Calcium sulfide oxidation method and apparatus

Abstract: CaS oxidation method and apparatus are disclosed wherein CaS particles are oxidized into CaSO 4 completely as far as to interior of the particle. Interior of an oxidation apparatus 1 is partially partitioned by a partition 22 to thereby form a first fluidized bed 20 on the inner side, a second fluidized bed 21 on the outer side and a freeboard portion 23 thereabove. A heat exchanger 27 having a baffle plate is disposed on the inner side of the partition 22 and an in-bed heat exchanger 33 is disposed on the outer side of same. A desulfurizing product-containing fine powder 204 and coarse powder 205 and a mixture gas 206 of nitrogen, oxygen and steam are supplied into the second fluidized bed 21. Also, coal 200 and coal char 201 are supplied into the first fluidized bed 20 from below. Of the particles 304 oxidized in the second fluidized bed 21 and supplied into the first fluidized bed 20 from below with flow of a mixture gas 208, the fine powder entrains into the freeboard portion 23 as entraining particles 300 and a major part thereof falls down into the second fluidized bed 21 as particles 207. The completely oxidized particles are discharged as discharged ash 303 and entraining ash 302.

Description: BACKGROUND OF THE INVENTION Field of the Invention: The present invention relates to a calcium sulfide oxidation method and apparatus for oxidizing calcium sulfide (CaS) generated at a power plant etc. to thereby obtain calcium sulfate (CaSO 4 ). Description of the Prior Art: One example of a prior art oxidation apparatus for oxidizing CaS generated at a power plant etc. into CaSO 4 is shown in Fig. 10. In Fig. 10, numeral 1 designates an oxidation apparatus, numeral 1A designates a fluidized bed formed therein and numeral 1D designates a plenum. Numeral 6 designates a heat exchanger disposed in the oxidation apparatus 1, numeral 7 designates a cyclone and numeral 8 designates a particle distributor. Numeral 9 designates a distributor plate disposed at a bottom portion of the oxidation apparatus 1. On this distributor plate 9, the fluidized bed 1A is formed, and limestone particles 100 containing char and CaS are supplied into the fluidized bed 1A through a nozzle 2. A mixture gas 101 of oxygen, steam and nitrogen is supplied into the plenum 1D through a nozzle 3. The mixture gas 101 is supplied into the fluidized bed 1A via the distributor plate 9 to effect a mixture combustion of the particles 100 vigorously in the fluidized bed 1A. Oxygen concentration of combustion gas 103 coming out of the fluidized bed 1A is set to 3 to 4% or more. Unless the oxygen concentration of 3 to 4% or more is kept, it will be difficult to burn the char constantly. In the fluidized bed 1A, there occurs a reaction of CaS + 2O 2 → CaSO 4 between CaS and oxygen in the gas. While a larger proportion of CaS is converted to CaSO 4 as a whole in the fluidized bed 1A, CaS remains still within the particles. The heat exchanger 6 is disposed in the fluidized bed 1A so that heat of the particles in the fluidized bed 1A is collected and a heating medium fluid 107 flowing in the heat exchanger 6 is heated. Combustion gas 108 coming out of the oxidation apparatus 1 enters the cyclone 7 to be separated into a dedusted combustion gas 109 and collected particles 110. The collected particles 110 are distributed by the particle distributor 8 into fine powder particles 111 to be extracted outside the system and coarse particles 112 to be returned into the fluidized bed 1A. The coarse particles 112 are supplied into the fluidized bed 1A via a nozzle 5. Coarse particles 102 in ash content of the char, which are not pulverized in the fluidized bed 1A but remain there as large as not to be elutriated by the gas 103, are extracted outside the system via a nozzle 4 which is fitted to the distributor plate 9. In the prior art apparatus as described above, there is contained in the particles 111 and 102 extracted outside the system a high concentration of CaS which has not been converted into CaSO 4 . This high concentration CaS contained in the particles 111 and 102 is gradually decomposed in the air to generate H 2 S, which results in a problem of unfavorable influence being given on the environment. Two reasons are considered why CaS remains in the particles discharged from the prior art oxidation apparatus. Firstly, CaSO 4 generated on a particle surface at an initial stage of reaction forms a dense shell there, so that oxygen is not supplied into an interior of the particle and CaS therein cannot react on oxygen. CaSO 4 , as compared with CaS, has a large molecular volume of 1.8 times and as reaction proceeds from CaS into CaSO 4 , gas diffusion pores existing in the particle clog and oxygen cannot be supplied into the interior of the particle. Secondly, a fine powder begins to entrain from the fluidized bed before ensuring a sufficient reaction time required for a complete oxidation of CaS and is discharged outside the oxidation apparatus as CaS contained in the fine powder is not completely oxidized yet. Also, in case a fuel supply rate varies, because it is necessary to maintain temperature and gas flow velocity in the fluidized bed within an appropriate range, it is preferable to change a heat transfer rate of heat which is transferred to the heating medium through the heat exchanger in the fluidized bed corresponding to the fuel supply rate. In the prior art, however, it has been