CO SHIFT CATALYST, CO SHIFT REACTION APPARATUS, AND METHOD FOR PURIFYING GASIFIED GAS

Abstract

A CO shift catalyst according to the present invention reforms carbon monoxide (CO) in gas. The CO shift catalyst has one of molybdenum (Mo) or iron (Fe) as a main component and has an active ingredient having one of nickel (Ni) or ruthenium (Ru) as an accessory component and one or two or more kinds of oxides from among titanium (Ti), zirconium (Zr), and cerium (Ce) for supporting the active ingredient as a support. The temperature at the time of manufacturing and firing the catalyst is equal to or higher than 550° C.

Claims

1. A method of producing a CO shift catalyst which reforms carbon monoxide (CO) in gas comprising: obtaining a complex oxide including titanium (Ti) and silicon (Si) as a support; and then supporting active ingredients including molybdenum (Mo) or iron (Fe) as a main component and nickel (Ni) or ruthenium (Ru) as an accessory component on the support of the complex oxide; and then firing them to obtain the CO shift catalyst at a high temperature from 550° C. to 800° C. to obtain a crystal structure of an anatase type.

2. The method of producing a CO shift catalyst according to claim 1, wherein a support amount of the main component of the active ingredient is 0.1 to 25 percent by weight, and a support amount of the accessory component is 0.01 to 10 percent by weight.

3. A method for purifying gasified gas, comprising: after smoke and dust in gasified gas obtained by a gasification furnace have been removed by a filter, further removing halogen in the gasified gas by a wet scrubber apparatus after removal of smoke and dust, subsequently removing carbon dioxide and hydrogen sulfide in the gasified gas after removal of halogen; and obtaining purified gas by performing the CO shift reaction for converting CO in the gasified gas after removal of carbon dioxide and hydrogen sulfide into CO.sub.2 by using the CO shift catalyst obtained by the method according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0022] FIG. 1 is a schematic diagram of a gasified gas purifying system including a CO shift reaction apparatus in which a CO shift catalyst has been filled according to the present embodiment.

[0023] FIG. 2 is a diagram of an exemplary coal gasification power generation plant.

DESCRIPTION OF EMBODIMENTS

[0024] The present invention will be described in detail below with reference to the drawings. The present invention is not limited to the embodiment below. Also, components of the embodiment below include a component that a person skilled in the art could have easily arrived at, and a component which is substantially identical to the components of the embodiment, that is, a component in the equivalent range. In addition, the components disclosed in the embodiment below can be appropriately combined with each other.

Embodiment

[0025] A CO shift catalyst according to an embodiment of the present invention and a CO shift reaction apparatus using the same will be described with reference to the drawings. FIG. 1 is a schematic diagram of a gasified gas purifying system including the CO shift reaction apparatus in which the CO shift catalyst has been filled.

[0026] As illustrated in FIG. 1, a gasified gas purifying system 10 includes a gasification furnace 11 for gasifying coal which is a fuel F, a filter 13 for removing smoke and dust in gasified gas 12 which is produced gas, a wet scrubber apparatus 14 for removing halogen in the gasified gas 12 which has passed through the filter 13, a gas purifying apparatus 15, a first heat exchanger 17 and a second heat exchanger 18 which increase the temperature of the gasified gas 12, a CO shift reaction apparatus 20 including a CO shift catalyst 19 for converting CO in the gasified gas 12 of which the temperature is increased at, for example, 300° C. into CO.sub.2 and making it to be purified gas 22. The gas purifying apparatus 15 includes an absorber 15A for absorbing and removing CO.sub.2 and H.sub.2S in the heat-exchanged gasified gas 12 and a regenerator 15B for regenerating them. Also, the gas purifying apparatus 15 has a regeneration superheater 16 on a side of the regenerator 15B. A reference sign 21 indicates water vapor in FIG. 1.

[0027] In the gasification furnace 11, the coal which is the fuel F has contact with a gasification agent such as air and oxygen so that the coal is burned and gasified. Accordingly, the gasified gas 12 is generated. The gasified gas 12 generated in the gasification furnace 11 has carbon monoxide (CO), hydrogen (H.sub.2), and carbon dioxide (CO.sub.2) as main components. However, a small amount of an element included in the coal (for example, a halogen compound and a heavy metal such as mercury (Hg)) and a small amount of an unburned compound at the time of coal gasification (for example, polycyclic aromatic such as phenol and anthracene, cyanogen, and ammonia) are included.

