Patent Application
20150291898
The present invention relates to a CO shift catalyst that converts CO in a gasification gas into CO2, a CO shift reactor, and a method for purifying a gasification gas.
Effective use of coal has been attracted as one of important countermeasures for recent energy problems.
On the other hand, to convert coal into an energy medium with a high value-added, an advanced technology such as a coal gasification technology and a gas purifying technology is necessary.
An integrated coal gasification combined cycle (IGCC) system, which generates power using the gasification gas, is suggested (Patent Literature 1).
The integrated coal gasification combined cycle (IGCC) represents a system in which coal is converted into a combustible gas in a high-temperature and high-pressure gasification furnace, and combined cycle power generation is performed by a gas turbine and a steam turbine by using the gasification gas as a fuel.
For example, the majority of hydrocarbon compounds that exist in the coal gasification gas (generated gas) is carbon monoxide (CO), and carbon dioxide (CO2) and hydrocarbon (CH4, CnHm) occupy only several percentage of the hydrocarbon compound. As a result, it is necessary to convert CO that exists in the generated gas into CO2 so as to recover CO2, and conversion into CO2 through the following reaction by using a shift catalyst while adding water vapor (H2O) is suggested (Patent Literature 2).
CO+H2OCO2+H2+40.9 kJ/mol (exothermic reaction) (1)
From a finding about a shift reaction in a chemical industry field until now, when an water vapor addition ratio (H2O/CO) at an inlet of a CO shift reactor is sufficiently increased to allow the reaction of (1) to progress, a desired conversion ratio of CO→CO2 is obtained.
For example, a Co-Mo/Al2O3-based catalyst has been typically used as a CO shift catalyst. However, this catalyst exhibits activity at a high-temperature region (for example, 350° C. or higher), and thus there is a concern of precipitation of C.
Therefore, it is necessary to add an excessive amount of water vapor (water vapor (H2O)/CO≧3) as a countermeasure against the precipitation of C.
On the other hand, an IGCC plant provided with a CO2 recovering facility is a power generation plant, and it is necessary to consider an environment (reduction in CO2 emission), and it is also necessary to put emphasis on power generation efficiency of the plant.
That is, as a water vapor addition source for realizing water vapor addition ratio (H2O/CO) while being supplied to the shift reactor, for example, pressurized steam in bleed air from a heat recovery steam generator (HRSG) is used. However, reduction in an amount of water vapor that is bled is an important factor for an improvement in plant efficiency, and thus it is demanded to reduce the amount of water vapor that is bled from the heat recovery steam generator (HRSG) as can as possible from the viewpoint of an increase in power generation efficiency.
Therefore, it is desired earnestly to provide a CO shift catalyst in which an improvement in durability against C precipitation is realized, and CO shift conversion is stably possible for a long period of time even in a case where a supply amount of water vapor greatly decreases approximately from water vapor (H2O)/CO=3 to water vapor (H2O)/CO=1.
The invention has been made in consideration of the above-described problem, and an object thereof is to provide a CO shift catalyst in which deterioration in a catalyst is not great even when an amount of water vapor is small and CO shift reaction can be carried in a stable and efficient manner, a CO shift reactor, and a method for purifying a gasification gas.
According to a first aspect of the present invention in order to solve the above mentioned problems, there is provided a CO shift catalyst that reforms carbon monoxide (CO) in a gas, including: an active component containing either molybdenum (Mo) or iron (Fe) as a main component, and either nickel (Ni) or ruthenium (Ru) as an accessory component; and a carrier which carries the active component and consists of oxides of titanium (Ti), zirconium (Zr), and cerium (Ce), wherein an average pore size of the carrier is 300 Å or more.
According to a second aspect of the present invention, there is provided the CO shift catalyst according to the first aspect, wherein in the active component, an amount of the main component that is carried is 0.1 wt % to 25 wt %, and an amount of the accessory component that is carried is 0.01 wt % to 10 wt %.
