SK124392A3 - Method and apparatus for desulfurization of exhaust gas by a dry way - Google Patents

Description

* < ΜΆΛΛη ·: .ΜΝι 'J! ·. ·:'. , '; -; r ’; 'í * 0 Γ " yi / ye-ee, 8695 ..Aparation and method for removing sulfur oxide from degassing by dry route »;

BACKGROUND OF THE INVENTION. * / s $ Dj (ť 'Χϊ;;; i

The present invention relates generally to a suction device and, in particular, to a suction device suitable for reducing the sulfur oxide content of a flue gas. Fossil fuels such as heavy oils and coal are widely used! in combustion plants, e.g. in thermal power plants. Gases that leave such combustion plants typically contain 100 to 5000 ppm of harmful acidic substances, such as sulfur oxides (SO2) and hydrochloric acid (HCl). ‘Such harmful substances, when discharged into the atmosphere, cause acid rain and photochemical smog. To be with. we dispose of such harmful substances we install a desalination device ^ The desulphurisation methods are roughly longer on wet-type and dry-type methods. A representative example of wet type desulphurisation is the limestone and gypsum producing method; Particularly, this method is considered to achieve highly efficient desulfurization. On the contrary, the main feature of the dry type method is the fact that it does not produce any aqueous waste and examples of dry type desulfurization methods include the activated carbon adsorption method and the alkali metal compounds or the like. In particular, the second method is economically advantageous if. are economic indicators related to the unit weight of the bound sulfur dioxide. In a typical example of this method, the exchanger degassing is cooled in an air heater and charged to a suction column. The desulfurizing agent to be slaked lime is dispersed into the chimney or into the duct, in the exchanger or into the diffusion column. At the same time, water from the water tube and air from the gas conduit are dispersed by water jets located on the split ring to cool off the flue gas while simultaneously increasing the moisture, which promotes the desulphurisation reaction.

The water may be supplied separately or together with a desiccant. In the latter case, it is supplied in the form of a slurry. The reacted desulfurizing agent is collected by a dust separator in the outgoing gas together with the ash. In some cases, a portion of the entrapped particulate that contains unreacted desulfurizing agent is fed back to the desiccant preparation plant and again injected into the leaving flue gas or desulfurization desulfurization column. The higher the relative humidity, the higher the desiccation rate. The reason for this is: When the moisture rises inside the desulfurization column, the water content adsorbed on the surface of the slaked lime particles entering the aspiration column also increases. The reaction between H2SO3 and Ca (OH) 2 is a neutralization reaction, and this reaction proceeds rapidly to produce CaSO4 SO2 is a stabilizer in this state When the water content of the slaked lime is high The amount of dissolved SO2 is also high, so high humidity is desirable, so formed CaSO4 increases its volume, so that the CaSO4 layer covering the slaked lime particles breaks itself down and the recovered surface of slaked lime is re-exposed to SO2, thus accelerating the desulfurization reaction.

Therefore, it is desirable to maximize the relative humidity. However, in the actual device, when the relative humidity of the air is high, water condenses either in the low temperature portion of the aspiration column, the subsequent dust separator, or the subsequent smoke duct. This brings about problems such as the formation of liquid waste, the formation of deposits and the corrosion of material caused by H2SO3 or H2SO4.

In addition, at high relative humidity, when the temperature in the lower portion of the desiccant column is reduced, the desulfurizing agent is effected as a result of this reduction in water vapor condensation on the sides of the reservoir, so that the powder desiccant then has reduced fluidity. This leads to difficulties in removing it from the bottom of the aspiration column.

Therefore, it is. it is customary to control the temperature of the bottom of the cartridge so as to be about 10 ° C higher than the saturation temperature at the outlet thereof. The relative humidity is maintained at about 60%. In conjunction with such temperature control, the relative humidity cannot be higher than this value, and therefore the aspiration rate is also small. -3- 8695 5¾; On the other hand, in order to increase the desulfurization performance and to keep the relative humidity at about 60%, a counterproposition (Japanese patent, not designated (unexamined) publication No. 2-152520, etc.) would be proposed. As coal or coal, the desulfurizing agent, such as slaked or quicklime, is included in the slurry to develop a high specific surface area of desulfurizing agent and thus a high slurry ability to absorb SO2. the desulfurizing agent is prepared according to the above procedure, it is necessary to heat the desulfurizing agent material to a high temperature above 100 ° C for a long time (from a little over ten hours to several tens of hours) as described in the Japanese patent no. . 2-152520. Thereby the desulfurization agent preparation becomes large and the energy consumption for heating increases. If the heating temperature is lower or the heating time is shorter, the desulfurization efficiency decreases. In addition, when sprayed into the slurry desulfurization apparatus, the spray nozzle is worn at a much greater rate than powder spraying, and there are also problems with sedimentation of the slurry in the pipe. At the same time, when using a high surface area desulfurizing agent, there is another problem with the fluid flowability that needs to be overcome by using more water. Compared to the method ,. in which the aspirating agent is supplied in powder form, the slurry must be additionally dried and the system becomes complicated and the cost of desulfurizing agent production increases.

According to what has been said, although the aspiration efficiency is increased together with the relative humidity in the aspiration column, the water can condense in the aspiration column and in the dust and ash separator and, as a result, the aspiration agent and ash deposit on the interior surface of the device, which then it corrodes. However, attention is not paid to these problems, and therefore, desiccation columns cannot operate for longer periods of time and the functionality of the entire system is often disrupted. However, if the temperature of the desiccant column is increased (i.e., relative humidity is reduced), deposits and corrosion may be somewhat suppressed, the desiccating efficiency is less.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dry type aspiration device that exhibits high desulfurization efficiency and prevents scale formation and corrosion build-up.

The above object of the invention can be achieved by one of the following devices [1] - [6].

[1] Dry method desalination apparatus and flue gas. consisting of a device for dispensing a desulfurizing agent into a furnace of a combustion apparatus or into a flue gas duct containing sulfur oxides from a furnace, a desulfurizing agent comprising at least one compound selected from the group consisting of alkali metal or caustic earth metal furnaces and fossil fuel furnaces (e.g. coal) containing sulfur compounds, an aspiration column located at the outlet side, a water spray incorporated in the aspiration column, and a vortex generating device within the flue gas stream in the desiccant column, forming high relative humidity regions within the desiccant column so that the desiccant containing the compound is mixed in high relative humidity.

[2] Dry-type flue gas extraction method comprising a desulfurizing agent supply step comprising at least one compound selected from the group of alkali metal or caustic earth metals, flue gas leaving the combustion apparatus to remove sulfur oxides from the flue gas, and recovering the desulfurizing agent and the coal ash in the dust separator, wherein the desulfurizing agent is fed to that portion of the flue gas whose temperature is not more than 200 ° C and the desiccant is trapped in the dust separator and subsequently recovered to the flue gas whose temperature is 500 ° C to 900 ° C to react with the sulfur oxides in the offgas.

[3] A dry method desulfurization apparatus comprising a desulfurizing agent spraying apparatus into a furnace of a combustion apparatus or into a smoke duct, wherein the desulfurizing agent comprises at least one compound included in the group.

tyyVitviíí; The alkali metal or caustic soil compounds are disposed on the outlet side of the apparatus, the water spraying device in the aspirator column to support the desulfurization reaction. flue gas sulfur, dust removal devices for capturing the reacted desulfurization agent, and apparatus for introducing the heating gas into the bottom 25 of the aspirating column. [4] A flue gas aspiration apparatus using a dry method and comprising a device for supplying a desulfurizing agent to the furnace. or to a flue gas duct that contains sulfur oxides from the furnace, wherein the scavenger comprises at least one compound comprised of an alkali metal or caustic earth compound. The desulfurization column is located at the outlet side and has an inlet and an outlet portion and is provided with a water spray device inside. a desiccant column, or in a collapsed inlet portion of the column.

This water causes a drop in the leaving gas, which encourages the reaction between the desulfurizing agent and the gaseous sulfur oxides in contact with them. This removes sulfur oxides. Furthermore, it is provided with a temperature detecting device V; The point at which the droplets of water dispersed by the spray device and the device for adjusting the amount of water sprayed under the measured temperature directly strike, thereby controlling the temperature of the gas at the outlet portion of the desulfurization plant. ! [5] A method of preparing a desulfurizing agent comprising the step of mixing a siliceous substance with at least one metal oxide of caustic soils to form a mixture, adding water to the mixture,. so that the oxide is brought into reaction with the siliceous substance by the hydration heat produced by the hydration of the caustic oxide, and at the same time excess water is evaporated from the mixture to form a powder.

[6] A flue gas desulfurization apparatus employing a dry method and comprising a sodium silicate addition apparatus comprising a caustic metal compound, a silicate and a water-supplying substance, and an apparatus for dispensing slurry or powder obtained therefrom into an S 'in,;·· . · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 8 8 8 8 8 9 8 9 8 9 8 9 8 9 8 9 8 9 8 9 8 9 8 9 8 9 8 The following effects are used to increase the suction performance.

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[1]; Considering the slaked lime (Ca (0H) 2 described herein), as an example of a desiccant, we can describe the desulfurization reaction of SO2 gas. The desulfurization reaction takes place as follows: £ • 1,

H 2 O + SO 2 ^ 2 ^ 3 Ca (OH) 2 + H 2 SO 3 - > CaSO 3 + H 2 O (D (2)

As shown by (1), SO 2 is absorbed by water v.a and sulfuric acid (2δ03) is formed. According to (2), siphic acid reacts with slaked lime to form calcium sulfate (CaSO 3). If high humidity areas are formed in the desiccant column, then the water content of the slaked lime particles is increased and the reaction of (1) is promoted, and the desiccation rate in such high humidity areas is increased. Moisture in other areas than in high humidity areas is low, but all the water supplied will evaporate at the outlet of the desiccant column and therefore the moisture will increase, so that a predetermined aspiration rate is achieved. Therefore, a high suction efficiency is achieved overall.

[2] In conventional technologies, the calcium sulphate shell or calcium sulphate is formed on the surface of the desulfurizing agent which has reacted with SO 2 in the flue gas at temperatures not higher than 200 ° C, and thus the contact of the desulfurizing agent with SO 2 is poor and no further desulfurization takes place. . However, if the desulfurizing agent is again dispersed in the flue gas whose temperature is between 500 and 900 ° C, a dehydration reaction occurs which disrupts the calcium sulfite shell so that good contact of the desulfurizing agent with SO 2 is restored and the SO 2 removal rate is increased. In addition, a portion of the calcium sulfite is oxidized to calcium sulfate and thus deposited in the landfill is easier.