difficult to change the heat transfer rate largely unless a height of the fluidized bed is changed. Further, even in this method of changing the fluidized bed height, it is necessary to put in or take out the fluid medium to or from the fluidized bed, which work requires much time and there has been a problem that the variation in the fuel supply rate cannot be followed well. SUMMARY OF THE INVENTION: In view of the shortcomings in the prior art, as described with respect to the apparatus shown in Fig. 10, it is an object of the present invention to provide a CaS oxidation method and an apparatus for oxidizing CaS into CaSO 4 by which CaS particles can be oxidized into CaSO 4 completely as far as to an interior of the particle. It is also an object of the present invention to provide an operation method of the CaS oxidation apparatus according to the present invention by which CaS can be oxidized into CaSO 4 efficiently. In order to attain said object, the present invention provides a following oxidation method using an oxidation apparatus forming therein a first fluidized bed, a second fluidized bed on an outer side of said first fluidized bed and a freeboard portion above said two fluidized beds. That is, CaS-containing particles fluidized by a gas flow in said first fluidized bed is caused to collide violently with a heat exchanger or a baffle plate, disposed either in said oxidation apparatus so as to traverse the gas flow, so that a dense shell of CaSO 4 generated on a surface of said particle is abraded and oxygen is spread as far as to an interior of said particle to thereby accelerate an oxidation reaction of CaS into CaSO 4 , said baffle plate having no heat exchange function and being applied by a surface coating made of a material of which hardness is higher than that of a fluid medium. Further, a flow velocity in said freeboard portion above said first fluidized bed is set to a terminal flow velocity or less of a fine powder entraining from said first fluidized bed to thereby cause the entraining fine powder soaring into said freeboard portion from said first fluidized bed to fall down into said second fluidized bed disposed on the outer side of said first fluidized bed. Also, a gas flow velocity in said second fluidized bed is set lower than that in said first fluidized bed so that the fine powder so fallen down into said second fluidized bed may not entrain again and a volume of said second fluidized bed is set such that a particle residence time in said second fluidized bed becomes such a value or more as calculated to a time required for a complete oxidation of the fine powder, and the fine powder, containing CaS, which has been supplied from outside of said oxidation apparatus is supplied into said second fluidized bed. Furthermore, an abrasion rate of the shell of CaSO 4 in said first fluidized bed is controlled by a gas flow velocity in said first fluidized bed and an in-bed fill of said heat exchanger and baffle plate. According to the CaS oxidation method described above, CaS is supplied into the second fluidized bed to be oxidized there and is then sent to the first fluidized bed. In the first fluidized bed, CaS particles collide with the heat exchanger or baffle plate and the shell of CaSO 4 generated on the surface of CaS particle is pulverized and abraded so that CaS particles are accelerated to be oxidized into CaSO 4 as far as to the interior of the particle. CaS particles so accelerated to be oxidized in the first fluidized bed soar into the freeboard portion from the first fluidized bed and then fall down into the second fluidized bed, so that the CaS particles are oxidized into CaSO 4 completely there with a lower gas flow velocity and with a sufficient time. According to the mentioned CaS oxidation method of the present invention, CaS particles can be oxidized completely as far as to the interior of the particle and CaS can be prevented from being discharged outside the system as it is. Also, in order to attain said object, the present invention provides an oxidation apparatus of the following construction. That is, the CaS oxidation apparatus according to the present invention is an oxidation apparatus that forms therein a first fluidized bed, a second fluidized bed on an outer side of said first fluidized bed and a freeboard portion above said two fluidized beds and comprises therein a partition for partitioning partially an interior of said oxidation apparatus into an inner side and an outer side. Said first fluidized bed is constructed on the inner side of said partition such that a heat exchanger or baffle plate is disposed in said first fluidized bed and particles received from said second fluidized bed on the outer side via a hole disposed below said partition are fluidized by an oxygen-containing oxidizing gas of air, oxygen or the like blown through a nozzle, and at the same time, while a fuel of coal, coal char or the like supplied through a nozzle is burnt and CaS contained in the particles is oxidized, the particles are pulverized and abraded by said heat exchanger or baffle plate and a pulverized and abraded fine powder is sent to said freeboard portion and a completely oxidized coarse powder is discharged outside said oxidation apparatus. Also, said second fluidized bed is constructed on the outer side of said partition such that a desulfurizing agent of limestone, dolomite or the like supplied via a particle supply pipe and CaS contained in the particles fallen