxygen ranges are classified into 6.8 to 7.5% (assuming an average of 7%), 7.6 to 8.5% (assuming an average of 8%) and 8.6 to 9.5% (assuming an average of 9%). The analysis was made considering the case where the excess oxygen changes when the combustible substance is combusted in the actual boiler. Overall, when the excess oxygen is increased, the amount of SO.sub.2 that is emitted is lowered.

[0111] In Comparative Example (Raw coal), the highest SO.sub.2 emission of 900 ppm was exhibited in the range of 6.8 to 7.5%, and the average SO.sub.2 emission was about 300 to 400 ppm in Example 1 (GTS-P 3), about 200 to 300 ppm in Example 2 (GTS-P 5), and about 300 to 500 ppm in Example 3 (GTS-W 0.3) and Example 4 (GTS-W 0.5).

[0112] FIG. 4 shows the reduction efficiency of SO.sub.2 emission in the excess oxygen ranges of FIG. 3 compared to Comparative Example. In Example 1 (GTS-P 3) and Example 2 (GTS-P 5) using the powder catalyst for desulfurization, SO.sub.2 reduction efficiency of about 60 to 70% was exhibited, and Example 3 (GTS-W 0.3) and Example 4 (GTS-W 0.5) using the liquid catalyst for desulfurization manifested SO.sub.2 reduction efficiency of about 50 to 60%.

[0113] FIG. 5 shows the results of average SO.sub.2 emission reduction efficiency in the entire excess oxygen range, rather than the SO.sub.2 emission reduction efficiency in individual excess oxygen ranges shown in FIG. 4.

[0114] As shown in FIG. 5, total SO.sub.2 reduction efficiency of 50% or more was exhibited, and SO.sub.2 reduction efficiency was about 60% or more in Example 1 (GTS-P 3) and Example 2 (GTS-P 5), using the powder catalyst for desulfurization, and about 50% or more in Example 3 (GTS-W 0.3) and Example 4 (GTS-W 0.5), using the liquid catalyst for desulfurization.

[0115] The SO.sub.2 reduction efficiency of FIG. 5 is slightly different from the average reduction efficiency of FIG. 2, which is based on a difference in test conditions between FIGS. 2 and 5.

[0116] FIG. 2 shows the reduction efficiency based on the average total amount of overall emitted SO.sub.2, and FIG. 5 shows the results of selective analysis of the amount of emitted SO.sub.2 considering emission of CO.sub.x and NO.sub.x due to incomplete combustion. This indicates that the SO.sub.2 emission reduction efficiency of FIG. 2 is shown in a situation in which there are changes in the excess oxygen and the combustion phenomenon when the combustible substance is combusted in the actual boiler, and also that the SO.sub.2 emission reduction efficiency of FIG. 5 is shown in a situation where stable operation of the excess oxygen is possible.

<Test Example 3> Test of Unburned Carbon Emission Upon Desulfurization Reduction Experiment

[0117] FIG. 6 shows the proportions of unburned carbon of Comparative Example and Examples 1 to 4.

[0118] The proportion of unburned carbon is regarded as a very important factor for evaluating the catalyst efficiency. The reason why sulfur oxide emission during combustion of the combustible substance is reduced is predicted to be based on whether the amount of unburned combustible substance, that is, the amount of unburned carbon, increases to thus reduce the amount of emitted sulfur oxide, or based on whether the amount of unburned carbon is constant or decreases to thus reduce the amount of emitted sulfur oxide, that is, based on the desulfurization effect of the catalyst.

[0119] As shown in FIG. 6, the proportion of unburned carbon was 31.1% in Comparative Example (Raw coal), 30.4% in Example 1 (GTS-P 3), 34% in Example 2 (GTS-P 5), 21.1% in Example 3 (GTS-W 0.3) and 19.5% in Example 4 (GTS-W 0.5).

[0120] The proportion of unburned carbon of Examples 1 and 2 was equal to or slightly greater than that of Comparative Example, which can be deemed to be due to the effect of the catalyst, rather than due to the unburned combustible substance upon combustion of the combustible substance.

[0121] Also, the proportion of unburned carbon of Example 3 (GTS-W 0.3) and Example 4 (GTS-W 0.5) using the liquid catalyst for desulfurization was lower than that of Comparative Example, from which it can be predicted that both the desulfurization effect and the combustibility-improving effect of improving the extent of combustion of the combustible substance are exhibited.

[0122] As is apparent from Test Examples 1 to 3, when the combustible substance (Russian coal, Comparative Example) is mixed with the catalysts for desulfurization of Examples 1 to 4 and then combusted, the desulfurization effect, that is, reduction efficiency ranging from 28% to 70%, was exhibited. Furthermore, as seen in Test Example 3, the reduction effect of sulfur oxide can be confirmed to be due to the actual effect of the catalyst for desulfurization, rather than due to the non-combustion of the combustible substance.

[0123] Although preferred embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.