[3] The desulfurizing agent scattered into the flue gas moistens the water in the aspiration column. " Part of Extraction! Γ: i J; i- -7- 8695 in? The reagent is not transferred to the dust separator but is stored at 1 ''. '' ''; . lower reservoir of desulfurization column. This wetting of the desulfurization * 1 reduces the flowability of the agent. If the temperature of the lower container of the desiccant column is reduced, water in the gas condenses on the surface of the desiccant so that the flowability of the desiccant is further reduced. As a result, the smooth desiccation of the desiccant agent from the container is impaired.

Miraoto is a bottom reservoir equipped with blowers for blowing flue gas or heated air up along the surface of the bottom reservoir wall, thereby removing the moisture of the sedimented desiccant, while keeping the temperature of this portion lower than the saturation flue gas temperature plus 5 " prevents condensation of water on the surface of the container wall. The above measures may increase the flowability of the desiccant and provide a smooth emptying of the container. In order to achieve this, the temperature at the bottom of the container is measured and the amount of sprayed flue gas or heated air is directed to the container portion.

[4] Water is sprayed to cool the outlet gases in the desulfurization column. When these water drops come into contact with the flue gas, evaporate! with flue gas heat. Thus, the water is converted into steam before it leaves the desulfurization column. In water and water vapor conversions, the temperature of the water droplets is not the same as the gas temperature, but is cooled by the latent heat of water and generally reaches the adiabatic saturation temperature. Therefore, measurement. The temperature of these droplets is useful for controlling the amount of water sprayed into the desulfurization column so as to prevent condensation of water while achieving high desulfurization efficiency. However, the size of the water drops in. the desulfurization column is several tens of pm and was. it would be difficult to measure their temperature with a common measuring technique. For example, if a rod thermometer were inserted into a column, only the gas temperature could be measured because the water droplets follow the gas stream.

Therefore, the temperatures of the various portions of the desulfurization column were thoroughly measured and a portion of the same temperature as the water droplets was found. It is the part on which the droplets drop directly. By measuring the temperature of this part, the temperature of the gas at the outlet of the desulfurization column is controlled; ; ·. . ··. , -8-8695 P. ^ * ^ Hr ^ '· - i • • · · gt gt gt gt gt gt gt · · ft »f ^ á! high relative humidity is maintained within the desulfurization furnace and at the same time there is no condensation of water, which promotes deposit formation. Thus, a high desulfurization efficiency is achieved. In conventional technologies, siliceous substances, such as coal ash, are added to the corrosive earth metal compound, such as slaked or quicklime, and then the mixture is heat treated in the presence of water. The reactivity between the caustic soil compound and the siliceous substance (silicon compound) is weak and heating to not less than 100 ° C must take place over a long period of time (ten to several hours to several tens of hours). In addition, since the desulfurizing agent prepared is in the form of a slurry, a lot of energy is needed to dry it and to turn it into powder. When the desulfurizing agent is supplied in the form of a slurry by a spray nozzle, it is subjected to heavy wear and the slurry particles precipitate in the tube. However, when sodium silicate is added to the above slurry, the slurry matures during agitation, the stability of the corrosive earth compound dispersion and the siliceous substance in the aqueous is improved and their reactivity is improved. Therefore, a high SO2 absorbing desulfurizing agent can be prepared in a shorter time and at a lower temperature by this maturation process. At the same time, if the slurry is heated, the stability of the particle dispersion (dispersibility) of the caustic soil compound and the siliceous substance in the water will also increase. The crumb thus prepared is injected into the duct and exhibits a high desulfurization ability.

The oxide of the caustic soil compound, the siliceous substance (coal ash, sodium silicate and the like) and water are mixed. Thus, the heat of hydration is released, causing a reaction between the desulfurizing agent and the siliceous substance, which also causes the evaporation of excess water. With this method, a desulfurizing agent with a high desulfurization capacity can be prepared more economically.

In this case, the sodium silicate is added in the form of an aqueous dispersion to the caustic earth oxide, so that the high heat of hydration is released and hence no further thermal equipment for evaporating excess water is required.

[6] Flue gases leaving the combustion. the apparatus comprising m-9-8695 - - - - - harmful acidic substances such as SO 2 are injected into the gas scrubber, heating the desulfurized flue gas leaving the desulfurization column, and lowering their temperature. Flue gas with such a woman:. the desulfurization column and SO 2 contained therein are removed by a desulfurizing agent containing fine particles of at least one compound selected from the group of X'zemin corrosive compounds. At the same time, in order to increase desulfurization capacity, the temperature of the flue gas injected into the desulfurization column is reduced by desulfurized flue gas leaving the desulfurization column. Thus, the flue gas leaving the desulfurization plant is heated in a mixed heat exchange before it enters the dust separator. Thus, the flue gas temperature at the outlet to the desulfurization column can be reduced to a value above the adiabatic saturation temperature and the desulfurization rate can therefore be very high. An overview of the drawings in the drawings

Fig. 1

A schematic view of the desulfurization plant in Examples 1 and 4.

Fig. 2A and 2B are views showing water spray conditions in the aspirator shown in FIG. First

Fig. 3 is a view showing the arrangement of water spray nozzles in the desulfurization column of Examples 2 and 3;

Fig. 4 is a view showing a water spray nozzle with a vortex separating gas pipe that surrounds the nozzles of FIG. Third

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V ^ 'Fig 1 r' ·: ν · >;. '-. FIGS. 5A and 5B are views showing the conditions under which the vortices are formed, and wherein the water is sprayed into the flue gas by the water nozzle shown in FIG. 4. 6 A view showing dispersion tapes that are positioned above the water nozzles shown in FIG. 4th

Fig. 7 is a diagram showing the dependence of the suction rate at the spray angle of the nozzle of FIG. 5th

Fig. 8 is a diagram showing the dependence of the aspiration rate on the mean diameter of the water droplets sprayed from the water spray nozzle shown in FIG. 5th

Fig. 9 is a diagram showing the dependence of the aspiration rate on the surface velocity using the water spray nozzles shown in FIG. 5th

Fig. 10 is a diagram showing the dependence of the aspiration rate on the angle of the exhaust gas nozzle using the water spray nozzles shown in FIG. 5th

Fig. 11 A view showing the water spray conditions in an exhaustion column of example 5.

Fig. 12 A diagram showing the results of the test of Examples 1 to 5.

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Fig. 13 Schematic view of the desulfurization plant according to Example 6. 14 Diagram showing the desulfurization rate dependence on the adiabatic saturation temperature. 15 Schematic view of a desulfurization plant according to Example 7. 16 Schematic view of a desulfurization plant according to Example 8. 17 Diagram showing the desulfurization rate dependence on flue gas temperature in the duct in Example 9. 18A and 18B Schematic views showing desulfurizing agent particles in Example 10. 19 Diagram showing relationship between the desulfurization rate and the desulfurization rate (Ca / S ratio) of Example 10. 20 Schematic view of the desulfurization plant of Example 13. 21 Schematic view of the desulfurization plant of Example 14. 22 Schematic view showing the modification desulfurization plant of Example 14. 23 Schematic a view of the desulfurization plant of Example 15. 24 A detailed view showing a portion of the desulfurization column shown in FIG. 23 with a spray device. ír-: ír-: 8695 -12- CÔbà. 25 Flowsheet of the apparatus for the right desulphuriser according to Example 17.

Fig. 26 Desulfurization Rate Dependence Diagram on Ca / S Ratio Example 18 and Method.

Fig. 27 Desulphurisation rate versus sodium silicate added diagram.

Fig. 28 Desulfurization Rate Dependence Diagram on Sodium Hydroxide Added by Example 29.

Fig. 29 Flowchart of the desulfurizing agent preparation device, example 21. s

Fig. 30 A diagram showing the relationship between desulfurization rate and the inside temperature of a hydration device according to Example 21.

Fig. 31 Flowsheet of a desulfurizing agent preparation device as in Example 24.

Fig. 32 Desulfurization rate versus Ca / S versus Example 25 plot and comparable example.

Fig. 33 Desulphurisation Dependence Diagram on both the amount and added sodium silicate of Example 26. «fc».

Fig. 34 Diagram showing the relationship between specific surface area and the amount of sodium silicate added according to Example 26.

Fig. 35 Desulphurisation Rate Dependency Diagram of Fired Lime Extinguishing Example 27 < r

Fig. 38 -13-8695

A schematic view of the suction device of Example 30.

The desiccation rate versus Ca / S ratio versus Example 31 and comparable examples.

The deposition rate versus mean residence time plot of the device relative to Example 32 and comparable examples.

Fig. 39 Departure Rate Dependence Diagram on Sodium Silicate Added in Example 37. • > v · '[L · i · .; - *, -l .. '·

Fig. FIG. 40 shows the desiccation rate versus shear rate versus slurry mixing diagram of the desulfurizing agent. FIG. 41 Schematic view of an aspirator device according to example 36.

Fig. 42 mx / · ':' ··: -1. . '.T ·) .- -, ..: · · · · · · · · · · · · · · · · · · · · · ·. ; U: · t · · .1 · W · · · · · ·; · -. ‘'Í · in Fig. 44

Fig. 43

Fig. 45

Departure Rate Dependency Diagram on Sodium Silicate Viscosity as in Example 36. Schematic view of an aspirator according to Example 37. Schematic view of an aspirator device according to Example 38. Departure Rate Dependency Diagram on Spray Positioning. ?? V >: Λ -: Λν..ί · m and v. * .- · >. 4.4 > ν. Ν · ·. ;--IN ··. He knows J ** · ~ -V -. · ..F ··· «. ≫ ·· :: w · Λ ·. ·. ·. ·· Í. - · -14- 8695 AM ·

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EXAMPLES OF THE INVENTION: Vv · Mv · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ■ · .4 ',, Λ-, - »» > :, / 4: 44- Α-.ί · '¾: · ί · & · γ r · r r r r r. . - / '1: " 'λ / aΛ; &, / l;;, Λ /Λ;, &ΛΛ, Λ *, &Λ, &, Λ, Λ, Λ, &, ·,. * · -U%; V »'' * * * * 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44 44. • in - 2 · · ·. ·; • • / '• ΐ.ν.ι' ·· «φ | · i * ® · ''. V *

EXAMPLE 1 The desulfurization apparatus in this example desulphurises the flue gas from a coal-fired boiler and uses slaked lime as a desulfurizing agent. FIG. 1, the flue gas from the boiler 1 is cooled in the air heater 3 and injected into the suction column 4 by means of the inlet pipe 6. The desulfurizing agent (slaked lime) 5 is fed to the duct 13 by the desulfurizing agent delivery pipe 10. The separator 21 provided with water spray nozzles 12 is. The water is fed through line 14 and sprayed with nozzles 12. Air or steam coming through the atomizing gas line 15 is also sprayed through the same nozzles. Water jet 12 is a two-fluid nozzle for atomizing water by air. The droplets dispersed by the nozzles 12 are brought into contact with the flue gas from the boiler at about 150 ° C and evaporate! with. The dispersing rod is positioned immediately above each atomizing nozzle 12. According to FIG. The stream of dispersed droplets leaving the nozzle is forced by the rod immediately above the nozzles to change the flow direction. Bars cause high turbulence. . The water droplets are vigorously mixed with the flue gas over the dispersing roller 16 and a large amount of high humidity vortex 17 (Karman vortices) is formed. Water droplets are trapped in these vortices 17 and evaporate! with. As a result of the formation of the swirls 17, the interior of the vortex is not mixed with the flue gas outside the vortex 17, and thus the interior of the vortex always has high humidity. The vortex 17 contains SO2 from the flue gas and the desulfurizing agent 5, which is agitated above the dispersing roller 16, reacts together under high humidity conditions and hence a high aspiration rate. Humidity in areas without vortex is low. Swirls 17 se. falling apart! as it moves towards the outlet of the aspiration column 4. After all the droplets have evaporated, the moisture will rise to an average water concentration and thus a desiccant reaction rate that corresponds to that humidity can be achieved. Namely, areas of high water concentration ie. High humidity vortex areas are preferred to form only the internal inside of the desiccant column 4, thereby increasing the reactivity within the vortex within the vortex column; .

and thus the total desulfurization rate at the outlet of the desulfurization column 4.

