Title of invention: Gas purification apparatus
Technical field
[0001]
　The present disclosure relates to a gas purification apparatus.
Background technology
[0002]
　Patent Documents 1 and 2 disclose catalysts capable of hydrolyzing both carbonyl sulfide (COS) and hydrogen cyanide (HCN). However, in such a catalyst, the optimum temperatures of the hydrolysis reactions of COS and HCN and
　　COS + H 2 O → H 2 S + CO 2　　(1)
　　HCN + H 2 O → NH 3 + CO (2)
are different, and the reaction (1) The optimum temperature of the reaction (2) is 240 ° C. to 320 ° C., and the optimum temperature of the reaction (2) is 280 ° C. to 350 ° C.
[0003]
　Patent Document 3, coal hydrogen sulfide (H by reaction of COS contained in the product gas obtained by gasification (1) 2 heat exchanger on the upstream side of the converter catalyst is filled to be converted to S) is It is described that the produced gas is cooled in this heat exchanger and the produced gas flows into the converter at an optimum temperature for the reaction (1).
Prior art literature
Patent documents
[0004]
Patent Document 1: Japanese Patent No. 2617216
Patent Document 2: Japanese Patent No. 5955026
Patent Document 3: Japanese Patent No. 4227776
Outline of the invention
Problems to be solved by the invention
[0005]
　When the converter described in Patent Document 3 is filled with the catalyst of Patent Document 1 or 2 to hydrolyze both COS and HCN, the common temperature of the optimum temperatures of the reactions (1) and (2) is 280 ° C. to It is conceivable to adjust the temperature of the produced gas in the range of 320 ° C. However, for example, when the concentration of either COS or HCN increases and it is necessary to promote the hydrolysis reaction of the component having the increased concentration, the temperature of the produced gas is adjusted in the configuration of Patent Document 3. Therefore, there is a problem that the component whose concentration has increased cannot be hydrolyzed preferentially.
[0006]
　In view of the above circumstances, at least one embodiment of the present disclosure aims to provide a gas purification apparatus capable of changing the reaction rate of the hydrolysis reaction of each component according to the change in the concentration of COS and HCN in the gas. And.
Means to solve problems
[0007]
　The gas purification apparatus according to at least one embodiment of the present invention includes a converter filled with a catalyst for hydrolyzing both COS and HCN, and a cooling fluid for cooling the gas and the gas before flowing into the converter. The cooling fluid that flows into the upstream heat exchanger based on the upstream heat exchanger that exchanges heat with, the reaction temperature estimation member for estimating the reaction temperature in the converter, and the estimated value by the reaction temperature estimation member. It is provided with a flow rate adjusting member for controlling the reaction temperature by adjusting the flow rate of the gas.
[0008]
　According to this configuration, the reaction temperature in the converter can be controlled by adjusting the flow rate of the cooling fluid that exchanges heat with the generated gas in the upstream heat exchanger, so that each of them responds to changes in the concentrations of COS and HCN in the gas. The reaction rate of the hydrolysis reaction of the components can be changed.
[0009]
　In some embodiments, the reaction temperature estimation member may be a temperature sensor provided between the upstream heat exchanger and the transducer and detecting the temperature of the gas flowing into the transducer. Since the catalyst is heated by the gas flowing into the transducer, the reaction temperature is considered to be approximately equal to the temperature of the gas flowing into the transducer in the steady state. According to this configuration, the reaction temperature can be estimated relatively accurately by using the temperature of the gas flowing into the converter as the estimated value of the reaction temperature.
[0010]
　In some embodiments, an analyzer provided on the upstream side of the converter and analyzing the COS concentration and the HCN concentration in the gas, and the set temperature range of the reaction temperature are determined based on the analysis result of the analyzer. Even if the flow rate adjusting member adjusts the flow rate of the cooling fluid flowing into the upstream heat exchanger so that the value estimated by the reaction temperature estimating member is within the set temperature range. Good. According to this configuration, the estimated value of the reaction temperature is controlled to be within the set temperature range determined based on the analysis result of the concentration of COS and the concentration of HCN in the gas, so that the estimated value of the reaction temperature is more accurately in the gas. The reaction rate of the hydrolysis reaction of each component can be changed according to the change in the concentration of COS and HCN.