[0028] The gasified gas 12 generated in the gasification furnace 11 is introduced from the gasification furnace 11 to the filter 13. In the gasified gas 12 introduced to the filter 13, smoke and dust are removed from the gasified gas 12. A cyclone, an electrostatic precipitator (EP), and the like may be used other than the filter.

[0029] After the filter 13 has removed smoke and dust, the gasified gas 12 is purified by the gas purifying apparatus 15. After that, the temperature of the gasified gas 12 is increased by the first and second heat exchangers 17 and 18.

[0030] Subsequently, after the water vapor 21 has been supplied by a water vapor supplying apparatus (water vapor supplying unit), the water vapor 21 is introduced to the CO shift reaction apparatus 20 having the CO shift catalyst 19. The CO shift reaction apparatus 20 reforms carbon monoxide (CO) in the gasified gas 12 and converts it into carbon dioxide (CO.sub.2) under the CO shift catalyst 19.

[0031] The CO shift catalyst 19 according to the present invention is the CO shift catalyst for reforming carbon monoxide (CO) in the gasified gas and has an active ingredient including molybdenum (Mo) or iron (Fe) as the main component and nickel (Ni) or ruthenium (Ru) as an accessory component and a complex oxide including two or more kinds from among titanium (Ti), zirconium (Zr), cerium (Ce), silica (Si), aluminum (Al), and lanthanum (La) for supporting the active ingredient as the support. The CO shift catalyst 19 is formed by firing them at a high temperature of equal to or more than 550° C., more preferably, equal to or more than 600° C.

[0032] As an exemplary complex oxide of the support, TiO.sub.2—SiO.sub.2, TiO.sub.2—ZrO.sub.2, TiO.sub.2—Al.sub.2O.sub.3, ZrO.sub.2—Al.sub.2O.sub.3, TiO.sub.2—CeO.sub.2, and TiO.sub.2—La.sub.2O.sub.3 are used.

[0033] Also, the firing temperature of the support is of 500° C. which is the normal firing temperature to equal to or higher than 550° C., and more preferably, equal to or higher than 600° C., More preferably, the firing at a high temperature which is equal to or higher than 700° C. is performed for a predetermined time.

[0034] It is preferable that the upper limit of the firing temperature be equal to or lower than 850° C. At 850° C., a crystal structure of the support is changed from an anatase type to a rutile type.

[0035] Also, it is preferable that the firing time be at least equal to or longer than one hour and preferably equal to or longer than two hours. More preferably, it is preferable that the firing time be equal to or longer than three hours.

[0036] In the present invention, the temperature of the catalyst firing is equal to or higher than 550° C. that is higher than the normal temperature of 500° C. Therefore, when the CO shift catalyst according to the present invention is used, an initial CO conversion rate becomes slightly smaller than that of the catalyst fired at 500° C. However, for example, the CO conversion rate after a hundred-hour durability test becomes higher than that of the catalyst fired at 500° C. The CO conversion rate after a hundred-hour durability test becomes higher because a carbon production reaction can be prevented due to the reduction in a specific surface area by firing at the high temperature.

[0037] Here, it is preferable that a support amount of molybdenum (Mo) or iron (Fe) which is the main component be 0.1 to 25 percent by weight, and more preferably, 7 to 20 percent by weight. It is preferable that a support amount of nickel (Ni) or ruthenium (Ru) which is the accessory component be 0.01 to 10 percent by weight, and more preferably, 2 to 10 percent by weight.

[0038] In this way, according to the CO shift catalyst 19 of the present invention, a CO shift conversion can be stably performed for a long time. Also, the amount of the water vapor to be supplied is reduced, and an efficient gas purifying process can be provided.

EXAMPLE OF TEST

[0039] An example of a test indicating an effect of the present invention will be described below.

[0040] 1) Manufacturing Method for Test Catalyst 1

[0041] After a Ti source which is TiOSO.sub.4 of 320.2 g has been mixed with water of 1441.8 g at a normal temperature, “SNOWTEX® O(product name)” (silica sol, SiO.sub.2=20 wt. %) of 200 g manufactured by Nissan Chemical Industries, Ltd. is mixed. After that, NH.sub.4OH having 9 vol. % is slowly dripped, and pH in the mixed liquid is made to be seven. Then, a deposit is generated, and the mixed liquid is stirred for two more hours and matured. After being filtered and sufficiently cleaned, the deposit obtained after maturing is dried and fired (for five hours at 500° C.). Accordingly, the support is obtained.