down from said freeboard portion are fluidized to be oxidized into CaSO 4 by an oxygen-containing oxidizing gas of air, oxygen or the like supplied via a nozzle. Further, said freeboard portion is constructed above said first fluidized bed and second fluidized bed such that a major part of the fine powder entraining from said first fluidized bed is caused to fall down into said second fluidized bed and remaining particles are elutriated by a gas from said first fluidized bed and second fluidized bed to be discharged outside said oxidation apparatus. And the outer side of said partition where said second fluidized bed is formed is constructed by a portion where a heat exchanger for temperature control is disposed and a portion where no such a heat exchanger is disposed. According to the present invention, the CaS oxidation apparatus is partitioned of its interior into the inner side and the outer side, the first fluidized bed is formed on the inner side, the second fluidized bed is formed on the outer side and the particles which have been oxidized in the first fluidized bed on the inner side and entrained into the freeboard portion thereabove fall down from the freeboard portion into the second fluidized bed on the outer side to be oxidized there completely and are then sent to the first fluidized bed to be extracted outside. In the first fluidized bed, the particles collide with the heat exchanger or baffle plate disposed in the first fluidized bed to be pulverized and abraded and oxidation as far as to the interior of the particle is accelerated. In the CaS oxidation apparatus according to the present invention, it is preferable for accelerating oxidation of particles containing less fine powder to make a height of the partition lower than that of a fluidized bed of the first and second fluidized beds, respectively. That is, in case where a proportion of fine powder in the particles to be treated is small so that it is difficult to follow a partial load, a particle circulation rate of the particles moving into the second fluidized bed from the first fluidized bed over the partition can be increased. Also, in the CaS oxidation apparatus according to the present invention, it is preferable for accelerating oxidation of the particles containing less fine powder to employ such a construction that a supply pipe of fuel of coal, coal char or the like is disposed on the outer side of the partition to thereby supply the fuel into the second fluidized bed on the outer side via a nozzle or, in addition thereto, such a construction that nozzles for supplying gas therethrough are disposed being distributed irregularly in the radial direction on the inner side of the partition. That is, if the fuel is supplied into the second fluidized bed through a nozzle disposed on the outer side of the partition, then the second fluidized bed becomes in a reduction atmosphere and CaO generated in the particle surface in that reduction atmosphere causes fine pores in the particle surface, thus oxygen becomes liable to spread through the fine pores as far as to the interior of the particle and oxidation to the interior of the particle is accelerated. Also, in addition to supplying the fuel on the outer side of the partition, nozzles for supplying the gas on the inner side of the partition are disposed being distributed irregularly in the radial direction to thereby form a portion of reduction atmosphere in the radial direction below the first fluidized bed and CaO is generated in the particle surface to thereby accelerate oxidation as far as to the interior of the particle, as mentioned above, in the first fluidized bed also. In the mentioned CaS oxidation apparatus according to the present invention, it is preferable for an efficient oxidation of CaS particles to do such an operation as follows. That is, a mean particle size of CaS-containing desulfurizing agent to be supplied is set in a range of 300 to 2000 µm, first. Also, in order to control abrasion of the particles in the first fluidized bed, a fill of a heat exchanger or a baffle plate which has no heat exchange function is changed and a gas flow velocity is changed in a range of 0.5 to 1.5 m/s. Further, a gas flow velocity in the second fluidized bed is set in a range of 0 to 1.2 m/s so as not to cause the pulverized particles to entrain therein and also a gas flow velocity in the freeboard portion is changed in a range of 0.1 to 0.3 m/s to thereby control an entraining-out amount outside the system. Also, the gas flow velocity in the first fluidized bed, the gas flow velocity in the second fluidized bed and the gas flow velocity in the freeboard portion are changed to thereby control a particle circulation rate from the first fluidized bed into the second fluidized bed. Further, in order to control a heat absorption rate of the entire CaS oxidation apparatus at the time of variable fuel supply, an electrical signal is sent from a fuel supply control device to a flow control device of gas to be supplied into a portion where the heat exchanger of the second fluidized bed is disposed to thereby change a gas flow velocity in said portion in a range of 0 to 1.2 m/s. By employing such an operation condition as mentioned above, CaS can be oxidized into CaSO 4 completely and efficiently by use of the apparatus according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS: Fig. 1 is a longitudinal cross sectional view showing an apparatus of a first embodiment according to