[0011]
　In some embodiments, H generated by the hydrolysis of COS from the effluent gas from the converter 2 and the hydrogen sulfide removal device for generating a purified gas by removing S, According to this configuration, since the purified gas that has been desulfurized in the hydrogen sulfide remover through the converter is used as the cooling fluid, the gas purification cost can be reduced as compared with the case where the cooling fluid is prepared separately. it can.
[0012]
　In some embodiments, it further comprises a source of steam that is cooler than the gas before it flows into the transducer, and the cooling fluid may be steam supplied from the source. In this case, the supply source may be a steam turbine. According to this configuration, if the equipment uses steam, a part of the steam can be used as a cooling fluid, so that the gas refining cost can be reduced as compared with the case where the steam is prepared separately. ..
[0013]
　In some embodiments, the gas before flowing into the transducer may be a product gas obtained by gasifying coal. According to this configuration, in a coal gasification combined cycle plant, the reaction rate of the hydrolysis reaction of each component can be changed according to the change in the concentration of COS and HCN in the produced gas.
The invention's effect
[0014]
　According to at least one embodiment of the present disclosure, the reaction temperature in the converter can be controlled by adjusting the flow rate of the cooling fluid that exchanges heat with the generated gas in the upstream heat exchanger, so that COS and HCN in the gas can be controlled. The reaction rate of the hydrolysis reaction of each component can be changed according to the change in the concentration of.
A brief description of the drawing
[0015]
FIG. 1 is a schematic configuration diagram of a gas purification apparatus according to a first embodiment of the present disclosure.
FIG. 2 is a graph schematically showing the relationship between the reaction temperature and the reaction rate of the catalyst charged in the converter of the gas purification apparatus according to the first embodiment of the present disclosure.
FIG. 3 is a schematic configuration diagram of a gas purification apparatus according to a second embodiment of the present disclosure.
Mode for carrying out the invention
[0016]
　Hereinafter, some embodiments of the present invention will be described with reference to the drawings. However, the scope of the present invention is not limited to the following embodiments. The dimensions, materials, shapes, relative arrangements, and the like of the components described in the following embodiments are not intended to limit the scope of the present invention to that alone, but are merely explanatory examples.
[0017]
(Embodiment 1)
　FIG. 1 shows a gas purification apparatus 1 according to the first embodiment of the present disclosure. The gas refining device 1 is a device for purifying the produced gas obtained by gasifying coal in the gasification furnace of an integrated coal gasification combined cycle plant, and more specifically, for removing COS and HCN in the produced gas. Is. In the gas purification device 1, the converter 2 filled with a catalyst for hydrolyzing both COS and HCN, and the produced gas before flowing into the converter 2 and the cooling fluid for cooling the produced gas exchange heat. Detection by the temperature sensor 4 provided between the upstream heat exchanger 3 and the converter 2 in order to detect the temperature of the generated gas flowing into the upstream heat exchanger 3 and the converter 2. A flow control valve 5 which is a flow rate adjusting member for adjusting the flow rate of the cooling fluid flowing into the upstream heat exchanger 3 based on the value is provided.
[0018]
　The catalyst charged in the converter 2 is a catalyst for hydrolyzing both COS and HCN. As this catalyst, a catalyst in which an active ingredient containing at least one of barium, nickel, ruthenium, cobalt, and molybdenum as a main component is supported on a titanium oxide-based carrier can be used. In this catalyst, the titanium oxide-based carrier is at least one of a composite oxide of titanium oxide and silicon oxide, a composite oxide of titanium oxide and aluminum oxide, and a composite oxide of titanium oxide and zirconium oxide, and is a titanium oxide-based carrier. At least one of barium carbonate, nickel carbonate, ruthenium nitrate, cobalt carbonate, and ammonium molybdate is added to the mixture.