[0042] Relative to the support, NiO and MoO.sub.3 are added so that four percent by weight of NiO and 14 percent by weight of MoO.sub.3 are supported relative to an amount of all powders which are finally obtained. After that, they are evaporated, dried, and impregnated on a ceramic dish. Then, after the obtained powder has been completely dried by a dryer, the powder catalyst is obtained by firing the obtained powder at 550° C. for three hours (temperature rising speed 100° C/h).

[0043] After the powder of the obtained powder catalyst has been fixed by a pressure molding apparatus of 30 ton, the power is crushed so that the particle size becomes within a range of a predetermined particle size (for example, 2 to 4 mm) and sieved. Accordingly, a test catalyst 1 is obtained.

[0044] Also, after the power is dried as mentioned above, the powder catalyst is obtained by firing at 600° C., 700° C., and then, 800° C. After that, an operation similar to that for manufacturing the test catalyst 1 is performed, and the test catalyst 1 having a different firing temperature is obtained.

[0045] 2) Manufacturing Method for Test Catalyst 2

[0046] In the manufacture for the test catalyst 1, ZrOCl.sub.2 corresponding to 40 g in terms of ZrO.sub.2 is used instead of a SiO.sub.2 source as the support. Other than that, the operation similar to that for manufacturing the test catalyst 1 is performed, and accordingly, the test catalyst 2 is obtained.

[0047] 3) Manufacturing Method for Test Catalyst 3

[0048] In the manufacture for the test catalyst 1, Al(NO.sub.3).sub.3.9H.sub.2O corresponding to 40 g in terms of Al.sub.2O.sub.3 is used instead of the SiO.sub.2 source as the support. Other than that, the operation similar to that for manufacturing the test catalyst 1 is performed, and accordingly, the test catalyst 3 is obtained.

[0049] 4) Manufacturing Method for Comparison Catalysts 1 to 3

[0050] In the test catalysts 1 to 3, the firing temperature of the support is assumed to be 500° C. Other than that, the comparison catalysts 1 to 3 are obtained by similarly performing the operation.

[0051] The catalyst is evaluated as follows.

[0052] Regarding the evaluation test, the catalyst of 3.3 cc is filled in a tubular reaction tube, and a catalytic activity is evaluated by a circulation type micro-reactor apparatus. The inside diameter of the tubular reaction tube is 14 mm.

[0053] The initial catalytic activity is compared by obtaining the CO conversion rates of gas flow rate change of an inlet and outlet of a catalyst layer.

[0054] The initial activity evaluation condition and the activity evaluation condition after durability are as follows.

[0055] The test is performed under the condition of 0.9 MPa, the temperature 250° C., SV=6, 000.sup.−1 while assuming that a gas composition be H.sub.2/CO/CO.sub.2=30/50/20 mole percent, H.sub.2S=700 ppm, and S/CO=1.0.

[0056] The CO conversion rate is obtained according to the following formula (I).

CO conversion rate (%)=(1−(CO gas flow velocity at outlet of catalyst layer (mol/time))/(CO gas flow velocity at inlet of catalyst layer (mol/time)))×100   (I)

[0057] Also, the durability (acceleration) test is performed under the condition below.

[0058] The test is performed under the condition that 0.9 MPa, the temperature 450° C., SV=2, and 000h.sup.−1 while assuming that a gas composition be H.sub.2/CO/CO.sub.2=30/50/20 mole percent, H.sub.2S=700 ppm, and S/CO=0.1.

[0059] A list of the composition of the catalyst and the result of the test are illustrated in Table 1.