According to a third aspect of the present invention, there is provided a CO shift reactor, including: a reactor tower filled with the CO shift catalyst according to the first or second aspect.
According to a fourth aspect of the present invention, there is provided a method for purifying a gasification gas, the method including: removing dust in a gasification gas, which is obtained in a gasification furnace, with a filter; purifying the gasification gas, which is subjected to a CO shift reaction, with a wet scrubber device; removing carbon dioxide and hydrogen sulfide in the gasification gas; and subjecting the gasification gas to a CO shift reaction which converts CO in the gasification gas into CO2 by using the CO shift catalyst according to the first or second aspect to obtain a purified gas.
In the CO shift catalyst according to the invention, an average pore size of the catalyst is set to be large, and thus even when carbon (C) precipitation occurs, it is possible to exhibit an effect in which durability is excellent, and CO shift reaction can be stably maintained for a long period of time.
Hereinafter, the invention will be described in detail with reference to the attached drawings. In addition, the invention is not limited to the following example. In addition, constituent elements in the following example include constituent elements which can be easily assumed by a person having ordinary skill in the art and substantially the same constituent elements, which are so-called equivalent range. Furthermore, constituent elements disclosed in the following example may be appropriately combined.
A CO shift catalyst according to an example of the invention, and a CO shift reactor using the CO shift catalyst will be described with reference to the attached drawings.
As illustrated in
In the gasification furnace 11, coal that is the fuel F is brought into contact with a gasification agent such as air and oxygen, and is combusted and gasified, whereby a gasification gas 12 is generated. The gasification gas 12 that is generated in the gasification furnace 11 contains carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2) as a main component. However, the gasification gas 12 also contains elements (for example, a halogen component and a heavy metal such as mercury (Hg)) contained in coal in a slight amount, non-combusted compounds (for example, polycyclic aromatic compounds such as phenol and anthracene, cyan, ammonia, and the like) during coal gasification, and the like in a slight amount.
The gasification gas 12 generated in the gasification furnace 11 is introduced into the filter 13 from the gasification furnace 11. Dust in the gasification gas 12 that is introduced into the filter 13 is removed from the gasification gas 12. In addition, in addition to the filter, a cyclone, an electrostatic precipitator (EP), and the like may be used.
After removal of dust with the filter 13, the gasification gas 12 is subjected to gas purification with the gas purifying device 15, and then a temperature of the gasification gas 12 is risen with the first and second heat exchangers 17 and 18.
Subsequently, the water vapor 21 is supplied by a water vapor supply device (water vapor supply means), and then the gasification gas 12 is introduced to the CO shift reactor 20 provided with the CO shift catalyst 19. Carbon monoxide (CO) in the gasification gas 12 is reformed with the CO shift reactor 20 to convert CO into carbon dioxide (CO2) under presence of the CO shift catalyst 19.
The CO shift catalyst 19 according to the invention is a CO shift catalyst that reforms carbon monoxide (CO) in a gas, and includes an active component containing either molybdenum (Mo) or iron (Fe) as a main component, and either nickel (Ni) or ruthenium (Ru) as an accessory component, and a carrier which carries the active component and consists of oxides of titanium (Ti), zirconium (Zr), and cerium (Ce). An average pore size of the carrier is set to be large.
As the carrier, oxides of TiO2, ZrO2, and CeO2 are preferable.
In the invention, the average pore pore of the carrier is set to be large. Accordingly, in a case of using the CO shift catalyst of the invention, even when an amount of water vapor is reduced (for example, approximately from water vapor (H2O)/C0=3 to water vapor (H2O)/C0=1), or even when carbon (C) precipitates to a pore having a large pore size, covering does not occur with respect to the entirety of the pore, and thus the active component is not covered. As a result, even when the CO shift reaction is allowed to proceed with a small amount of water vapor for a long period of time, carbon precipitation occurs, but clogging does not occur in the entirety of pore. Accordingly, CO shift reaction efficiency does not greatly decrease, and thus satisfactory CO shift reaction can be allowed to proceed.