[0019]
　Regarding the hydrolysis reaction of COS and HCN using the catalyst charged in the converter 2, the relationship between the reaction temperature and the reaction rate of COS and HCN is schematically shown in the graph of FIG. From the relationship between the reaction temperature and the reaction rate and the relationship with other components contained in the produced gas, the optimum temperature range of the COS hydrolysis reaction when the catalyst charged in the converter 2 is used (hereinafter, "COS conversion"). The optimum temperature) is 240 to 320 ° C., and the optimum temperature range for the hydrolysis reaction of HCN (hereinafter referred to as “optimal HCN conversion temperature”) is 280 to 350 ° C. The optimum COS conversion temperature and the optimum HCN conversion temperature are different from each other, although they have a common temperature range (280 to 320 ° C.).
[0020]
　Therefore, in the transducer 2, it is important to control the reaction temperature in order for the catalyst to function so as to obtain the target reaction rates for each component of COS and HCN. However, it is difficult to accurately detect the reaction temperature. Since the catalyst is heated by the produced gas flowing into the converter 2, the reaction temperature is considered to be substantially equal to the temperature of the produced gas flowing into the converter 2 in the steady state. Therefore, in the first embodiment, as shown in FIG. 1, the temperature of the generated gas flowing into the converter 2 is detected by the temperature sensor 4, and this detected value is used as an estimated value of the reaction temperature. Therefore, the temperature sensor 4 constitutes a reaction temperature estimation member for estimating the reaction temperature in the converter 2.
[0021]
　As the cooling fluid that exchanges heat with the produced gas in the upstream heat exchanger 3, any fluid can be used as long as it is a fluid having a temperature lower than that of the produced gas. In the first embodiment, as the cooling fluid, a purified gas that has been desulfurized after the generated gas has flowed through the converter 2 is used. The gas purification device 1 is a purification facility 10 for purifying the produced gas after flowing through the converter 2 to generate a refined gas, and a downstream side where the produced gas flowing out of the converter 2 and the purified gas exchange heat. It further includes a heat exchanger 6. Purification equipment 10, the generated gas and water washing tower 11 for cooling in contact with water, cooled from the product gas H produced in the hydrolysis of COS 2 hydrogen sulfide removal device for generating a purified gas by removing S It has twelve.
[0022]
　A branch pipe 8 communicating with the upstream heat exchanger 3 branches from the middle of the pipe 7 through which the refined gas that has exchanged heat with the generated gas flows in the downstream heat exchanger 6. The branch pipe 8 is provided with the above-mentioned flow rate control valve 5. The pipe 7 joins the pipe 9 through which the refined gas that has exchanged heat with the generated gas flows in the upstream heat exchanger 3. The pipe 9 communicates with the gas turbine of the integrated coal gasification combined cycle power plant.
[0023]
　Next, the operation of the gas purification apparatus 1 according to the first embodiment will be described.
　As shown in FIG. 1, the gas produced from the gasifier contains COS and HCN. The concentrations of COS and HCN in the produced gas are approximately determined by the type of coal charged into the gasifier. Therefore, the concentrations of COS and HCN in the produced gas assumed when the standard coal type of coal to be charged into the gasification furnace is used are defined as the planned values ​​of the concentrations of COS and HCN. An appropriate reaction rate of each component is determined based on this planned value, and a set temperature range of the reaction temperature of the converter 2 is determined from each reaction rate.
[0024]
　In the first embodiment, when the standard coal type coal is put into the gasification furnace, that is, when the concentrations of COS and HCN in the produced gas are the planned values, both the hydrolysis reaction of COS and HCN is carried out. The gas purification apparatus 1 is operated under conditions that promote it. In this case, the set temperature range of the reaction temperature is set to the common temperature range (280 to 320 ° C.) of the COS conversion optimum temperature and the HCN conversion optimum temperature (see FIG. 2). It should be noted that such a set temperature range is merely an example, and the set temperature range when the concentration of each component is a planned value may be determined by an arbitrary method.