the present invention. Fig. 2 is a longitudinal cross sectional view showing an apparatus of a second embodiment according to the present invention. Fig. 3 is a transverse cross sectional view taken along line A-A of Fig. 2. Fig. 4 is a diagrammatic view showing an apparatus of a third embodiment according to the present invention. Fig. 5 is a longitudinal cross sectional view showing an apparatus of a fourth embodiment according to the present invention. Fig. 6 is a longitudinal cross sectional view showing an apparatus of a fifth embodiment according to the present invention. Fig. 7 is an explanatory view showing influence of particle size and time given on CaS oxidation reaction rate in the apparatus of the first and second embodiments. Fig. 8 is a diagram showing influence of gas flow velocity and in-bed heat exchanger given on CaS particle pulverization rate in the apparatus of the first and second embodiments. Fig. 9 is a diagram showing relationship between gas flow velocity in a second fluidized bed and heat transfer rate of the oxidation apparatus with respect to the third embodiment. Fig. 10 is a longitudinal cross sectional view showing a prior art apparatus. DESCRIPTION OF THE PREFERRED EMBODIMENTS: Herebelow, the present invention will be described concretely based on embodiments shown in Figs. 1 to 9. (First Embodiment) A first embodiment will be described with reference to Fig. 1. In Fig. 1, numeral 1 designates a CaS oxidation apparatus and this CaS oxidation apparatus 1 has therein a partition 22, which partitions an interior of the apparatus so as to form a first fluidized bed 20 on an inner side of the partition 22 and a second fluidized bed 21 on an outer side of the same, and also has in an upper portion therein a space which forms a freeboard portion 23. The partition 22 disposed between the first fluidized bed 20 and the second fluidized bed 21 is covered by a fire resistant material, is cooled by a heating medium fluid and is supported by a supporting member 24 which is cooled by a heating medium fluid flowing therein. The portion forming the second fluidized bed 21 consists of a portion 21a which has an in-bed heat exchanger 33 and a portion 21b which has no such a heat exchanger. Within the first fluidized bed 20, there is provided a heat exchanger 27, and coal 200 and coal char 201, carried by a nitrogen-containing gas, are supplied into the first fluidized bed 20 from below the fluidized bed. Numeral 25 designates a plenum and numeral 26 designates a distributor plate, and a mixture gas 202 of nitrogen, oxygen and steam is supplied through the plenum 25 and the distributor plate 26, so that the first fluidized bed 20 is formed and the fuel burns. Upon burning of the coal 200 and the coal char 201, so supplied, a combustion surface temperature of the particle becomes high and the particles melt partially to thereby generate an agglomerated substance, called a clinker, which may worsen the fluidization. In order to prevent generation of the clinker, the gas flow velocity in the first fluidized bed 20 is set to 0.7 to 1.5 m/s at the lowermost portion of the bed. Also, in order to make the particles more easily abraded, the gas flow velocity at the upper portion of the bed where the heat exchanger 27 is disposed is set to 0.5 to 0.9 m/s. The combustion heat is heat-exchanged by a heating medium fluid 203 flowing in the heat exchanger 27 which is disposed within the first fluidized bed 20. The heat exchanger 27 is of a coiled tube type and between the coiled tubes, there is provided a baffle plate of a staggered lattice shape. The baffle plate is applied by a surface coating made of a material of which hardness is higher than that of the fluid medium. In order to completely oxidize CaS contained in the particles 304 flowing from the second fluidized bed 21 through below the partition 22, the temperature of the first fluidized bed 20 is set to 870 to 1000°C. The particles which have been oxidized completely in the first fluidized bed 20 are extracted from below the bed as a discharged ash 303 or is discharged from the upper portion of the apparatus as an entrained ash 302. A fine powder which has been completely oxidized in the second fluidized bed 21 and sent to the first fluidized bed 20 and a fine powder which has been pulverized and abraded in the first fluidized bed 20 entrain into the freeboard portion 23 from the first fluidized bed 20 to become entrained particles 300. High temperature particles 207 which constitute a major part of the entrained particles 300 fall down along a wall surface of the freeboard portion 23 to come into the second fluidized bed 21. The remaining portion of the entrained particles 300 is elutriated by a combustion gas 301 to become the entrained ash 302 to be taken out of the apparatus. Also, a fine powder 204 of mean particle size of 100 µm containing desulfurizing products consisting of CaS, CaO, CaCO 3 , etc. (hereinafter referred to as "fine powder") and a coarse powder 205 of mean particle size of 300 to 2000 µm containing desulfurizing products consisting of CaS, CaO, CaCO 3 , etc. (hereinafter referred to as "coarse powder") are supplied, together with a nitrogen-containing carrying gas, into the second fluidized bed 21 from the upper portion of the second fluidized bed 21 through nozzles 28, 29. The fine powder 204 and the coarse powder 205, so supplied, are products produced by desulfuration in a coal gasification and one example of