This method contrasts with the conventional method in which good mixing of droplets and flue gas is ensured to increase the rate of evaporation, thereby rapidly achieving a uniform distribution of water concentrations but with this inventive method a high desulfurization efficiency can be achieved.

Desulphurisation test. this equipment was operated under the following conditions. Coal A is burned in boiler 1 (SO2 concentration in flue gas is 2000 ppm). The slaked lime is used as desulfurizing agent 5, and this slaked lime is sprayed in molar amounts twice that of SO 2 (hereinafter "Ca / S" ratio). Water is sprayed in the water spray nozzles 12 so that the exhaust gas outlet temperature of the desulfurization column is 70 ° C. The liquid / gas ratio (flow rate of water / flue gas stream containing sulfur through the flue gas) is a 0.04 1 H 1 / m 2 flue gas and the average water droplet size is 30 µm, while the nozzles 12 are located 1.5 m from the gas inlet the desulfurization column 4, and the dispersion angle of the water dispersion through the nozzle 12, A, is 50 °, and the surface velocity of the gas γ desulfurization column 4 is 2 m / s. As shown in FIG. 2B, the water dispersion angle of the water dispersion through the nozzle 12, A is the angle of the vertical cut of the water dispersion above the nozzle.

The SO 2 concentration measured in the gas from which the water vapor was removed at the outlet of boiler 1, and at the outlet of the dust collector 8, was 2000 ppm and 400 ppm respectively. Thus, this process removes 80% SO 2 from the flue gas. The use of Ca in the desulfurizing agent particles obtained from the bottom of the dust separator 8 is 40%

Example 2

FIG. 3 to FIG. 5B, the distributor 21 is located within the desulfurization column such that the water spray nozzles face the gas flow. As shown in detail in FIG. 4, the mouth of the water tube 14 is disposed in the middle of the atomizing nozzle 12 and the mouth of the tube 15 supplying the atomizing gas surrounds the mouth of the water tube 14. Therefore, the water supplied by the water line 14 is atomized by the gas tube 15 and ejected from the nozzle 12. \ t - -16- 8695 I'1 ·. · ,. The vortex tube 18 surrounds the spraying water nozzle 12 and therefore the vortexes containing the fine water particles spaced from the mouth, the nozzles 12 can be easily separated from the nozzle 12.

Since atomized water is sprayed in a direction opposite to that of the flue gas, stable vortices 17 are formed near the water spray nozzle 12, as shown in FIG. 5A and 5B. Because the stable beliefs 17 contain! sprayed droplets and because they separate! from the nozzle 12, a high humidity swirl 17 is formed. FIG. 5A water is sprayed at nozzle angle 180 " with respect to the flue gas flow and to FIG. 5B, water is ejected at a nozzle angle of 135 “relative to the flue gas flow. The nozzle angle means the angle between the particle trajectory coming out of the nozzle in its axis direction and the flue gas flow direction in the desulfurization column. Stable vortex 17 is formed on the same site and practically does not mix with the environment. Accordingly, a gas is introduced into the vortex separating tube 18, which separates the vortices 17 'near the water nozzle 12. The right vortexes 17 are entrained upwards by the flue gas and hence the fresh vortices 17 which have high humidity are repeatedly formed. Although the gas separating vortices may flow smoothly, a greater effect is obtained by interrupting the flow of this gas. The water is injected into vortex 17 with high humidity against the flue gas flow. That's why they are. droplets of water are immediately decelerated and then entrained in the flue gas. As a result of the vortex formation 17, the desulfurizing agent and the SO 2 -containing flue gas are well mixed and enter the vortexes 17. As water droplets are present in these vortices 17, the relative humidity - close to 100% - can easily be achieved. The swirls 17 spaced apart from the nozzle 12 are limitedly mixed with the surrounding flue gas, flowing through the flue gas, and maintaining high humidity. Therefore, the inside of these vortices. shows a high desulfurization efficiency. High humidity swirls 17 are mixed with the surrounding flue gas at the outlet of the desulfurization column 4, the water concentration increases to a uniform level and therefore a high total desulfurization efficiency is achieved.

Since the diameter of desulfurization column 4 is relatively large in < RTI ID = 0.0 >amp; < / RTI > ,. J V J J J J J J J J J J J

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- í í í ·.. > · * - *, ·· - - »In i.,. In comparison with the diameter of the duct 13, the velocity of the flow in the connecting expanding portion is slowed down and a return flow region is formed. Therefore, the desulfurizing agent particles 5 flowing through the duct 13 enter the return flow region and thus become stagnant, ie. it floats and forms an area in which the concentration of desulfurizing agent is high. This region extends from the inlet of the duct 13 to a distance generally equal to the diameter of the desulfurization column. As a result of water spraying in this region, the high concentration desulfurizing agent is introduced into; contact with swirls of high relative humidity and hence higher desulfurization efficiency can be achieved. The device's desulfurization test was performed under the same conditions as in Example 1. The SO 2 concentration was measured in the gas from which the water vapor was removed from the boiler 1 outlet and at the dust collector outlet 8. 2000 ppm and 400 ppm concentrations were determined . Thus, 80% SO 2 in the flue gas was removed by a three-step process. The use of Ca in the desulfurizing agent particles obtained from the bottom of the dust separator 8 is 40%. Comparative Example The desulfurization test of a conventional coal A desulphurisation plant was carried out under the same conditions as in. Example 1. The desulfurizer used in the comparative example was different from that used in Example 1 in that the water spray nozzles of the water separator inside the desulfurization column are adapted to inject water parallel to each other in the same direction as the flue gas flows. !; ≪; The current SO2 concentration at the outlet of the dust separator was 800 ppm and a desulfurization efficiency of 60% was achieved. The use of Ca in the desulfurizing agent particles obtained from the bottom of the dust separator is 30%. -17- 8695

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EXAMPLE 3 Desulfurization equipment similar to that described in Example 2 is used in this Example. sprayed inside the desulfurization column in a direction opposite

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I '; | à;.' ·· > · -..... 'Sífľ4í- ‘·' ·. '!’ ··. im? - - & - v > - - < A '·· <' -. · * -¾1? 1 '' ·. Flue gas flow. The coal A test is carried out in the same manner as in Example 1. As shown in FIG. 6, this example differs from Example 2 in that the dispersion tape 16 is positioned immediately above each water jet to form a vortex 17. Atomized water droplets are subjected to the dispersion tape 16 flow it and then flow together with the flue gas stream. These water droplets are intensively mixed with the flue gas on the dispersion tape 16 and a high number of swirls 17 is formed. As a result of this process, the interior of the vortex 17 maintains high humidity and the reaction between SO2 and the desiccant is promoted. In the desulphurisation test, the SO2 concentration at the outlet of the dust separator was 300 ppm and the utilization of Ca in the particulate removal agent obtained from the bottom of the dust separator was 42.5%. As already mentioned, when water and atomizing gas are shaded in the flue gas in the opposite direction than the flue gas flows, high humidity areas are formed. Therefore, the aspiration tests for the various directions of injection and test for comparison in which the water was injected parallel to the flue gas flow were carried out in the apparatus of Example 2. The parameters used are as follows: The spraying angle A (see Fig. 2B) of the water spray nozzle was 10, 20, 30, 50, 70, 120, 140, 160, 180 °, the mean water droplet diameter was 10, 20, 30, 50, 70 , 100, 140, 170 and 200 µm, and the mean gas step velocity was 0.5, 1.0, 3.0, 5.0, 7.0, 10.0, and 15 m / s. The results of these tests are shown in FIG. 7, 8, and 9. It was. . It has been found that spraying water against the flue gas direction results in a higher aspiration efficiency compared to co-jet injection. Spray angle of water jet A: 20-90 " Medium diameter of droplet droplets: 20 to 140 µm Gradual flue gas velocity in the desiccant columns: 1 to 10 m / s:: - JS ... f * > (.. · "..

Example 4

In order to find a suitable angle for mounting the water spray nozzle 12 relative to the flue gas flow, as shown in FIG. 5B, a desulfurization test with different mounting angles was performed. The desulfurization assay was performed with carbon A under the same conditions as in Example 2. The results of this assay are shown in FIG. 10. If the water-containing fluid is sprayed at an angle of between 40 and 180 " higher desulphurisation efficiency is achieved than with co-current flow.

The SO2 concentration at the outlet of the dust separator was 400 ppm and the desulfurization efficiency achieved was 80%. The utilization of Ca in the particles of the sulfurizing agent obtained from the bottom of the dust separator is 40%. . j.

It is not practical if the liquid / gas ratio is less than 0.02 1: 1 water / 1 mJN flue gas, then the flue gas temperature becomes high, and desulfurization efficiency decreases. On the other hand, when the liquid / gas ratio is greater than 0.05 1 water / 1 m 2 N then the flue gas temperature approaches the adiabatic saturation temperature and the water content often reaches the dew point, which is also not practical. Accordingly, the liquid / gas ratio should be in the range of 0.02 to 0.05 1 water / 1 m 2 N flue gas.