[0025]
　The generated gas from the gasifier is heat-exchanged with the refined gas as the cooling fluid in the upstream heat exchanger 3 and cooled to a temperature within the set temperature range of the reaction temperature. In the temperature control of the generated gas, the temperature of the generated gas flowing out from the upstream heat exchanger 3 is detected by the temperature sensor 4, and the opening degree of the flow rate control valve 5 is adjusted so that the detected value is within the set temperature range. It is done by. For example, when the detected value of the temperature sensor 4 is higher than the set temperature range (for example, 350 ° C.), it is necessary to increase the cooling capacity of the generated gas in the upstream heat exchanger 3, so that the opening degree of the flow control valve 5 is increased. By increasing the size, the flow rate of the purified gas flowing into the upstream heat exchanger 3 is increased. On the contrary, when the detected value of the temperature sensor 4 is lower than the set temperature range (for example, 250 ° C.), it is necessary to suppress the cooling capacity of the generated gas in the upstream heat exchanger 3, so that the flow control valve 5 is opened. By reducing the temperature, the flow rate of the purified gas flowing into the upstream heat exchanger 3 is reduced.
[0026]
　When the generated gas controlled to a temperature within the set temperature range in the upstream heat exchanger 3 flows into the converter 2, the catalyst filled in the converter 2 is heated by the generated gas, and in a steady state, the temperature of the catalyst is increased. The temperature becomes the temperature of the produced gas, that is, the temperature within the set temperature range. As a result, the reaction temperature in the converter 2 is controlled within the set temperature range. In the converter 2, COS and HCN are hydrolyzed by the catalyst. Each hydrolysis reaction proceeds at a reaction rate (see FIG. 2) corresponding to the reaction temperature. In each hydrolysis, COS is H 2 S and CO 2 is converted to, HCN is NH 3 is converted to and CO.
[0027]
　The generated gas flowing out of the converter 2 is heat-exchanged with the refined gas in the downstream heat exchanger 6 to be cooled. Thereafter, the product gas is cooled and flows to the water scrubber 11, then, H flows into the hydrogen sulfide removal device 12 2 by the S is removed, the purified gas is produced. As described above, the purified gas is heated by exchanging heat with the generated gas in the downstream heat exchanger 6. The purified gas heated in the downstream heat exchanger 6 flows through the pipe 7, and a part of the purified gas flows into the upstream heat exchanger 3 through the branch pipe 8 to exchange heat with the generated gas as described above. Heated by. The purified gas heated in the upstream heat exchanger 3 flows out from the upstream heat exchanger 3 and flows through the pipe 9. The remaining refined gas flows into the pipe 9 after flowing through the pipe 7, and merges with the refined gas flowing through the pipe 9. The refined gas flows through the pipe 9 and flows into the gas turbine.
[0028]
　When the type of coal to be charged into the gasifier is changed, the concentrations of COS and HCN in the expected produced gas may change. When the concentration of one of COS and HCN increases, it is necessary to change the set temperature range of the reaction temperature so as to promote the hydrolysis reaction of the component whose concentration increases.
[0029]
　For example, assume that the concentration of HCN does not change and the concentration of HCN becomes higher than the planned value. In this case, as shown in FIG. 2, the set temperature range is changed to, for example, 280 to 350 ° C. in order to increase the reaction rate of the hydrolysis reaction of HCN. In this temperature range, the reaction rate of the COS hydrolysis reaction may decrease to some extent compared to the temperature range before the change (280 to 320 ° C.), but HCN hydrolysis corresponds to an increase in HCN concentration. Priority is given to increasing the reaction rate of the reaction. On the contrary, when the concentration of COS is higher than the planned value without changing the concentration of HCN, the set temperature range is changed to, for example, 240 to 320 ° C. in order to increase the reaction rate of the hydrolysis reaction of COS. In this case, the reaction rate of the hydrolysis reaction of HCN may decrease to some extent, but the increase in the reaction rate of the hydrolysis reaction of COS is prioritized in response to the increase in the concentration of COS.
[0030]
　As shown in FIG. 1, when the set temperature range of the reaction temperature is changed, the opening degree of the flow rate control valve 5 is changed so as to change the temperature of the generated gas flowing into the converter 2, and the upstream side. The flow rate of the purified gas, which is the cooling fluid flowing into the heat exchanger 3, is changed. By changing the set temperature range of the reaction temperature, the reaction rate of the hydrolysis reaction of either COS or HCN is changed according to the change in the concentration of COS and HCN.
[0031]
　In this way, the reaction temperature can be controlled by adjusting the flow rate of the purified gas, which is a cooling fluid that exchanges heat with the generated gas in the upstream heat exchanger 3, so that each component can be controlled according to the change in the concentration of COS and HCN in the gas. The reaction rate of the hydrolysis reaction of the above can be changed.