Here, a carried amount of molybdenum (Mo) or iron (Fe), which is a main component, is preferably set to 0.1 wt % to 25 wt %, and more preferably 7 wt % to 20 wt %, and a carried amount of nickel (Ni) or ruthenium (Ru), which is an accessory component, is preferably set to 0.01 wt % to 10 wt %, and more preferably 2 wt % to 10 wt %.
As illustrated in the following test example, the average pore size is preferably set to 300 A or more.
To make large the average pore size, the carrier is fired for a predetermined time at a typical firing temperature of 500° C. to 550° C., preferably 600° C. or higher, and more preferably a high temperature of 700° C. or higher.
In addition, the upper limit of the firing temperature is preferably set to 850° C. or lower at which a crystal structure of the carrier is converted from an anatase type to a rutile type.
In addition, the firing time is set to at least one hour or more, preferably two hours or more, and still more preferably three hours or more.
As described above, according to the CO shift catalyst according to the invention, when converting CO in gasification gas 12 gasified in the gasification furnace 11 into H2, even in a case where a great decrease occurs approximately from water vapor (H2O)/C0=3 to water vapor (H2O)/C0=1, and precipitation of carbon occurs, since the pore size of the carrier is set to a predetermined size or greater, an improvement in durability against C precipitation is realized, and CO shift conversion is stably possible for a long period of time. In addition, an amount of water vapor that is supplied is reduced, and thus it is possible to provide a gas purifying process with high efficiency.
[Test Examples]
Hereinafter, test examples illustrating the effect of the invention will be described.
1) Manufacturing Method of Test Catalyst 1 100 g of titanium oxide (TiO2 (trade name: MC-90), manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 4 wt % of NiO was carried and 14 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 600° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst.
The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Test Catalyst 1.
2) Manufacturing Method of Test Catalyst 2
100 g of titanium oxide (TiO2 (trade name: MC-90) manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 4 wt % of NiO was carried and 14 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 700° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst.
The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Test Catalyst 2.
3) Manufacturing Method of Test Catalyst 3 100 g of titanium oxide (TiO2 (trade name: MC-90), manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 4 wt % of NiO was carried and 14 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 800° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst.
The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Test Catalyst 3.
4) Manufacturing Method of Test Catalyst 4 100 g of titanium oxide (TiO2 (trade name: MC-90), manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 2 wt % of NiO was carried and 7 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 700° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst.
The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Test Catalyst 4.
5) Manufacturing Method of Test Catalyst 5
100 g of titanium oxide (TiO2 (trade name: MC-90), manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 10 wt % of NiO was carried and 20 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 700° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst.
The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Test Catalyst 5.
6) Manufacturing Method of Test Catalyst 6
With regard to the manufacturing method of Test Catalyst 2, before impregnation, 100 g of titanium oxide (TiO2 (trade name: MC-90)) was put into a porcelain dish and was fired at 700° C. for three hours (a temperature rising rate of 100° C./h). Subsequently, nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the fired titanium oxide in such a manner that 4 wt % of NiO was carried and 14 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then Ni and Mo were subjected to an impregnation treatment with an evaporation to dryness method. After drying, firing was performed at 500° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining Test Catalyst 6.
7) Manufacturing Method of Comparative Catalyst 1 100 g of titanium oxide (TiO2 (trade name: MC-90), manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 4 wt % of NiO was carried and 10 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 500° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst. The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Comparative Catalyst 1.
8) Manufacturing Method of Comparative Catalyst 2
100 g of titanium oxide (TiO2 (trade name: MC-90), manufactured by ISHIHARA SANGYO KAISHA, LTD.) was put into a porcelain dish, and nickel nitrate hexahydrate (NN) and ammonium molybdate tetrahydrate (MA), which were dissolved in 150 ml of water, were added to the titanium oxide in such a manner that 4 wt % of NiO was carried and 14 wt % of MoO3 was carried on the basis of the total amount of powders which were finally obtained, and then the resultant mixture was subjected to evaporation to dryness and impregnation on the porcelain dish. In addition, powders thus obtained were completely dried with a dryer, and were fired at 850° C. for three hours (a temperature rising rate of 100° C./h), thereby obtaining a powder catalyst.