composition thereof is CaS 40%, CaCO 3 30%, CaO 30%, etc. The fine powder 204 is that collected from a cyclone and the mean particle size is approximately 100 µm. If the mean particle size of the coarse powder 205 is smaller than 300 µm, the first fluidized bed 20 will be made in a turbulent fluidized bed, which results in a narrow range of the gas flow velocity therein and less freedom of the operation. If the mean particle size of same is larger than 2000 µm, it will become difficult to oxidize CaS completely in the first fluidized bed 20. The second fluidized bed 21 is fluidized by a mixture gas 206 of nitrogen, oxygen and steam which has been supplied via a plenum 30 and a distributor plate 31 and its temperature is 750 to 950°C. In the portion 21b of the second fluidized bed 21 where no in-bed heat exchanger 33 is disposed, the gas flow velocity is set to 0.05 to 1.2 m/s in order to make the entrained particles as little as possible, so that a moderate fluidized bed is formed there. In the portion 21a of the second fluidized bed 21 where the in-bed heat exchanger 33 is disposed, the high temperature particles 207 which fall down from the freeboard portion 23 are heat-exchanged by a heating medium fluid 305 which flows in the in-bed heat exchanger 33. Control of a heat absorption rate of this oxidation apparatus is done by changing the gas flow velocity in the range of 0 to 1.2 m/s in the portion 21a of the second fluidized bed 21 where the in-bed heat exchanger 33 is disposed. If said gas flow velocity is made to 0 m/s, the portion 21a of the second fluidized bed 21 where the in-bed heat exchanger 33 is disposed becomes a fixed bed and the heat transfer rate is reduced greatly. In the second fluidized bed 21, as compared with the first fluidized bed 20, the gas flow velocity is lower and the gas contained in the fluidized bed is less, hence the specific gravity of the fluidized bed becomes larger. Thus, the particles in the second fluidized bed 21 can be supplied into the first fluidized bed 20 smoothly through below the partition 22. In the first embodiment, in order to move the particles more smoothly into the first fluidized bed 20 from the second fluidized bed 21, there is provided a nozzle 32 in an outer wall portion of the second fluidized bed 21 and a mixture gas 208 of nitrogen, oxygen and steam is supplied therethrough. (Second Embodiment) Next, a second embodiment will be described with reference to Figs. 2 and 3. This second embodiment is an example of case where a reaction rate of CaS and oxygen is large. In the second embodiment, differently from the first embodiment, a coarse powder 205 carried by a nitrogen-containing gas is supplied into a portion 20a below a first fluidized bed 20 through a nozzle 29. The coarse powder 205 collides with a mixture gas 202 of nitrogen, oxygen and steam which blows out of a distributor plate 26. If CaS in the coarse powder 205 is placed in a high oxygen concentration, an exothermic reaction of CaS + 2O 2 → CaSO 4 occurs very rapidly on a surface of the particles, hence the CaS particle in the coarse powder 205 supplied into the portion 20a below the first fluidized bed 20 is suddenly temperature-elevated to cause thermal stresses therein and becomes liable to be pulverized and abraded. Also, if the particles in the portion 20a below the first fluidized bed 20 are slow in movement, transfer of heat becomes worse and the surface of particle melts partially, so that an agglomeration phenomenon where the particles stick to each other occurs and the operation becomes obstructed. Thus, in order to accelerate pulverization and abrasion of CaS which has been made liable to be pulverized and abraded due to the thermal stresses and to prevent said agglomeration phenomenon, the gas flow velocity in the portion 20a below the first fluidized bed 20 is set to 1.0 to 1.5 m/s and a turbulent fluidized bed is formed there. Also, in the second embodiment, differently from the first embodiment, a fine powder 204 carried by a nitrogen-containing gas is supplied swirling (Fig. 3) into a second fluidized bed 21 through a nozzle 28, so that sticking between the particles is prevented by the swirling flow. In order to form such a swirling flow, an in-bed heat exchanger 33 is disposed below the swirling flow in the second fluidized bed 21. Construction of other parts of the second embodiment shown in Fig. 2 than those described above is same as in the first embodiment. (Third Embodiment) A third embodiment will be described with reference to Fig. 4. Fig. 4 is a view for explaining an operation method in a case where a supply rate of fuel, such as coal, char, etc. varies in the first and second embodiments. In Fig. 4, fuel 401 from a fuel supply hopper 40 is extruded by a screw feeder 41 and an extruded fuel 402 is sent to an injector 43 and is then carried therefrom into the first fluidized bed 20 as a fuel 404 by a nitrogen-containing gas 403. The fuel supply rate is converted into an electrical signal 500 by a fuel supply control device 42 and the electrical signal 500 is sent to a flow control device 44. The flow control device 44 controls a flow rate of a mixture gas 405 of nitrogen, oxygen and steam to be supplied thereinto and a mixture gas 206, so controlled, is supplied into the portion of the second fluidized bed 21 where the heat exchanger is disposed. If the fuel is decreased, the mixture gas 206 is decreased and heat transfer rate of the oxidation apparatus is