The location of the water spray nozzles 12 will be described for example. for the desulfurization column construction shown in FIG. 3. If the sprayed water is sprayed up to the wall of the desulfurization column, or other construction within the desulfurization column 4, it will moisten and allow dust particles to collect and deposit on the wet section. In order to avoid this, the moisture in the plane perpendicular to the flue gas flow must descend from the central part of the column to its wall. Also, the outlet temperature of the column must be kept higher than the saturation temperature. To ensure this, the nozzle 12 is thus positioned in a plane perpendicular to the gas flow within the desulfurization column, just in the plane along the gas flow, that the wall portion of the column is as low as possible. Further, the effective length of the desulfurization column from the nozzles, considered in the gas flow direction, is required to be of a guaranteed size. If the water nozzles 12 are high, the overall height of the desulfurization column is increased, which is uneconomical.

Therefore, the water spray of the nozzle would be preferred so that the L / D (distance from the inlet / desulphurization diameter) was not greater than 1 (see FIG. 3). In the actual plant, which has a processing capacity of not less than a few tens of thousands: m ?N per hour, the nozzles should be placed within 5 m of the inlet flue gas desulfurization column. -in-:· · *

Example 5 In the example shown in FIG. 11, the groups of water jets 12 are disposed opposite one another, so that in this desulfurization column 4 the water jets are sprayed against each other. Stable vortices are formed at the outlet of the water nozzles 12 downstream

> V 4 flue gas. By impacting from the nozzles, the pressure in this impact section rises, so that the jet streams fluctuate up, down, and left. Because of these fluctuations of the stable vortex 17, they are separated from the proximity of the nozzles 12, moving upwardly; ’” 'So that swirls 17 are repeatedly formed. As a result, the effect of closing the droplets into the vortexes 17 and the total desulfurization efficiency at the outlet of the desulfurization column is increased as in the previous examples.

The device's desulfurization test was performed using charcoal A under the same conditions as in Example 1.

The SO2 concentration at the dust dust separator outlet is 400 ppm and the desulfurization is 80%. The use of Ca in the desulfurization agent obtained from the bottom of the dust separator is 40%.

Fig. 12 shows the test results described in the preceding examples. It will be appreciated that the desulfurization rate achieved with the present invention is higher than with conventional methods.

To summarize, the reaction between SO2 and desulfurizing agent is; supported by the formation of vortices inside the flue gas stream in the desulfurization column. In these whirlpools, regions of higher relative humidity are formed which, upon admixing the desulfurizing agent, promote a desulfurization reaction. This achieves a high desulfurization efficiency.

In order to effectively control the amount of water supplied and the water-dispersing fluid stream, we should equip the desulfurization column or its outlet with at least one of temperature, humidity, or water concentration sensors. Thereafter, the amount of water and the amount of fluid to disperse it is adjusted according to signals from such sensors.

Example 6

Fig. 13 shows the application of the present invention to a commercial boiler. SOX-containing coal or oil-containing flue gases leaving boiler 1 are cooled to 150 DEG C. in an air heater 3. In coal combustion, the water content in the flue gas is about 7-10%, in heavy oil combustion 12-13%. The flue gas is injected into the heat exchanger 30 where the heat is exchanged between the gas leaving the desulfurization column and the incoming flue gas and, consequently, the flue gas temperature is further reduced. Flue gas entering the desulfurization column 4 and desulfurizing agent 5, slaked lime or the like, and water are injected into the desulfurization column so that SOX is removed from the flue gas. In this case, the desulfurization efficiency is strongly dependent on the temperature inside the desulfurization column 4, the difference between the inside temperature of the column and the adiabatic saturation temperature. The device is characterized in that the desulfurized flue gas leaving the desulfurization column is heated in the heat exchanger 30 by the heat of the flue gas entering the desulfurization column before it enters the dust separator. In this device, the outlet temperature of the desulfurization column may be reduced to a value above the adiabatic saturation temperature so that the above variation is large (small) and a high desulfurization rate is achieved. The relationship between the desulfurization rate and the difference from the adiabatic saturation temperature was investigated for various gas reaction temperatures using a device for accurate humidity control. The results of these experiments are shown in FIG. The desulfurization rate strong depends on this temperature difference and it is clear that when the desulfurization column temperature is near adiabatic saturation temperature then the desulfurization rate is high.

The hot air of 200 Nm @ 2 / h, which contains 10% water vapor, is produced in the heavy oil furnace and the SO 2 gas is mixed into the hot air from the SO 2 cylinder. This results in simulated flue gas corresponding to the flue gas leaving the boiler in which the concentration of 2000 ppm SO2. The temperature of the simulated flue gas is maintained by the condenser at approximately 150 eC, which corresponds to the temperature of the actual flue gas at the outlet of the air heater 3 (see Fig. 13; see, supra).

When simulated flue gas is injected into the heat recovery heat exchanger (Jungstorm preheater) under the above conditions, the flue gas temperature at the outlet drops to 90 ° C. Then the simulated flue gas is injected into the desulfurization column. The slaked lime is supplied in an amount such that the molar ratio of slaked lime to SO 2 is 2. Based on the temperature information in the central desulfurization column, the water supply is controlled to 5 ° C higher than the adiabatic saturation temperature. In this case, the adiabatic saturation temperature was 59 ° C.

The SO 2 concentration at the outlet of the desulfurization column is 350 to 360 ppm and the desulfurization efficiency is about 83%.

On the other hand, the temperature of the flue gas leaving the heat exchanger is about 90 ° C and is about 30eC higher than the adiabatic saturation temperature. Immediately after the test, the dust separator was disassembled and subjected to a visual inspection. No condensation was found.

Comparative test

A comparative test was performed in the above device. In this case, a heat exchanger was not used and instead the flue gas was directly fed to the dust separator. While monitoring the temperature, the water was continuously added to wl

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* · '·· viiVi'r ^' i; ·, · v., - ··. ·., · ÍJkV * ..; ·. / * · '·· Vrt' ^ '···,: 1 - ./•in·*'. * > ‘- · *. The gas temperature at the outlet of the desulfurization column was 10eC higher; than the adibatic saturation temperature (in this case 64 ° C), which would prevent the corrosion caused by the T condensation inside the dust collector in the real scale device. The SO 4 concentration at the desulfurization plant outlet is 850 µ-V. ppm and desulfurization efficiency is 58%, which is not much. · R; Example 7 In this example shown in FIG. 15, lime 5 serving as desulfurizing agent is added to boiler 1 to cause high temperature desulfurization and water 9 is injected into desulfurization column located downstream of duct 13 to cause low temperature desulfurization. The heat exchanger is positioned between the air heater 3 and the desulfurization column 4. This exchanger cools the flue gas coming into the desulfurization column and heats the effluent; gas. Also in this example, the reaction temperature inside the desulfurization column 4 can be reduced and a similar effect to that of Example 6 can be achieved. In Examples 6 and 7, condensation inside the dust separator 8 can be prevented even when the temperature in the desulfurization column is reduced tightly to the adiabatic saturation temperature. This is ensured by the exchange of heat between the flue gas entering the desulfurization column 4a and the flue gas leaving the desulfurization column 4. Thus, even with the unit in which the desulfurization column is integral with the dust separator, the desulfurization column will not be impaired by the corrosion of the dust separator. that desulfurization efficiency depends on relative humidity, the water content required to achieve the same moisture can be reduced by lowering the temperature at the inlet to the desulfurization column and the desulfurization efficiency can be increased. i. . «. '·' ·. in

Example 8 The desulfurization efficiency is evaluated in the apparatus shown in FIG. 16. The device releases a portion of the particles (trapped in the dust separator 8 and is therefore called " trapped particles ") containing unreacted and reacted desulfurizing agent and ash, and the remainder is injected through conduit 6 into duct 6,

and -24- 8695 in which the flue gas temperature is 600 to 900 ° C, and then reacts again. acidic pollutants, such as SO 2, in the flue gas.

A desulfurization test was carried out on this device; when burning B (sulfur content at this angle is 0.8%). Extinguished lime was used as the desulfurizing agent and the Ca / S primer was the amount of water sprayed up to 3% of the flue gas, and the water could be sprayed with either two fluid nozzles in common with air or single fluid nozzles. The temperature at the outlet of desulfurization column 4 was 70 ° C. Half of the particles (by weight) trapped in the dust separator 8 were drained and the residue re-injected from line 22 into duct 6, where the flue gas temperature reached 600eC.

After removing the water from the offgas at the outlet of the boiler 1 and at the outlet of the dust separator 8, the concentrations of 640 and 60 ppm SO 2 were measured. Thus, desulfurization efficiency was 91%.

Example 9

Using the same apparatus as in Example 8, the desulfurization rate is measured under the same conditions as in Example 8. However, the location to which the trapped particles are injected is altered. The dependence of desulfurization efficiency and flue gas temperature in duct 6 is investigated. The results are shown in FIG. T7. The desulfurization rate depends on the temperature of the flue gas in the duct 6 and it appears that the temperature range of 500 to 900 ° C should be preferred. Similar investigations have been made with other types of coal and desulfurizing agents, and it has been found to be advantageous to operate at a temperature range of 500 to 900 ° C.

In fact, when the temperature is high, the dehydration reaction expressed by the following equation takes place when slaked lime is used as the desulfurizing agent.

Ca (0H) 2 - > CaO + H 2 O In this case, when the water evaporates, the shell of calcium sulphate and calcium sulphate covering the surface of the desulfurizing agent is destroyed and the pores of the desulfurizing agent particles 5 increase in volume. Consequently, the contact efficiency of the desulfurizing agent with SO 2 in the flue gas increases (see Figure 18A). When the flue gas temperature is low, high desulfurization efficiency cannot be achieved (see Figure 18B). . On the other hand, at temperatures above 900 ° C. carbon dioxide CO2 reacts with a desulfurizing agent to form CaCC 3, which results in a reduction in the amount of desulfurizing agent that it has reacted; with SO 2, and at a high temperature, the particles of the desiccant are sintered, which prevents an increase in the volume of the porous material. Therefore, in a conventional manner, where the entrapped particles are mixed into the slurry and sprayed into the boiler at a gas temperature of 1000 to 1200 ° C, high desulfurization efficiency cannot be achieved. with

Example 10

Using the same apparatus as in Example 8, the desulfurization rate was measured under the same conditions as in Example 8. However, the amount of desiccant used expressed in Ca / S molar ratio was from 1 to 3. The results are shown in FIG. 19. The desulfurization rate is about 80% using a Ca / S = 1 ratio.