[0032]
(Embodiment 2)
　Next, the gas purification apparatus according to the second embodiment will be described. The gas purification apparatus according to the second embodiment analyzes the concentrations of COS and HCN in the produced gas flowing into the converter with respect to the first embodiment, and controls the reaction temperature based on the analysis result. It was done. In the second embodiment, the same components as those of the first embodiment are designated by the same reference numerals, and detailed description thereof will be omitted.
[0033]
　As shown in FIG. 3, the gas purification apparatus 1 according to the second embodiment is an analyzer 21 provided between the gasifier and the upstream heat exchanger 3, the analyzer 21, and the temperature sensor 4, respectively. It is provided with a set temperature range determining unit 22 electrically connected to the unit. The analyzer 21 is for analyzing the concentrations of COS and HCN in the produced gas. The set temperature range determination unit 22 is for determining the set temperature range of the reaction temperature based on the analysis result of the analyzer 21, and is incorporated in, for example, a computer that controls the operation of the integrated coal gasification combined cycle plant. .. Other configurations are the same as those in the first embodiment.
[0034]
　In the first embodiment, when the concentrations of COS and HCN in the produced gas can be changed, such as when the coal type to be charged into the gasification furnace is changed, the operation of the coal gasification combined cycle plant is controlled on a computer. It is assumed that the set temperature range of the reaction temperature is changed manually in. However, in the second embodiment, the analyzer 21 measures the concentrations of COS and HCN in the produced gas during the operation of the gas purification apparatus 1, and the set temperature range determining unit 22 sets the set temperature range based on these concentrations. It is different from the first embodiment in that it is determined and the flow rate of the purified gas flowing into the upstream heat exchanger 3 is adjusted so that the reaction temperature in the converter 2 is within the set temperature range. The operation different from the first embodiment will be described below.
[0035]
　For example, when the concentration of HCN becomes higher than the planned value, the set temperature range determining unit 22 changes the set temperature range to, for example, 280 to 350 ° C. in order to increase the reaction rate of the hydrolysis reaction of HCN. .. For example, when the concentration of COS becomes higher than the planned value, the set temperature range determining unit 22 changes the set temperature range to, for example, 240 to 320 ° C. in order to increase the reaction rate of the hydrolysis reaction of COS. .. The set temperature range may be finely determined according to the concentration of each component, instead of determining the set temperature range depending on whether the concentrations of HCN and COS are higher or lower than the planned value. The operation of adjusting the flow rate of the purified gas flowing into the upstream heat exchanger 3 in order to control the reaction temperature within the changed set temperature range is the same as that of the first embodiment.
[0036]
　In this way, the reaction temperature is controlled so as to be within the set temperature range determined by the analysis results of the COS concentration and the HCN concentration in the produced gas, so that the COS and HCN concentrations in the gas are more accurately controlled. The reaction rate of the hydrolysis reaction of each component can be changed according to the change.
[0037]
　In the first and second embodiments, the temperature sensor 4 is provided on the upstream side of the upstream heat exchanger 3, but the present invention is not limited to this embodiment. When the concentrations of COS and HCN in the produced gas are on the order of ppm, the calorific value during the hydrolysis reaction in the converter 2 is small, so the temperature of the produced gas flowing into the converter 2 and the converter 2 It is almost the same as the temperature of the generated gas flowing out from. Therefore, the temperature sensor 4 may be provided on the downstream side of the converter 2, that is, between the converter 2 and the downstream heat exchanger 6. Further, depending on the configuration of the converter 2, a temperature sensor 4 may be provided so that the temperature inside the converter 2 can be detected.
[0038]
　In the first and second embodiments, the reaction temperature estimation member is the temperature sensor 4, but the present invention is not limited to this embodiment. The reaction temperature estimation member may be one that calculates the temperature of the generated gas flowing into the converter 2 by calculation. For example, if the temperature and flow rate of the produced gas from the gasifier and the temperature and flow rate of the refined gas flowing into the upstream heat exchanger 3 are known, the generated gas flowing out from the upstream heat exchanger 3, that is, conversion. The temperature of the generated gas flowing into the vessel 2 can be calculated. In this case, a detector that detects the temperature and flow rate of the generated gas, a detector that detects the temperature and flow rate of the purified gas flowing into the upstream heat exchanger 3, and a converter based on the values ​​detected by each detector. A calculation unit that calculates the temperature of the generated gas flowing into 2 constitutes a reaction temperature estimation member.