The powder catalyst thus obtained was fixed with a compression molding machine set to 30 tons, and was pulverized to have a particle size in a predetermined particle size range (for example, 2 mm to 4 mm). Then, the pulverized powder was sieved to obtain Comparative Catalyst 2.
Evaluation of the catalysts was performed as described below.
An evaluation test was performed as follows. 3.3 cc of catalyst was filled in a reaction tube with a tubular shape having an inner diameter of 14 mm, and then catalytic activity was evaluated with a flow type microreactor device.
In comparison of initial catalytic activity, a CO conversion ratio that is a variation between gas flow rates on an inlet side and an outlet side of a catalyst layer was obtained.
Evaluation conditions about initial activity and activity after endurance were set as follows.
A gas composition was set to H2/CO/CO2=30/50/20 in terms of mol %, H2S was set to 700 ppm, S/CO was set to 1.0, and a test was performed under conditions of 0.9 MPa, a temperature of 250° C., and SV=6,000 h−1.
A CO conversion ratio was obtained by the following Expression (I)
CO conversion ratio (%)=(1−(flow velocity (mol/hour) of a CO gas on an outlet side of a catalyst layer))/(flow velocity (mol/hour) of the CO gas on an inlet side of the catalyst layer))×100 (I)
In addition, a durability (acceleration) test was performed under the following conditions.
A gas composition was set to H2/CO/CO2=30/50/20 in terms of mol %, H2S was set to 700 ppm, S/CO was set to 0.1, and a test was performed under conditions of 0.9 MPa, a temperature of 450° C., and SV=2,000 h−1.
Composition lists of the catalyst and test results are shown in Table 1.
As shown in Table 1, in Catalysts 1 to 6 according to present test examples, it was confirmed that even in a small amount of water vapor, a decrease in a CO conversion ratio after an endurance test of 100 hours was small, and the CO shift reaction was maintained in a satisfactory manner.
In any catalyst, a deterioration ratio in the CO conversion ratio was satisfactory as 85% to 95%, and a great decrease was not found.
Particularly, in Mo—Ni-based catalysts of Test Catalysts 2 to 5, the initial activity was satisfactory, and a decrease in the CO conversion ratio after the endurance test for 100 hours was very small.
In contrast, in Comparative Catalyst 1 according to a comparative example, the CO conversion ratio greatly decreased (deterioration ratio was 75%). In addition, Comparative Catalyst 2 was subjected to a high-temperature treatment (850° C.), and thus a crystal structure of a carrier was changed to a rutile type, and thus there was almost no catalytic activity.
As is clear from
Accordingly, in the CO shift catalyst according to this test, the average pore size of the catalyst was set to be large, and thus even when carbon (C) precipitation occurred, it was proved that the CO shift catalyst is excellent in durability and thus the CO shift reaction can be stably maintained for a long period of time.
<Coal Gasification Power Generation Plant>
A coal gasification power generation plant provided with the CO shift reactor 20 according to this example will be described with reference to the attached drawing.
Coal that is a fuel F, and air 54 from a gasification air compressor 53 are supplied to the gasification furnace 11 and the coal is gasified in the gasification furnace 11, thereby obtaining the gasification gas 12 that is a generated gas. In addition, in the gasification furnace 11, the air 54 is separated into nitrogen (N2) and oxygen (O2) with an air separating device 55 and N2 and O2 are appropriately supplied to the gasification furnace 11. In the coal gasification power generation plant 50, the gasification gas 12 obtained in the gasification furnace 11 is supplied to the filter 13 to remove dust, and then the gasification gas is supplied to the COS converting device 51 to convert COS contained in the gasification gas 12 into H2S.
Then, the gasification gas 12 containing H2S is supplied to the CO shift reactor 20, and water vapor 21 is supplied to the CO shift reactor 20 to allow a CO shift reaction, which converts CO in the gasification gas 12 into CO2, to occur in the CO shift reactor 20.