Example 11

Using the same apparatus as in Example 8, the desulfurization rate was measured under the same conditions as in Example 8, but other charcoal was used, namely a second batch of až-.. TAB. 1 shows the sulfur content of these coal, the SO2 concentration in the flue gas at the outlet of the boiler 1a at the outlet of the dust separator 8, the calcium sulfate ratio (hereinafter referred to as " oxidation ratio ") in the reacted desulfurizing agent (calcium sulphate and sulphite) which is discharged from Dust separators 8. High desulphurisation rates were achieved for all coal. , / «. ... > · *, «,% //, v '. .mmW'- '' -26- 8695 V; í »·! * ...... t · '; ..- V · 'Vj ·' *? i '' .ψ ''! · &: ·: $ & í-. ·· 1; —- · 4 * · /?-.- v7 > · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · → · Γ * " * · '' s, χ · .... - - * or. .Fi. .. I.:ív:v i: ... I · «» '. 1 '' .'f, i. , *, ŕ * - · - - -J »" - '' i: * '·. ·' >, r TAB. 1 .fa; Coal type C D E F G Sulfur content (%) 0.3 0.5 0.5 2.0 3.1 ;; S02 at boiler outlet (ppm) 230 400 420 1680 2550 SO2 at the outlet of the dust separator (ppm) 25 35 40 155 230 Oxidation ratio (%) 92 90 85 88 85

Example 12

Using the same equipment as in Example 8 and under the same conditions as in Example 8, the aspiration rate was pickled. However, other CaO, CaCO3, NaOH, and Mg (OH) 2 aspirators were used and their aspiration capacity was tested. The results are presented in TAB. 2. TAB. 2

Desulfurizing agent CaO CaCO3 NaOH Mg (OH) 2 SO2 concentration at the outlet of the separator (ppm) 50 120 40 50 ‘ΊΛ · · - ··. > · V · i ·; ': ii. · * ·. »- · ·: * P .. BbB.:·· m ^ lv · - •'« •, '1' · ^ - · .. '·' i ··: ' :. ,:? / < & >; «· / ''

Comparative Example 2

In the same apparatus as in Comparative Example 1, the oxidation and desulfurization efficiencies are measured using six different second coals B to G under the same conditions as in Experiments 8 and 11. Water was added at 3% by weight. The flue gas is sprayed into the flue gas duct 6 and 50% of the weight particles trapped in the separator is again fed to the flue gas collector 4 via line 22. The results are shown in the TAB. 3. The oxidative and aspiration efficiencies found are inferior to those achieved in the examples illustrating the present invention. ilgáifí-XV --v1 · * > · ': " t, ·. * »+ ··. . 7 - ·· * · ···; ;} C; ,IN- :. .V, · * - '· -27- 8695 * / κΐ ^' Λ. · '···,. · TAB. 3

about/·/ : . . K · · · · ·. ··: · i; V} - * v * '¾' '· > -I- · ·: £ -, '"' • '• ÍK V-.v -i; ··:, * -. · I' S #; · '":'? ≫.; S ·· -V *, .- ·. 2 · *. -il-U · *. Coal Type BCDEFG Sulfur Content (%) 0.8 0.3 0.5 0.5 2.0 3.1 S02 at Boiler Outlet (ppm) 640 230 400 420 1680 2550 S02 at Dust Separator Output (ppm) 330 170 190 220 860 1350 Oxidation ratio (%) 25 21 15 22 13 22 i: i

Comparative Example 3

In the same apparatus as in Comparative Example 1, the aspiration efficiency for carbon B is measured under the same conditions as in Example 10. The results are shown in FIG. 19. Compared to the aspiration efficiency achieved by the method of the present invention, the aspiration efficacy in this experiment is lower in all conditions and there is a tendency to suggest that the difference 1 between the methods is greater when less desulfurizing agent is used.

i ΧΨ ·. ; &Quot; ««. ·! f c .V :. m z '.

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Comparative Example 4 In the same apparatus as in Comparative Example 1, the aspiration efficiency for carbon B is measured under the same conditions as in Example 12 using CaO, CaCO 3, NaOH, and Mg (OH) 2 desulfurizing agents. The results of these experiments are shown in TAB. 4. In comparison to the aspiration method of the present invention, the aspiration rate in this comparative experiment was always low and the SO 2 concentration at the outlet of the separator 8 is high.

0 -28-8695 ΤΑΒ. 4

Desulphurizer CaO CaCO3 NaOH Mg (OH) 2 SO7 concentration at the outlet of the separator (ppm) 295 410 250 355

Example 13

Unlike the device shown in FIG. 16, where the entrapped particles in the dry powder form are sprayed into the duct 6 where the temperature is 600eC, the entrapped particles can be mixed with water to form a slurry which is then sprayed into the duct 6. As shown in FIG. 20, one portion of the entrapped particles is injected from the separator into an apparatus for preparing the desiccant 37 and is mixed with the water supplied through the conduit 28 to form a slurry. This slurry is then fed to the duct 6 by pump 29. This method of spraying the slurry into duct 6 is advantageous in that the reaction product shell on the surface of the desiccant particle is readily removable and that the desiccant particles do not readily react with CC 2 in the flue gas. As a result, high aspiration efficiency can be achieved.

Note also the recycle of the desulfurizing agent introduced through line 10. After the water has been added to the trapped particles, they are again dried, the skin of the desulfurization reaction product is disrupted, and the particles are re-injected into the duct 6. With this method, the particles do not agglomerate due to the destruction of the shell product of the desiccating reaction during drying. This improves the spray characteristics of the desiccant. . Example 14 In this example shown in FIG. 21, the flue gas from the boiler 1 is cooled by an air preheater 3. The desulfurizing agent 5 by the incoming pipe 19 is sprayed from the nozzle 11. The desulfurizing agent 5 flows through the duct 13 to the aspiration column 4. Inside the desiccant column 4, water is sprayed through the nozzles 12 to cool the flue gas and thereby promote the reaction between desulfurization -29-8695 and the sulfur oxides in the flue gas. The reacted desulfurization agent is trapped in the dust separator 8 and discharged from the process. The flue gas is discharged through the chimney 7.

In the above-mentioned desulphurization process, the wetted powder exhibiting a volatile fluidity is deposited in the lower part of the desulfurization column 4 as described above. In order to smoothly drain this wetted powder, it is necessary to maintain the temperature of the lower container by 5eC above. than the saturation flue gas temperature. Therefore, a portion of the flue gas is conducted through conduit 23 and injected into the lower ... part of the desulfurization column 4 using a blower 24. In this case, the annular distributor 26 is located at the bottom of the container and the flue gas is blown up along the container cone from the circular distributor 26. The current is controlled. a plurality of flue gases supplied by the separator 26 under a temperature sensor 27 located at the bottom of the container. In other words, in order to keep the bottom temperature of the container 5 ° C above the saturation temperature of the flue gas, the amount of flue gas injected is controlled by the auxiliary blower 24 at the temperature of that portion of the container detected by the sensor 27. The desulfurizing agent 5 deposited at the bottom of the desulfurization column is drained a discharge line 25.

After 100 hours of continuous operation, the powder can be removed smoothly from the lower reservoir. At the end of the experiment, the interior of the desulfurization column was inspected and no solids were found as desulfurizing agent 5.

Fig. 22 shows an example in which an aeration system is used to deliver flue gas to the bottom of the desulfurization column reservoir 4.

Example 15 In the examples shown in FIG. 23 and 24, the flue gas from the boiler I flows through the duct 6 and is cooled in the air preheater 3 and injected into the desulfurization column 4 through the duct 13.

The slaked lime desulphurizing agent 5 is sprayed from nozzle II into the desulfurizing agent feed tube 13. The desulfurizing agent 5 is entrained in desulfurization column 4 by a duct 13. In the desulfurization column, water is sprayed from nozzles 12 of distributor 21 to reduce the temperature flue gas. Simultaneously, the temperature at the point 55 at which the water spray droplets fall is measured by the thermocouple 57. The signal from thermocouple 57 is fed to detector 58 and to a computer device that counts the amount of water sprayed. This amount is controlled by the control valve 60, so that the temperature at the outlet of the desulfurization column 4 can be higher than this detected temperature.

The exhaust gas discharged from the exhausting column 4 is injected into the dust separator. The desulfurizing agent 5 reacts with the deleterious acid gases such as SC > 2 within the desulfurization column 4, and the reacted ash desulfurizer is trapped by the dust separator 8 and discharged. The flue gas is discharged through the chimney 7.

The desulfurization test was performed on this apparatus. Coal A was burned (SO2 concentration in the flue gas is 2000 ppm). Slaked lime was used as desulfurization agent 5. It was supplied in a " Ca / S " The temperature at the exit of desulfurization column 4 was controlled to be 10 ° C higher than the temperature at site 55 detected by thermocouple 57 and the amount of water sprayed through nozzles 12 was adjusted by the signal from the thermocouple.

After the water was removed from the gas at the outlet of the boiler 1 and at the outlet of the separation device 8, the corresponding SO2 concentrations were 2000 and 400 ppm. Thus, 80% SO2 in the flue gas was removed.

After 100 hours of continuous operation, the interior of the desulfurization column 4 was inspected and found: no solids as desulfurizing agent 5.

Example 16

The desulfurization rate was measured on the same equipment and under the same conditions as in Example 15. However, the gas outlet temperature of the desulfurization column was controlled to be 5 ° C higher than the point 55 that is detected by thermocouple 57 and the amount of water spaced by the nozzles 12, the signal from the thermocouple 57 is adjusted.

After the water was removed from the gas at the outlet of the boiler 1 and at the outlet of the separation device 8, the corresponding SO 2 concentrations were 2000 and 200 ppm. Thus, 90% SO 2 in the flue gas ;; " í · ;: " ^ íoylo removed. -31- 8695

i1 Vi '· ···' W; > ' as in Example 15, the interior of the desulfurization column 4 was inspected after 100 hours of continuous operation and no solids were found as desulfurizing agent 5. Comparative Experiment 5 S:

The same equipment as in Comparative Example 1 was used and the desulfurization test was performed for Coal A under the same conditions as Example 15. As in Example 15 after 100 hours of continuous operation, the interior of the desulfurization column 4 and the interior of the dust separator were inspected and found 2 kg of solids such as desulfurizing agent 5 (about 1% of the desulfurizing agent used in the experiment. Furthermore, corrosion of the nozzle tube surface was observed in the desulfurization column.

Comparative Example 6 *: vty-: ", i ' - "; · · · · = = = = = = =:::::::::::::: . · -: - ¾ / --7 ---. • > /: * ·· ':; - ·,' ι ií.'v · '. ·)' &Quot; .ff ·. * ·· 'i' i * '· »1 in' ·· * ' r · / '-' ·. ··. -in M · . · Lf ^:,; · n ér ·. -í; . '·' · * ≫ · .. »» > ... . -i ‘.. · > ' .i- ·· »·. ' ·. , " * i '·. '. ·: ≫: h ·· > . ú - :, · -, · '" - 1i.

· * 1; -! yt in “J • t ·.