TABLE-US-00001 TABLE 1 ACTIVE INGREDIENT SUPPORT SUPPORT FIRING AMOUNT AMOUNT WEIGHT TEMPERATURE METAL (wt %) METAL (wt %) SUPPORT RATIO (° C. × 3 h) TEST Mo 14 Ni 4 TiO.sub.2—SiO.sub.2 80:20 550 CATALYST 600 1 700 800 TEST ↑ ↑ ↑ ↑ TiO.sub.2—ZrO.sub.2 80:20 550 CATALYST 600 2 700 800 TEST ↑ ↑ ↑ ↑ TiO.sub.2—Al.sub.2O.sub.3 80:20 550 CATALYST 600 3 700 800 COMPARISON ↑ ↑ ↑ ↑ TiO.sub.2—SiO.sub.2 80:20 500 CATALYST 1 COMPARISON ↑ ↑ ↑ ↑ TiO.sub.2—ZrO.sub.2 80:20 500 CATALYST 2 COMPARISON ↑ ↑ ↑ ↑ TiO.sub.2—Al.sub.2O.sub.3 80:20 500 CATALYST 3 RATIO OF CO CO CONVERSION INITIAL INITIAL CONVERSION RATE AFTER 100 H AVERAGE SPECIFIC CO RATE AFTER C DURABLIITY RELATIVE PORE SURFACE CONVERSION 100 H DEPOSITION TO INITIAL CO DIAMETER AREA RATE DURABILITY AMOUNT CONVERSION RATE (Å) (m.sup.2/g) (%) (%) (wt %) (%) TEST 72 118 81.8 64 0.79 78 CATALYST 79 109 81.6 63.9 0.81 78 1 92 91 80.8 64.2 0.83 79 110 80 79.6 63.8 0.95 80 TEST 161 115 83.2 65.7 0.79 79 CATALYST 178 106 82.0 63.8 0.81 78 2 225 94 80.9 62.7 0.81 78 250 86 79.9 62.6 0.93 78 TEST 186 111 82.3 65.4 0.8 79 CATALYST 192 101 81.6 64.1 0.83 79 3 201 89 80.2 63.7 0.87 79 163 78 78.2 62.2 0.97 80 COMPARISON 79 121 83.8 62.9 1.15 75 CATALYST 1 COMPARISON 78 118 82.9 59.7 1.21 72 CATALYST 2 COMPARISON 81 112 81.7 63.2 1.18 77 CATALYST 3

[0060] As illustrated in Table 1, it has been confirmed that the catalysts 1 to 3 according to the example of the test have small reduction in the CO conversion rates after the hundred-hour durability test and that the CO shift reaction is excellently maintained at each high firing temperature.

[0061] Also, since the carbon production reaction can be prevented by decreasing the specific surface area by firing at the high temperature, the high CO conversion rate after the hundred-hour durability test can be maintained.

[0062] Therefore, the CO shift catalyst according to the test has the complex oxide as the support, and the temperature of firing the support is a high temperature equal to or higher than 600° C. Accordingly, it has been found that the CO shift catalyst has an excellent durability and the CO shift reaction can be stably maintained for a long time even in a case where a carbon (C) deposition occurs.

[0063] As described above, the specific surface area is reduced by firing at the high temperature as in the present invention. As a result, the carbon production reaction can be prevented.

[0064] <Coal Gasification Power Generation Plant>

[0065] A coal gasification power generation plant having the CO shift reaction apparatus 20 according to the present embodiment will be described with reference to the drawing. FIG. 2 is a diagram of an exemplary coal gasification power generation plant. As illustrated in FIG. 2, a coal gasification power generation plant 50 includes a gasification furnace 11, a filter 13, a COS converter 51, the CO shift reaction apparatus 20, a gas purifying apparatus (H.sub.2S/CO.sub.2 recovery unit) 15, and a combined power generation facility 52.

[0066] The coal which is a fuel F and air 54 from a gasified air compressor 53 are supplied to the gasification furnace 11, and the coal is gasified by the gasification furnace 11. Then, the gasified gas 12 which is produced gas is obtained. Also, an air separator 55 separates the air 54 into nitrogen (N.sub.2) and oxygen (O.sub.2), and N.sub.2 and O.sub.2 are appropriately supplied into the gasification furnace 11. The coal gasification power generation plant 50 supplies the gasified gas 12 obtained by the gasification furnace 11 to the filter 13 and removes dust from the gasified gas 12. After that, the coal gasification power generation plant 50 supplies the gasified gas 12 to the COS converter 51 and converts COS included in the gasified gas 12 into H.sub.2S.

[0067] After that, the gasified gas 12 including H.sub.2S is supplied to the CO shift reaction apparatus 20, and the water vapor 21 is supplied into the CO shift reaction apparatus 20. A CO shift reaction for converting CO in the gasified gas 12 into CO.sub.2 in the CO shift reaction apparatus 20 is caused.

[0068] The CO shift reaction apparatus 20 uses the CO shift catalyst 19 according to the present invention. Therefore, even when the amount of the water vapor is largely reduced as described above, reformed gas can be efficiently generated for a long time.