decreased. If the fuel is increased reversely, the mixture gas 206 is increased and heat transfer rate of the oxidation apparatus is increased. Fig. 9 shows the relationship between heat transfer coefficient and gas flow velocity in the second fluidized bed 21 of the third embodiment according to the present invention. As shown there, as the gas flow velocity decreases, the heat transfer coefficient decreases. Where the heat transfer rate of the entire oxidation apparatus is Q, the heat transfer coefficient of the heat exchanger of the first fluidized bed is H 1 , the heating area is A 1 , the heating medium temperature is TS 1 , the first fluidized bed temperature is T 1 , the heat transfer coefficient of the heat exchanger of the second fluidized bed is H 2 , the heating area is A 2 , the heating medium temperature is TS 2 and the second fluidized bed temperature T 2 , the following relationship can be obtained: Q = H 1 × A 1 × (T 1 -TS 1 ) + H 2 × A 2 × (T 2 -TS 2 ) Accordingly, if the fuel supply rate varies, the gas flow velocity in the portion of the second fluidized bed where the in-bed heat exchanger is disposed is changed so that the heat transfer rate transferred to the heating medium is changed, thereby it becomes possible that the heat transfer rate of the entire oxidation apparatus is changed. (Fourth Embodiment) A fourth embodiment according to the present invention will be described with reference to Fig. 5. This fourth embodiment is an example of case where a proportion of the fine powder in the supplied particles is small and it is difficult to follow a partial load. In this embodiment, the height of the fluidized bed of the first fluidized bed 20 and the second fluidized bed 21, respectively, is made higher than the partition 22 by 0 to 0.5 m approximately, thereby circulation rate of particles from the first fluidized bed 20 into the second fluidized bed 21 is increased. The second fluidized bed 21 may be constructed only by the portion where the in-bed heat exchanger 33 is disposed. Control of the circulation rate of particles is done by a differential gas flow velocity between the first fluidized bed 20 and the second fluidized bed 21. If supply of coal 200 and char 201 varies, the gas flow velocity in the second fluidized bed 21 is changed and the circulation rate is controlled. (Fifth Embodiment) A fifth embodiment according to the present invention will be described with reference to Fig. 6. This fifth embodiment is an example of case where oxidation of CaS is insufficient in the fourth embodiment because of a large CaS content in Ca compound in the supplied particles and the like. In the fourth embodiment, the fluidized bed height of the first fluidized bed 20 and the second fluidized bed 21, respectively, is made higher than the partition 22 by 0 to 0.5 m approximately, as mentioned above, thus a portion of the coarse particles in the first fluidized bed 20 also is circulated into the second fluidized bed 21. In the fourth embodiment, a proportion of the fine powder in the second fluidized bed 21 becomes smaller and residence time of the fine powder becomes less, hence if the CaS content in the Ca compound in the supplied particles becomes 80% or more, oxidation of CaS becomes insufficient. Thus, in the fifth embodiment, in order to accelerate oxidation of CaS, fuel 401 of coal, char and the like is supplied into the second fluidized bed 21 so that the second fluidized bed 21 is made in a reduction atmosphere. Thereby, a portion of CaSO 4 on the fine powder surface and hydrogen in the reduction gas in the second fluidized bed 21 make a reaction, such as CaSO 4 + H 2 → CaO + H 2 O + SO 2 , to thereby generate CaO. As CaO has a smaller molecular volume, there are formed in the particle surface fine pores through which oxygen may spread. Thus, the fine pores are formed in the fine powder surface in the second fluidized bed 21 and oxygen spreads as far as to the interior of the fine powder in the first fluidized bed 20, hence the fine powder is oxidized quickly. In order to accelerate the oxidation of CaS, a reduction atmosphere may be formed in the first fluidized bed 20. In this case, nozzles for blowing a mixture gas 202 of nitrogen, oxygen and steam into the first fluidized bed 20 are provided, being distributed irregularly in the radial direction, thereby a reduction atmospheric portion may be formed in the radial direction below the first fluidized bed 20. In the above, the invention has been described concretely based on the embodiments as illustrated, but the invention is not limited to said embodiments but may be added with various modifications to the concrete structure and construction within the scope of claims as hereinafter set forth. As described above, according to the present invention, following effect can be obtained. In the CaS oxidation method and apparatus according to the present invention, such oxidation apparatus is used as comprises therein the first fluidized bed formed on the inner side, the second fluidized bed formed on the outer side of the first fluidized bed and the freeboard portion disposed above these two fluidized beds and oxidation is effected in these two fluidized beds of the first and second beds, thereby CaS can be oxidized completely. According to the present invention, CaS in the fine powder supplied into one of the first and second fluidized beds, the second for example, is oxidized in the second fluidized bed and is sent to the other, that