Using the same conventional apparatus as in Comparative Example 1, a desulfurization test was carried out for coal A under the same conditions as in Example 16. As in Example 16 after 100 hours of continuous operation, the interior of the desulfurization column 4 and the interior of the dust collector were inspected and found 10 kg of solids such as desulfurizing agent 5 (about 5% of the desulfurizing agent used in the experiment. In addition, corrosion of the nozzle tube surface was observed in the desulfurization column. Thermocouple 57 can be placed anywhere if droplets of sprayed water fall on it) In order to avoid deposition of desulfurizing agent on the internal walls of the desulfurization column using a conventional method, the temperature at the outlet of the desulfurization column is about 10-20 ° C higher than the saturation temperature. However, the arrangement of the present invention allows for a stable operation even if the λ 'λ' > The temperature

So he can. In the -32- 8695 only 5 ° C higher than the adiabatic saturation apartment, high desulfurization efficiency is achieved. temperature.

Example 17

Fig. 25 shows an example of a device for preparing a desulfurizing agent. The limestone is heated in a heating furnace to produce burnt lime. Then the lime is mixed in the mixer with coal ash. This blend of burnt lime and coal ash is supplied from the blender to a hydrating facility where the burnt lime and coal ash (and the water overhang) react! and forming a high specific surface desulfurizing agent.

In order to form burnt lime, the limestone in the preparation of the desulfurizing agent in the apparatus shown in FIG. 25 deprived of CO2 in the heating furnace. Any type of heating furnace can be used if it can decompose limestone. If the desulfurizing agent particles agglomerated from the hydrating device are used, a powdering device can be used to disperse again.

The desulfurization efficiency of the apparatus in which the desulfurizing agent prepared in this manner was delivered by spraying it into the flue gas in the duct 13 (FIG. 1) was tested for coal A. The amount of limestone corresponded to the molar ratio of " Ca / S = 2. in an amount corresponding to 60% of quicklime (burnt lime: ash = 5: 3). The amount of water corresponded to three times the molar amount of quicklime. The mean residence time of the particles in the hydrating device was 1 hour. Other conditions were the same as in Example 1.

The SO 2 concentration was measured in a gas from which water vapor was removed at a droplet volume of 1, 2000 ppm, and at the outlet of the dust separator, 200 ppm. Thus, 90% SO2 in the flue gas was removed by this procedure.

Example 18

Using the same apparatus as in Example 17, desulfurization efficiency is tested under the same conditions as in Example 17. However, the amount of calcined lime used, Ca / S ratio, is varied. The ratio of calcined lime to ash 8695 -33-. (Coal) was the same as in Example 17. The results are shown in Figure 26. The higher the Ca / S, the higher the desulfurization efficiency. efficiency greater than 75% is achieved with Ca / S = 1.

Example 19

Using the same apparatus as in Example 17, desulfurization efficiency is tested under the same conditions as in Example 17. However, sodium silicate is added to water which is injected into a hydration apparatus to prepare a desulfurizing agent. Fig. 27 shows the desulfurization efficiency dependence on the added amount of sodium silicate (in weight percent based on calcined lime). The 0% added sodium silicate corresponds to the addition of water in a molar ratio of 3.5 to the amount of calcined lime. An increase in desulfurization efficiency can be seen with the addition of 0.01%. When adding 10 to 20%, the desulfurization efficiency is maximized. From the point of view of economical desulphurisation, it has been found in tests with other types of coal that the amount of sodium silicate relative to. the amount of quicklime should be between 5 and 20%.

Example 20

Using the same apparatus as in Example 17, desulfurization efficiency is tested under the same conditions as in Example 17. However, sodium hydroxide is added to the water which is injected into the hydration apparatus in which the desulfurizing agent is prepared. Fig. 27 shows the desulfurization efficiency dependence on the added amount of sodium hydroxide (in weight percent based on calcined lime). An increase in desulfurization efficiency is apparent already at an added amount corresponding to 0.01%. When adding 10 to 20%, the desulfurization efficiency is maximized. In terms of economical desulphurisation, tests with other types of coal found that the amount of sodium hydroxide relative to the calcined lime should be between 5 and 20%.

Example 21 Example 17 does not control the temperature of the hydration process at 8695-34- • ovacího. By introducing temperature control, the quality of the desulfurizing agent may be increased. Fig. 29 shows such an example. The moisturizer is equipped with steam heating and water cooling. The desulfurization assay is performed under the same conditions as in Example 17, but a desulfurizing agent prepared according to this example is used. The desulfurization efficiency dependence at the temperature inside the desulfurizing agent is shown in FIG. 30. It is preferred that the internal temperature of the desulfurizing agent is between 80 and 130 ° C. Desulfurization efficiency is reduced when the temperature is outside this range. In the same apparatus as in Example 17, a desulfurization test is carried out under the same conditions as in Example 1. In this case, a second coal having a different sulfur content was used. The results are shown in TAB. 5. TAB. 5

Type of coal H I J K L Sulfur content (%) 0.3 0.3 0.8 1.0 3.0 Desulphurisation efficiency (%) 94 94 90 92 88

Example 23

In the same apparatus as in Example 1, desulfurization test using magnesium carbonate (MgCO 3) and magnesium sodium carbonate (CaCO 3 .MgCO 3) was carried out under the same conditions as in Example 1. The results are shown in TAB. 6. TAB. 6

Desulfurizing agent MgCO3 CaC03MgC03 Desulphurisation efficiency (%) 86 89 8695 -35-

Example 24

Fig. 31 shows an example of a device for preparing a clarifying agent. The limestone is heated in a heating furnace to produce burnt lime. Burnt lime is supplied to the mixer. An aqueous solution of sodium silicate is added to the burnt lime in the mixer and the quicklime is reacted with sodium silicate in an aqueous sodium silicate solution. The mixture is further stirred for a period of time. to provide a desulfurizing agent having a high specific surface area. In the apparatus for preparing the desiccant shown in FIG. 31, limestone is deprived of carbon dioxide in the heating furnace. Any type of furnace can be used if it can remove carbon dioxide from limestone. The shard may be arbitrary if it can mix powders.

The desulfurizing agent thus prepared is injected into the flue gas in the boiler duct 13, see FIG. 1. Thus, the desulfurizing agent is used for desulfurization.

With this desiccant, the coal extraction efficiency using coal M (1.9% sulfur, 12.4% ash content) was tested and burned in the plant shown in FIG. 1. Limestone (slaked lime) is supplied to the kiln in an amount that provides a Ca / S molar ratio of 1.5. Sodium silicate (water glass) is added to the mixer in an amount corresponding to 5% by weight of the calcined lime. The amount of water supplied in the sodium silicate solution is 2.5 times (molar) greater than the amount of quicklime. An amount corresponding to 3% by weight of flue gas is sprayed in the aspiration device 4. This water is fed through line 14. 50% of the particles trapped in the dust separator 8 are returned to the aspiration column 4 through tube 22 and the remainder is discharged. The unreacted desulfurizing agent contained in the particles trapped by the separator 8 is not counted as a Ca / S value.

After the water was removed from the gas at the outlet of the boiler 1 and at the outlet of the separation device 8, the corresponding SO 2 concentrations were 1540 and 180 ppm. Thus, 88% SO 2 in the flue gas was removed. 0 -36-8695 / Example 25

The desulfurization efficiency was measured in the same apparatus and under the same conditions as in Example 24 except that the amount of burnt lime used was varied, i.e. the Ca / S ratio was varied. The results are shown in Fig. 32. The desulfurization rate is generally higher than that measured in the comparative experiments described later. The higher the Ca / S, the higher the desulfurization efficiency. Desulfurization efficiency greater than 70% was achieved in experiments even with Ca / S = 1.0.

Example 26

The desulfurization efficiency was measured in the same apparatus and under the same conditions as in Example 24 except that the amount of sodium silicate used in the preparation of the desulfurizing agent was altered. Fig. 33 shows the dependence of desulfurization efficiency on the amount of sodium silicate used. The 0% added sodium silicate corresponds to the addition of water in a molar amount of 2.5 to the amount of calcined lime. An increase in desulfurization efficiency can be seen with the addition of 0.01%. When adding 10 to 20%, the desulfurization efficiency is maximized. If the amount of sodium silicate is greater than 50%, the desulfurization efficiency is at the same level or lower than the silicate-free reagent. In terms of economical desulphurisation, tests with other types of coal have found that the amount of sodium silicate should be between 1 and 20%. Although the desire to reduce desulfurization efficiency using a higher amount of sodium silicate is not clear, it is believed that the pores already formed are closed off with excess sodium silicate. Fig. 34 shows the dependence of the specific surface area measured by the N2BET method on the amount of sodium silicate. It appears that the specific surface once formed decreases.

Example 27

The desulfurization operation was measured on the same equipment and under the same conditions as in Example 24 except that the limestone -37-8695 was first carbon-free and then cooled and the temperature of the calcined lime to be added to the mixer changed after adding an aqueous calcium silicate solution to the calcined lime. 35 shows the dependence of desulfurization efficiency on warm calcined lime when adding an aqueous solution in calcium silicate. If the calcined lime temperature is less than 100 ° C, the aspiration efficiency tends to decrease somewhat. It is preferred that the sodium silicate solution to be added has a temperature of not less than 100 ° C.

Example 28

The desulfurization efficiency was measured on the same equipment and under the same conditions as in Example 24 using a second coals having different sulfur content. The results are shown in TAB. ^ 7. TAB. 7

Type of coal H I J K L Sulfur content (%) 0.3 0.3 0.8 1.0 3.0 Extraction efficiency (%) 90 91 87 90 84 í. ',

Example 29

The desulphurization activity was measured on the same equipment and under the same conditions as in Example 24, using magnesium carbonate and (MgCO 3) and magnesium-calcium carbonate (CaCO 3. MgCO 3). The results are shown in TAB. 8. TAB. 8

Desulfurizing agent MgCO 3 CaCO 3. MgCO 3 Desulfurization efficiency (%) 82 85

S -38-8695

Comparative Example 7

In the same apparatus as in Comparative Example 1, the aspiration efficiency for coal M is measured under the same conditions as in Example 24. The aspiration efficiency achieved for the various Ca-S aids is shown in FIG. 32. The aspiration efficiency found compared to that obtained in the experiments of this invention is lower.