[0069] After the CO shift reaction apparatus 20 has converted CO in the gasified gas 12 into CO.sub.2, the obtained reformed gas is supplied to the H.sub.2S/CO.sub.2 recovery unit which is the gas purifying apparatus 15. Then, the H.sub.2S/CO.sub.2 recovery unit removes CO.sub.2 and H.sub.2S in the reformed gas.

[0070] The purified gas 22 after purified by the gas purifying apparatus 15 is supplied to the combined power generation facility 52. The combined power generation facility includes a gas turbine 61, a steam turbine 62, a generator 63, and a heat recovery steam generator (HRSG) 64. The combined power generation facility 52 supplies the purified gas 22 to a combustor 65 of the gas turbine 61 which is a power generating unit. Also, the gas turbine 61 supplies air 67, which is supplied to the compressor 66, to the combustor 65. The gas turbine 61 generates high-temperature and high-pressure combustion gas 68 by combusting the purified gas 22 by the combustor 65 and drives a turbine 69 by the combustion gas 68. The turbine 69 is coupled to the generator 63, and the generator 63 generates the power by driving the turbine 69. Since flue gas 70 after the turbine 69 has been driven has the temperature of 500 to 600° C., the flue gas 70 is sent to the heat recovery steam generator (HRSG) 64, and heat energy is recovered. The heat recovery steam generator (HRSG) 64 generates steam 71 by the heat energy of the flue gas 70, and the steam turbine 62 is driven by the steam 71. After being used by the steam turbine 62, the steam 71 is discharged from the steam turbine 62 and cooled by the heat exchanger 72. After that, the steam 71 is supplied to the heat recovery steam generator 64. Also, after NOx and the like in the flue gas 73 has been removed by a denitration apparatus (not illustrated) and the like, the flue gas 73 of which the heat energy is recovered by the heat recovery steam generator 64 is discharged into the atmosphere via a stack 74.

[0071] In this way, the coal gasification power generation plant 50 having the CO shift reaction apparatus 20 according to the present embodiment converts CO included in the gasified gas gasified by the gasification furnace 11 into CO.sub.2 while preventing the deterioration of the CO shift catalyst even when the amount of the water vapor is reduced (water vapor (H2O/CO)=about 1) in the CO shift reaction apparatus 20. Then, the CO shift reaction of the reformed gas can be stably performed for a long time.

[0072] Accordingly, regarding the CO shift reaction, the CO shift reaction can be stably continued with small amount of water vapor. Therefore, the amount of the water vapor to be extracted from the HRSG 64 can be reduced, and the coal gasification power generation plant 50 can be operated with an improved energy efficiency.

[0073] The CO shift reaction apparatus 20 is not limited to be placed between the COS converter 51 and the gas purifying apparatus (H.sub.2S/CO.sub.2 recovery unit) 15 (on the front stream side of H.sub.2S/CO.sub.2 recovery unit) and may be placed on the back stream side of the gas purifying apparatus (H.sub.2S/CO.sub.2 recovery unit) 15.

[0074] Also, in the present embodiment, a case has been described in which the purified gas 22 discharged from the gas purifying apparatus (H.sub.2S/CO.sub.2 recovery unit) 15 is used as gas for the turbine. However, since the CO shift reaction apparatus 20 converts a large amount of CO included in the gasified gas 12 into CO.sub.2, the purified gas 22 may be used as material gas used to synthesize a chemical product such as methanol and ammonia other than the gas for the turbine.

[0075] In the above, a case has been described in which the CO shift reaction apparatus 20 according to the present embodiment converts CO in the gasified gas 12 generated by gasifying the fuel F such as coal by the gasification furnace 11 into CO.sub.2. However, the present invention is not limited to this. For example, the present invention can be similarly applied to the CO shift reaction apparatus to convert gas including CO into CO.sub.2 in a fuel cell and the like.

REFERENCE SIGNS LIST

[0076] 10 gasified gas purifying system

[0077] 11 gasification furnace

[0078] 12 gasified gas

[0079] 13 filter

[0080] 14 wet scrubber apparatus

[0081] 15A absorber

[0082] 15B regenerator

[0083] 15 gas purifying apparatus

[0084] 19 CO shift catalyst

[0085] 20 CO shift reaction apparatus

[0086] 21 water vapor

[0087] 22 purified gas