is, the first fluidized bed. The fine powder which has been sent to the first fluidized bed and oxidized completely entrains from the first fluidized bed and is discharged out of the system or extracted from below the first fluidized bed. Fig. 7 shows the influence of particle size and time given on the oxidation reaction rate of CaS in the case where the particles are so sent to the first fluidized bed from the second fluidized bed. In the prior art oxidation apparatus, the entrained particles of about 100 µm reside in the fluidized bed only about 10 minutes on an average. As shown in Fig. 7, residence time of about 10 minutes can afford only an insufficient oxidation, while in the present invention, the fine powder is introduced into the second fluidized bed, for example, and thereby the average residence time becomes about 2 hours, so that it is understood that a sufficient oxidation can be attained. The coarse powder in the desulfurizing agent is supplied into the second fluidized bed to be oxidized only on the particle surfaces and is sent to the first fluidized bed as in the first embodiment or is directly supplied into the first fluidized bed as in the second embodiment. The particles of the coarse powder sent to the first fluidized bed reside in the first fluidized bed as long time as sufficient for completion of the oxidation and CaS of 300 µm, for example, is oxidized completely, as shown in Fig. 7. The coarse powder, while it resides in the first fluidized bed, is moved vigorously by the gas and collides violently with other particles and with the heat exchanger and the baffle plate having no heat exchange function, both disposed in the fluidized bed. Thereby, CaSO 4 shell generated on the coarse powder surface is pulverized and abraded, which results in that oxygen may easily spread to the interior of the particle and oxidation of CaS into CaSO 4 is accelerated. The coarse powder which has been oxidized completely is extracted from the first fluidized bed. Fig. 8 shows influence of the gas flow velocity, the heat exchanger and the baffle plate given on the pulverization rate of CaS particles in the first fluidized bed of the present invention. The "relative pulverization rate" of the vertical axis means a relative value of rate in which particles having particle sizes of under-pass or less per unit volume of the fluidized bed are generated. According to the present invention, the gas flow velocity is increased and the heat exchanger and the baffle plate are disposed in the first fluidized bed, thereby the CaSO 4 shell on the CaS particle surface is accelerated to be pulverized and abraded in the first fluidized bed, as shown in Fig. 8. Thus, the shell of CaSO 4 generated on the particle surface of CaS which resides in the first fluidized bed is abraded and oxidation reaction is made liable to occur as far as to the interior of CaS particle, and at the same time the particle size of the particles residing in the first fluidized bed becomes smaller so that time required for the oxidation becomes shorter and complete oxidation of CaS into CaSO 4 becomes facilitated. As described above, according to the present invention, it has become possible to oxidize CaS into CaSO 4 completely, hence there is no need of discharging CaS outside the system.

Claims: A method for oxidizing CaS into CaSO 4 in a fluidized bed, comprising the steps of: using an oxidation apparatus (1) in which is formed a first fluidized bed (20), a second fluidized bed (21) on an outer side of said first fluidized bed (20), a freeboard portion (23) above said first and second fluidized beds (20,21), and a heat exchanger (27) or a baffle plate disposed in said first fluidized bed (20) so as to traverse a gas flow, said baffle plate having no heat exchange function and being applied with a surface coating made of a material having a hardness which is higher than that of particles to be fluidized in said fluidized bed; causing CaS-containing particles fluidized by a gas flow in said first fluidized bed (20) to collide violently with said heat exchanger (27) or said baffle plate, so that a dense shell of CaSO 4 generated on the surface of said particles is abraded and oxygen is spread to the interior of said particles to thereby accelerate an oxidation reaction of CaS into CaSO 4 ; setting a flow velocity in said freeboard portion (23) above said first fluidized bed (20) to a value equal to or less than a terminal flow velocity such that a fine powder entrained from said first fluidized bed (20) into said freeboard portion (23) falls down into said second fluidized bed (21); setting a gas flow velocity in said second fluidized bed (21) to a value lower than that in said first fluidized bed (20) so that the fine powder fallen down from said freeboard portion (23) into said second fluidized bed (21) is not entrained again; and setting a volume of said second fluidized bed (21)_such that a particle residence time in said second fluidized bed (21) becomes equal to or higher than a time calculated to be required for a complete oxidation of the fine powder; supplying a CaS-containing fine powder (204,205) into said second fluidized bed (21) from an outside of said oxidation apparatus; and controlling an abrasion rate of the shell of CaSO 4 generated on the surface of said particles in said first fluidized bed (20) by controlling a gas flow velocity in said first fluidized bed (20) and by selecting an extent to which said heat exchanger (27) and baffle plate fills said first fluidized bed (20). An apparatus for oxidizing CaS into CaSO 4 in a fluidized bed, comprising: a partition (22) for partially partitioning an interior of said oxidation apparatus (1) into an inner side where a first fluidized bed (20) is formed, and an outer side where a second fluidized bed (21) is formed, and a space above said partition (22) and said two fluidized beds (20,21) where a freeboard portion (23) is formed; a nozzle means through which an oxygen-containing oxidizing gas of air, oxygen or the like can be blown into said first fluidized bed (21) by which particles received from said second fluidized bed (21) via a space disposed below said partition (22) and a fuel of coal (200) coal-char (201) or the like supplied into said first fluidized bed (20) via a nozzle means are fluidized such that the fuel is burnt, CaS contained in the particles is oxidized, the particles are pulverized and abraded by hitting against a heat exchanger (27) or baffle plate disposed in said first fluidized bed (20), and the pulverized and abraded fine powder is sent to said freeboard portion (23) and a completely oxidized powder is discharged to an outside of said oxidation apparatus (1); a nozzle means for supplying an oxygen-containing oxidizing gas (206) of air, oxygen or the like into said second fluidizing bed (21) such that a desulfurizing agent (204,205) of limestone, dolomite or the like supplied into said second fluidized bed (21) via a particle supply pipe and CaS contained in the particles falling down from said freeboard portion (23) are fluidized to be oxidized into CaSO 4 ; said freeboard portion (23) is constructed above said first fluidized bed (20) and second fluidized bed (21) such that a major part of the fine powder entrained from said first fluidized bed (20) is caused to fall down into said second fluidized bed (21) and remaining particles are lutriated by a gas from said first fluidized bed (20) and said second fluidized bed (21) to be discharged to the outside of said apparatus (1); and said outer side of said partition (22) where said second fluidized bed (21) is formed comprises a portion (21a) where a heat exchanger (33) for temperature control is disposed and a portion where no such heat exchanger is disposed. An apparatus for oxidizing CaS into CaSO 4 according to claim 2, wherein said partition (22) has a height which is lower than that of a fluidized bed of said first fluidized bed (20) and said second fluidized bed (21), respectively. An apparatus for oxidizing CaS into CaSO 4 according to claim 3, further comprising a pipe for supplying fuel (401) of coal, coal-char or the like to said second fluidized bed (21) formed on the outer side of said partition (22). An apparatus for oxidizing CaS into CaSO 4 according to claim 4, further comprising nozzles for supplying gas (202) into said first fluidized bed (20) formed on the inner side of said partition (22), said nozzles being distributed irregularly in the radial direction. A method of operating an apparatus for oxidizing CaS into CaSO 4 as defined in claim 2 or 3, comprising the following steps: setting a mean particle size of CaS-containing desulfurizing agent (204,205) to be supplied into said second fluidizing bed (21) to a range of 300 to 2000 µm, selecting an extent to which said heat exchanger (27) and baffle plate fills said first fluidized bed (20) and setting a gas flow velocity in said first fluidized bed (20) in a range of 0.5 to 1.5 m/s to thereby control abrasion of the particles in said first fluidized bed (20); setting a gas flow velocity in said second fluidized bed (21) in a range of 0 to 1.2 m/s so as not to cause the pulverized particles to be entrained in said second fluidized bed (21) and setting a gas flow velocity in said freeboard portion (23) in a range of 0.1 to 0.3 m/s to thereby control an amount of particles entrained to the outside of the apparatus; controlling the gas flow velocity in said first fluidi±ed bed (20), the gas flow velocity in said second fluidized bed (21) and the gas flow velocity in said freeboard portion (23) to thereby control a particle circulation rate from said first fluidized bed (20) into said second fluidized bed (21); and controlling an amount of gas supplied into said portion (21a) where said heat exchanger (33) of said second fluidized bed (21) is disposed to thereby change a gas flow velocity in said portion in a range of 0 to 1.2 m/s in accordance with a rate of fuel supplied into said apparatus in order to control a heat absorption rate of the entire CaS oxidation apparatus (1) at the time of variable fuel supply.

Inventors: FUJIOKA YUICHI, ISHIGAMI SHIGEYASU, KOBAYASHI YOSHINORI, SETOGUCHI TOSHIHIKO, SHINODA KATSUHIKO, TAGASHIRA KENJI, TSUCHIYAMA YOSHIHIKO, FUJIOKA, YUICHI, ISHIGAMI, SHIGEYASU, KOBAYASHI, YOSHINORI, SETOGUCHI, TOSHIHIKO, SHINODA, KATSUHIKO, TAGASHIRA, KENJI, TSUCHIYAMA, YOSHIHIKO, Fujioka, Yuichi Nagasaki Research &amp; Dev. Center, Ishigami, Shigeyasu Nagasaki Ship. &amp; Machin. Works, Kobayashi, Yoshinori Nagasaki Ship.&amp; Machin. Works, Setoguchi, Toshihiko Nagasaki Res. &amp; Dev. Center, Shinoda, Katsuhiko Nagasaki Research &amp; Dev. Center, Tagashira, Kenji Nagasaki Research &amp; Dev. Center, Tsuchiyama, Yoshihiko Nagasaki Res. &amp; Dev. Center
Applicants: MITSUBISHI HEAVY IND LTD, MITSUBISHI HEAVY INDUSTRIES, LTD.
Application year: 1998
Main classification: C01F11
IPC codes: F23C10, B01J8, C01F11, B01D53