Comparative Example 8

According to the same procedure as in Comparative Example 7 (but Ca / S = 1.5), the aspiration efficiency was measured in experiments with five types of coal as shown in Example 28. The results are shown in TAB. 9. Compared to the method of the present invention, the desulfurization efficiency is lower for all types of coal. TAB. 9

Type of coal H I J K L Sulfur content (%) 0.3 0.3 0.8 1.0 3.0 Desulfurization efficiency (%) 32 39 36 30 30

J

Comparative Example 9

In the same apparatus as in Comparative Example 1, the aspiration efficiency for coal is controlled under the same conditions as in Example 28. The results are shown in TAB. 10. Compared to the desulfurization efficiency of the present invention, it is apparent that the aspiration efficiency found is lower. TAB. 10

Desulfurizing agent MgCO 3 CaCO 3 .MgCO 3 Desulfurization efficiency (%) 30 32

In contrast to the above examples 17 to 19, where limestone is heated to form burnt lime, it is also possible to use slaked lime to heat it to produce burnt lime. and use this lime. In addition, any suitable clay material may be used if, upon heating or the like, corrosive earth oxide is formed. F

EXAMPLE 30 In this example, the desiccant is heated by mixing the ash from coal and slaked lime. The spray is then sprayed into the flue gas in the duct and the flue gas generated by the combustion of coal in the boiler is desulfurized.

FIG. 36, the flue gas from the boiler 1 is cooled in the air heater 3 and injected into the aspiration column 4. Slaked lime, coal ash, desulfurizing agent particles obtained: in the separator 8, water and sodium silicate are injected into the desulfurizing agent preparation 37 and mixed in a mixer. The missionary can be arbitrary if he can. process. This mixture is a desiccant slurry having a high specific surface area and injected into the duct 13 or into the desiccant column 4 to react with harmful acidic substances such as SO 2 · Current water can be injected into the duct 13 or the desiccant column 4 to it cooled the flue gas and increased the humidity. The desulfurizing agent which has partially reacted is trapped together with the ash in the flue gas in the dust separator 8, and a portion is supplied to the desulfurizing agent manufacturing plant 37. The remaining desulfurizing agent and the coal ash are discharged. The desulfurizing agent preparation plant comprises slaked lime, coal ash, water and sodium silicate. Using this apparatus, the combustion efficiency of coal combustion was measured. An amount of slaked lime was used to make the Ca / S ratio = 1.5. Sodium silicate (water glass) was supplied in an amount of 5 wt. % to the amount of solids in the desulfurizing agent preparation 37. The water was sprayed in an aspirating column in an amount corresponding to 3 weights. % flue gas. The prepared desiccant was fed to the duct 13 via line 22. In the desulfurizer preparation device, the slurry was treated with water to include 30 weights. percent reagent and is heated to 100 ° C; the mean residence time of the particle in this device is 2 hours. The shear rate achieved in the milling apparatus for desulfurizing agent 37 is 10 s. 50% of the particles collected in the particle separator 8 are returned to the desulfurizing agent preparation device 37; the rest is drained. The unreacted desulfurizing agent contained in the particles collected by the dust separator 8 is not counted as a Ca / S value.

The SO 2 concentration was measured in the gas samples from which the water vapor was removed, at the outlet of the boiler 1, 1540 ppm, and at the outlet of the dust separator, 150 ppm. Thus, 90% SO 2 in the flue gas was removed by this procedure. The specific surface of the desiccant prior to desulfurization reaction is 65 m / g. From the fact that the specific surface of slaked lime and ash from coal is a unit or little more than 10 m / g, it can be assumed that the desulfurizing agent maturation procedure described increases its specific surface area.

Example 31

In the same apparatus as in Example 30, desulfurization efficiency is measured under the same conditions as in Example 31. However, the amount of slaked lime (Ca / S) used is varied. The results are expressed by line (a) in FIG. 37. The higher the Ca / S ratio, the higher the desulfurization achieved. Desulphurization efficiency not less than 75% was achieved even with a Ca / S ratio of 1. FIG. 37 shows the desulfurization efficiency that was achieved when only coal ash and water were mixed in a desulfurizing agent preparation (without the use of sodium silicate, line (b)).

When using the apparatus as in Example 30, desulfurization efficiency is measured under the same conditions as in Example 30. However, the mean residence time is varied by varying the retention time in the desulfurizing agent preparation apparatus 37. The desulfurization efficiency dependence on the mean residence time is shown in FIG. 38 by line (a). Sufficient high desulfurization efficiency can be achieved even when the mean residence time is short. Fig. 38 also shows the desulfurization efficiency values when the desulfurizing agent is prepared from coal and water ash which is blended with the addition of a sodium silicate, (b) T " Example 33 ·· * *; Using the apparatus as in Example 30, the aspiration-efficiency is measured under the same conditions as in Example 30. However, the amount of sodium silicate added (relative to the solid particles) is altered. The results are shown in FIG. 39. An increase in desulfurization efficiency is already apparent at the addition of 0.1% solids. In the case of coal M, even if more than 10 weights are added. % no longer increases the aspiration rate. Thus, from an economic point of view, it is advisable to add 0.1 to 10 weights. %. Similar investigations were conducted in experiments with coal grades that differed in sulfur content. It has been found that sodium silicate can advantageously be added in amounts corresponding to 0.1 to 30% by weight based on the amount of solid particles.

Example 34

In the same apparatus as in Example 30, the aspiration efficiency is measured under the same conditions as in Example 30. However, the rotational speed of the mixer stirrer in the desulfurizing agent preparation apparatus 37 is varied and the dependence of the desulfurization efficiency on shear rate is tested. The results are shown in FIG. 40. At high shear rates, dispersion of the slurry is good, and therefore the aspiration efficiency is increased. From the point of view of desulphurisation, good mixing should be ensured at shear rates of not less than 10 s ~.

Example 35

In the same apparatus as in Example 30, the aspiration efficiency is measured under the same conditions as in Example 30 using five types of coal having different sulfur content. The results are presented in TAB. 11

Type of coal H I J K L Sulfur content (%) 0.3 0.3 0.8 1.0 3.0 Desulfurization efficiency (%) 94 95 93 92 88

Example 36

Using the device shown in FIG. 41 shows the desulfurization efficiency in the coal M experiments. In this example, the sodium silicate added is mixed with the water in the viscosity-adjusting reservoir 38 and then fed to the desulfurizer preparation plant 37. The viscosity of the aqueous sodium silicate solution is strong dependent on its concentration. When a high viscosity aqueous solution is supplied to the desulfurizing agent preparation 37, the sodium silicate cannot readily be dissolved in the slurry. Therefore, the concentration of silicate is increased locally and consequently the slaked or burnt lime particles agglomerate and thus the high surface area desulfurizing agent cannot be prepared. To avoid this, sodium silicate is diluted with water in reservoir 38 so that the viscosity of the solution is not greater than 10 Pa.s. It has been found that the above-described problem can be solved by adding the thus treated sodium silicate solution to the desulfurizing agent preparation 37.

Fig. 42 shows the desulfurization efficiency dependence on the sodium silicate viscosity (adjusted by varying the viscosity adjustment ratio in the reservoir 38. The desulfurization conditions are the same as in Example 30). When the viscosity exceeds 10 Pa.s, then the specific surface of the desulfurizing agent gradually increases. Therefore, the viscosity of the sodium silicate solution should not exceed 10 Pa.s.

Example 37

The desulfurization efficiency was measured on the apparatus shown in FIG. 43 with the use of coal M. In this example, a wet mill 39 is used to enter the desulfurizing agent preparation plant 37 and slaked lime, water and sodium silicate are processed in the presence of coal ash. The ground slurry is fed from the mill 39 to a desulfurizing agent preparation device 37 and heated during milling to produce a high specific surface desulfurizing agent. Milling slaked lime and coal ash increases its reactivity so that a desulfurizing agent with high SO2 absorption capacity can be prepared. Under the same conditions as in Example 30, desulfurization efficiency is measured in M and TAB charcoal experiments. 12 shows desulfurization efficiency in the addition, without or without grinding, of sodium silicate. Even under the same conditions, the desulfurization efficiency is enhanced by the addition of sodium silicate. TAB. 12 No sodium silicate 5% sodium silicate No grinding 35% 90% Grinding 58% 96%

The heating mantle around the mill 39 causes the man to mature. run simultaneously with milling in the mill 39 and desulfurizing agent preparation 37 may be omitted. Although in the previous cases the desulfurizing agent is sprayed as a slurry into the duct 13 or desulfurization column 4, the slurry leaving the desulfurization preparation plant 37 can be dried to a powder and sprayed into a duct or desulfurization column 4.

Example 38 In this example shown in FIG. 44, instead of heating the desulfurizing slurry in the desulfurizer preparation apparatus 37 according to Examples 30 to 37, the slaked lime, coal ash, water and sodium silicate are mixed in the mixer 33 and then the slurry is sprayed into the furnace furnace 1 or in the duct 13. Thus, the same ripening effect can be achieved, but in a shorter time. The missionary 35 merely mixes the particles and can be "Afljà" '' ·· > ' less than that used in the apparatus for preparing the desiccant 37 and the mixer 35 may be a pipe mixer. Fig. 45 shows the dependence of the desulfurization efficiency on temperature when the "desulfurizing agent prepared from the same conditions as Example 30 (except for heating) is dispersed into the boiler or into the duct 13. From the point of view of desulfurization efficiency, this temperature should be in the range of 300 to 1000 ® C. At temperatures above 1000eC, the particles of the desiccant are sintered and the reaction between the slaked lime and the coal ash does not occur at temperatures below 300 ° C. We believe that if the operating conditions are outside this range, the aspiration efficiency is reduced for these reasons.

Comparative Example 10

According to the same procedure as in Comparative Example 1 (but Ca / S = 1.5), the aspiration efficiency was measured in the five types of charcoal experiments shown in Example 35. The results are shown in TAB. 13. In comparison with the examples of the present invention, the desulfurization efficiency in the comparative experiments is lower in all cases. TAB. 13

Type of coal H I J K L Sulfur content (%) 0.3 0.3 0.8 1.0 3.0 Extraction efficiency (%) 40 47 44 39 32

In the above examples 30 to 38, although slaked lime was used as a corrosive earth metal compound and coal ash as a siliceous substance, limestone, calcium sulfate and calcium sulfate can be used as metal compounds " caustic soils and coal ash, quartz sand , bentonite or kaolin as siliceous substances. Of course, two or more compounds may be used in combination. Further, although waterglass (JIS Nb.l) was used, another type of sodium silicate may be used.

Although in the above examples 1 to 38, lime, burnt lime, magnesium carbonate or carbonate 5s # * * * v " The alkali metal or caustic earth metal hydroxide or carbonate such as sodium hydroxide and sodium carbonate can be used as the desulfurizing agent. In the present invention, f. + < ·, · ?, oxide, '• r' x ': · »'. • / - - with *;: - w- · ;. In order to achieve a higher suction efficiency compared to a conventional aircraft, the suction device can be smaller as well as a smaller amount of desiccant used. The desiccating efficiency is increased due to the location of high humidity areas. including i;: ·· / »'. i- · · * - «.» · '; · ;; ú · /

rSfr; ·. ··: V;

A'f ‘í ·· 1 * " 1 · · ·

[2] The unreacted desiccant is trapped by a dust separator and is again sprayed into the flue gas at 500 to 900 ° C, resulting in a dehydration reaction (Ca (0H) 2 - > CaO + H 2 O) and destruction of the calcium sulphate / sulphate shell so contact of the desulfurizing agent and SO 2 with. improved, which will increase the desulfurization efficiency.