In the CO shift reactor 20, the CO shift catalyst according to the invention is used. Accordingly, even when an amount of water vapor is greatly reduced as described above, it is possible to efficiently generate a reformed gas for a long period of time.
The resultant reformed gas, which is obtained after converting CO in the gasification gas 12 into CO2 in the CO shift reactor 20, is supplied to a H2S/CO2 recovery unit that is the gas purifying device 15 to remove CO2 and H2S in the reformed gas with the H2S/CO2 recovery unit.
A purified gas 22, which is purified with the gas purifying device 15, is supplied to the combined power generation facility 52. The combined power generation facility 52 includes a gas turbine 61, a steam turbine 62, a power 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 that is a power generating means. In addition, the gas turbine 61 supplies air 67, which is supplied to a compressor 66, to the combustor 65. The gas turbine 61 combusts the purified gas 22 with the combustor 65 to generate a high-pressure and high-temperature combustion gas 68, and a turbine 69 is driven with the combustion gas 68. The turbine 69 is connected to the power generator 63, and thus when the turbine 69 is driven, the power generator 63 generates power. A flue gas 70 after driving the turbine 69 has a temperature of 500° C. to 600° C. Accordingly, the flue gas 70 is transmitted to the heat recovery steam generator (HRSG) 64 to recover thermal energy. In the heat recovery steam generator (HRSG) 64, steam 71 is generated by the thermal energy of the flue gas 70, and the steam turbine 62 is driven with the steam 71. After being used in the steam turbine 62, the steam 71 is discharged from the steam turbine 62, and is cooled with a heat exchanger 72. Then, the steam 71 is supplied to the heat recovery steam generator 64. In addition, with regard to the flue gas 73 from which thermal energy is recovered with the heat recovery steam generator 64, NOx and the like in the flue gas 73 are removed with a denitrification device (not illustrated) and the like, and then the flue gas 73 is discharged to the air through a chimney 74.
As described above, according to the coal gasification power generation plant 50 provided with the CO shift reactor 20 according to this example, even in a case where an amount of water vapor is reduced in the CO shift reactor 20 (water vapor (H2O)/C0=approximately 1), with regard the gasification gas 12 that is gasified with the gasification furnace 11, CO contained in the gasification gas 12 is converted into CO2 while suppressing deterioration of the CO shift catalyst, and thus it is possible to stably perform the CO shift reaction with respect to a reformed gas for a long period of time.
According to this, with regard to the CO shift reaction, it is possible to continuously perform the CO shift reaction with less water vapor in a stable manner, and thus it is possible to reduce an amount of water vapor that is bled from HRSG 64. Accordingly, it is possible perform an operation in which energy efficiency of the coal gasification power generation plant 50 is improved.
In addition, an installation position of the CO shift reactor 20 is not limited to a position between the COS converting device 51 and the gas purifying device (H2S/CO2 recovery unit) 15 (on a front end side of the H2S/CO2 recovery unit), and the CO shift reactor 20 may be installed downstream of the gas purifying device (H2S/CO2 recovery unit) 15.
In addition, in this example, description has been given to a case where the purified gas 22 discharged from the gas purifying device (H2S/CO2 recovery unit) 15 is used as a gas for a turbine. However, a large amount of CO contained in the gasification gas 12 is converted into CO2 in the CO shift reactor 20, and thus the purified gas 22 may be used as a raw material gas, which composes chemicals such as methanol and ammonia, in addition to the gas for a turbine.
Hereinbefore, description has been given to a case where in the CO shift reactor 20 according to this example, CO contained in the gasification gas 12, which is generated by gasification of the fuel F such as coal with the gasification furnace 11, is converted into CO2. However, the invention is not limited to this, and for example, the invention may be similarly applied to a CO shift reactor which converts a CO-containing gas into CO2 with a fuel cell, and the like.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2012/084232 | 12/28/2012 | WO | 00 |