[0039]
　In the first and second embodiments, the cooling fluid used in the upstream heat exchanger 3 is a refined gas desulfurized after the generated gas has passed through the converter 2, but the cooling fluid is not limited to the purified gas. Absent. As described above, any fluid can be used as the cooling fluid as long as it is a fluid having a temperature lower than that of the produced gas, but for example, steam having a temperature lower than that of the produced gas may be used. In order to supply steam to the upstream heat exchanger 3, a supply source having an arbitrary configuration may be provided in the gas purification device 1.
[0040]
　When the gas purification device 1 is a part of a coal gasification combined power plant, the steam supply source can be a steam turbine, and the steam extracted from the outlet of the high-pressure turbine or the medium-pressure turbine of the steam turbine. Can be the cooling fluid. In this case, the gas purification cost can be reduced as compared with the case where steam is prepared separately.
[0041]
　In the first and second embodiments, the gas refining apparatus 1 has been described as a part of the integrated coal gasification combined cycle power plant, but the present invention is not limited to this embodiment, and the gas refining apparatus 1 can be provided in any equipment.
Description of the sign
[0042]
1 Gas refiner
2 Converter
3 Upstream heat exchanger
4 Temperature sensor (reaction temperature estimation member)
5 Flow control valve (flow control member)
6 Downstream heat exchanger
7 Piping
8 Branch pipe
9 Piping
10 Generation equipment
11 Washing tower
12 Hydrogen sulfide remover
21 Analyzer
22 Set temperature range determination unit
The scope of the claims
[Claim 1]
　A converter filled with a catalyst for hydrolyzing both carbonyl sulfide and hydrogen cyanide, and
　an upstream heat exchanger in which the gas before flowing into the converter and the cooling fluid that cools the gas exchange heat.
　The reaction is performed
　by adjusting the flow rate of the cooling fluid flowing into the upstream heat exchanger based on the reaction temperature estimation member for estimating the reaction temperature in the converter and the estimated value by the reaction temperature estimation member. A
gas purification device including a flow control member for controlling the temperature .
[Claim 2]
　The gas purification according to claim 1, wherein the reaction temperature estimation member is a temperature sensor provided between the upstream heat exchanger and the converter and detecting the temperature of the gas flowing into the converter. apparatus.
[Claim 3]
　An analyzer provided on the upstream side of the converter and analyzing the concentration of carbonyl sulfide and the concentration of hydrogen cyanide in the gas, and
　a setting for determining the set temperature range of the reaction temperature based on the analysis result of the analyzer.
Further provided with a temperature range determining unit
　, the flow rate adjusting member measures the flow rate of the cooling fluid flowing into the upstream heat exchanger so that the estimated value by the reaction temperature estimating member is within the set temperature range. The gas purification apparatus according to claim 1 or 2, which is adjusted.
[Claim 4]
　From the hydrogen sulfide removing device that produces a purified gas by removing hydrogen sulfide generated by hydrolysis of carbonyl sulfide from the gas flowing out of the converter, and from the gas
　flowing out of the converter and the hydrogen sulfide removing device. A downstream heat exchanger for heat exchange with the outflowing purified gas is
further provided, and the
　cooling fluid is the purified gas after heat exchange with the gas flowing out from the converter in the downstream heat exchanger. The gas purification apparatus according to any one of claims 1 to 3.
[Claim 5]
　The
　cooling fluid further comprises a source of steam that is cooler than the gas before flowing into the transducer, and the cooling fluid is the steam supplied from the source, according to any one of claims 1 to 3. The gas purification apparatus according to the description.
[Claim 6]
　The gas purification apparatus according to claim 5, wherein the supply source is a steam turbine.
[Claim 7]
　The gas refining apparatus according to any one of claims 1 to 6, wherein the gas before flowing into the converter is a produced gas obtained by gasifying coal.