[3] A portion of the flue gas or heated air is fed to the bottom of the fumigation column. Thus, even when the relative humidity inside the desiccant column is high, it is possible to prevent condensation at the bottom of the desiccant column and to deposit the desiccant on the walls. Also, the moisture of the settling agent is reduced, and its fluidity is improved. As a result, the lower part of the aspiration column will not be closed or blocked and therefore the settled desulfurizing agent may be smoothly removed from the aspiration column and thus the aspiration efficiency can be maintained at a high level.

[4] The temperature at the spot directly dropped / sprayed is measured. and the amount of spray water supplied: is controlled at this temperature. Thus, the temperature at the outlet of the aspiration column is maintained at a level above the condensation point 41 'of water. This prevents condensation of water and deposits due to this condensation. Therefore, it is possible to maintain a high relative humidity inside the desalinating column. Thus, the aspiration efficiency is increased and the aspiration column can operate for a long time and the device can be designed compact.

V V · -46- - '· I. 8695 · · Λ V *: -.-. in; ú5 ') The siliceous substance is mixed with at least one of the alkali metal or caustic earth metals and water is added to the mixture. As a result, the two substances are reacted and the reaction heat released by the hydration of the oxide removes excess water. In this way, a high surface area desiccant is prepared. Therefore, high aspiration efficiency can be achieved. [6] Sodium silicate is added to the desiccant containing calcium-containing particles so that the dispersibility of the calcium-containing or siliceous particles in the water is increased. As a result, their reactivity to one another is increased and the desulfurizing agent having a higher desulfurization efficiency can be prepared more economically (at lower temperatures and in less time). Even if the Ca / S ratio is small, and when the mean particle retention time of the slurry is high, high aspiration efficiency can be achieved.

[7] Sodium silicate dispersibility, calcium and silicon-containing substances in water are further enhanced by heating. Furthermore, the dispersibility of calcium-containing and silica-containing substances is further enhanced by the fact that the slurry is vigorously mixed in a high-shear or wet milling mixer.

Claims (1)

- 1 - HD cj 1 * > i o f - • < = > c < o sgd CT > < P? 3 i cn · Ού. 5 > m [to & N o < K} Method of Dry Type Desulphurisation of Gaseous Spiins in Y So t. i m on - .w -, - in .....- in - - -. In that the desulfurizing agent is sprayed, the compound of the invention comprises one compound from the group consisting of one or more meshes of the metal and alkaline earth metal in the combustion chamber. in the flue gas range, and together with the ash, the dust deterioration and / or the dust, and / or the dust, respectively, are allowed to occur. introduces into the flue gas duct ΐ; with a temperature of 500 to 900 ° C. X · Τ'Ίϊ y '. A method as claimed in claim 1, characterized in that C is added to the portions encased in the dust separator. ; · '". and the resulting slurry is then fed to a portion of the duct, in the liquid state. 'T' '' " Which is a temperature between 500 and 900 ° C. characterized in that water, added in the dust separator, is added to the container. The slurry is sprayed into a slurry portion of the slurry and the slurry is sprayed into a slurry containing a temperature of 500-900 microns. If a desulfurizing agent is used, a different extinguishing agent is prepared to form one or more alkali metal oxides of the alkali metal oxide. adding water which is formed from the product formed by the hydration heat of the alkaline earth metal oxide according to claim 1, characterized in that the silicon dioxide is present in the silicon dioxide. the alkaline solution is added to the substance and the alkaline metal oxide. The process according to claim 4 and 5, wherein the siliceous substance is at least one layer. and a substance, from a set of charcoal, siliceous sand, bentonite, and kaolinite. and · ιηβ 1 o u in ml n. the alkaline earth metal oxide and the siliceous substance of the method of claim 4, characterized by e: 2e; ee sets the dehydration temperature to 80 to 130 ° c. A method as claimed in claim 4 or 5, characterized in that the method is in accordance with the present invention. that ee sodium silicate as a siliceous substance, the difference τ '" in water, with alkaline earth metal oxide. (10V) In the case of both of the claims 9, 3 ', ", " · S 9 dissolved in an alkaline earth metal carbonate heated and mixed with an aqueous solution of sodium oxide and then added with an aqueous solution of sodium silicate for temperature jRafefr ** '&!' '* * *' i *? v # ** i; ne ž íoo; c. '•' • i '·?' '^ iJ *!'? '· The process according to claim 9, wherein the sodium silicate is present in an amount by weight of < RTI ID = 0.0 > < / RTI > 0.01 to 50 sec, calculated on the amount of oxide effluent Slft. for dry type desulphurisation of the gaseous combustion gases according to claims 1 to 11, characterized in that the apparatus (5) for supplying the desulphurizing agent is a furnace Ováni ^ Λ'ΠίίΛβρβ 1 ions of fossil fuels contain sulfur compounds and / or 1 ® ® into the flue gas (13) through which the flue gas flows contain oxides; From the desulfurization of the column (4), the flue gas stream from the apparatus (21) for dispersing the water in the separating column (4) is disposed of from the dispersing means (16). ) disposing the flue gas flue gas in the desulfurization column (4) and the flue gas. * 8 $ * »l · 'r. Apparatus as claimed in claim 12, characterized in the water spraying device (21) comprises a spray nozzle (12) located at a distance of from 1 to 5 m from the inlet to the column (4) which is deposited on the column the output side '' '' '' '' '' '' '' '' '' 4 ''. · · · · · · · · · · · · · · · · · · · · · · ·. ft «r. Eni ‘nároku nároku eni eni eni eni eni eni eni eni eni eni eni eni eni eni eni eni eni eni eni " iWki wU j · * :: ·: ** ···, - ·. that the water spraying device (21) comprises water spray nozzles and water dispersion fibers (16) located in the water flow direction from the nozzles (12). '·. ·'; Apparatus according to claim 14, characterized in u j i c s s e - '.-fV · :. that the dispersing members (16) are located on the periphery of the periphery wk ' 'IN'''·· .- . . . · ÄJi'j®, *, /. ____, /. «N \ t w, j tŕyeek, - (12). · to spray water 4.f., k, ..v • 7Γ1 T íu'’r * > Apparatus according to claim 12, characterized in that the device (21) for spraying water has two groups of "5" in which the nozzles (12) are provided. they are mounted opposite to each other in the interior of the column (4). from the claims of any one of claims 12 to 15, yvg / yvz. It has a heat exchanger. ir ^ (" ä. "); it comprises a low flow rate into the heat exchanger column (4) for heating the desulfurized flue gas from the effluent column (4). A device for a dry-type desulphurisation process for flue gas desulfurization plants. The compositions of claim 1, wherein the desulfurizing agent in the furnace according to claims 1 to 11 has become effective. y z n a u j i c i. The 'desulphurisation column (4) is located. current direction τχ ::: r- v. The melt is dispersed inside the column (4) by means of a sprayer. In order to spray the water, the device has separators having a moisture-absorbing agent, and the reacted desulfurizing agent and the traction of the heated medium for the lower part of the desulfurization column is according to claim 20 or 21; It is also desirable to have columns in the lower part (4). is a . located injected includes the same. media, network > - ‘· - 1 ·; '- · ν ·; · W? : vvt / í · m '; ® ^ Hho & temperature sensor and regulator ..v ···········································! a dry-type desulphurisation process according to claims 1 to 11, consisting of a nebulizer, a desulfurization agent, an agent in the furnace and / or a flue gas duct, in the form of a flue gas desulfurization agent; .j í -; i. WMW; -ΛΜ '; * f y; ≫ ·· 4 £ $, 1 * «'« *; ··, · ν < . · / '/ · “·”? -ν 'Äiià'M: · l ^ vW ^ / V V ** 1 *' * J in * ^ ***! - 's! ·· IN; ≪ > * VM V · '*: " ''. · '' · '' '· 1' '· · 1 · · 1 · · 1 · 1 · 1 · · 1 · · 1 · 1 · 1 · · 1 · · 1 · 1 ) for spraying water in the desulfurization and temperature measuring devices in a knife onto the sprayed water and water control devices * the ground temperature of the knife falls on the droplets of sprayed water. 1¾ Γ ^ ΛΤ ·· 1 '! * ≫'?; Γν '' 'S5 ·' 1 V; & 1 & Y. '-. For the dry type of desulphurization of the gaseous combustion plants, the process has been carried out. «r ... > > · '» «· /; A method according to any one of claims 1 to 11, characterized in that it has a casting of sodium silicate to form a suspension comprising an alkaline earth metal compound and a siliceous substance and water. ≫ Vf. colony (4) crystals; until a powder is formed and a powder is injected into the furnace combustion apparatus (1) and / or the powder, <, " 1 in * 77 " " 7 $ $ j 7 Ä W 7 ď 7 7 7 7 7 7 7 7 7 7 7 7 22 22 22 22 22 22 22 22 22 22 22 The dry gas desulphurisation apparatus of claim 1, wherein the flue gas from the furnace (1) is discharged from the furnace (1). for the addition of the sodium silicate to the suspension containing the alkaline earth metal compound and the siliceous substance and water, or a spray suspension to the furnace (i) / phiH furnace to the flue gas duct (13) through which the flue gas from the furnace is de-lysed (λ). yt '·. *. >.,'; Coming for the belt q b of the dry type desulphurisation of gaseous gases 'nWW' 'S1' '' / ‘r 'fl * | V'. D, d, d, d, d, d, d, d, d, d, d, d, d, d, d, d, d, d i d i d i c i s i t i m i. that it has a sodium silicate to be added to the slurry containing the sodium silicate; the alkaline earth metal and the siliceous substance and the water, and to produce a powder coating obtained by drying the slurry into the furnace (1) and / or into the duct (13), the duct from the furnace (1). i /.- i: · · · · · · · · · · · · · · · · · · · · · · · * :. : »To. 'V'i, ·· »/. · ·' /. ./Λ·α&gt ;; *. . ----Ásásás ^ * * x x'..---V--------------------------------------------------------------------------------- .í '/ VJm.t ‘A- .u ./wc í: Λ- ·. · 'I * r i' ; . · Μ &$; $ Μ% $ ϊ7 $ ν, 'ľ. 'In -'? * £ 5 '> * ·. * ·! . 1¾¾¾ ¾%. :. ^ * Γ ·, ',. k: gt; í í. } / "Vt