KR20230068545A - Fluidized bed boiler hydrogen chloride generation reducing agent using oyster shell, method for reducing hydrogen chloride generation in fluidized bed boiler furnace using the same and binder composition using the combustion residues - Google Patents

Abstract

The present invention relates to a hydrogen chloride generation reduction agent for a fluidized bed boiler using oyster shell, a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace using the same, and a binder composition using combustion residues. According to the present invention, oyster shell powder acquired through drying and grinding of discarded shells without separate washing and firing processes is used as a hydrogen chloride generation reduction agent for a fluidized bed boiler and the hydrogen chloride generation reduction agent containing the oyster shell powder is introduced into a fluidized bed boiler furnace to be mixed with solid fuel for combustion to reduce hydrogen chloride generation in the fluidized bed boiler furnace in a dry form, so that a method for reducing hydrogen chloride gas emissions by spraying liquid slaked lime and the like in a downstream process, which is performed to reduce atmospheric emissions of hydrogen chloride (HCl) gas generated after combustion in a conventional fluidized bed boiler using solid fuel, can be replaced, thereby implementing effects of a reduction in processing costs of oyster shells and a reduction in operation costs of the fluidized bed boiler.

Description

Fluidized bed boiler hydrogen chloride reduction agent using oyster shell, method for reducing chlorine generation in fluidized bed boiler furnace using the same, and binder composition using the combustion residue FLUIDIZED BED BOILER FURNACE USING THE SAME AND BINDER COMPOSITION USING THE COMBUSTION RESIDUES}

The present invention relates to an agent for reducing hydrogen chloride generation in a fluidized bed boiler using oyster shells, a method for reducing generation of hydrogen chloride in a fluidized bed boiler furnace using the same, and a binder composition using the combustion residue, and more particularly, in a case where recycling is insufficient due to a complicated pretreatment process. The oyster shell powder obtained through the drying and crushing process of the discarded shells as they are without the separate washing and firing process is used as a hydrogen chloride generation reducer for the fluidized bed boiler, and the hydrogen chloride generation reducer including the oyster shell powder is used as a solid fuel. It relates to a binder composition that reduces the generation of hydrogen chloride in a fluidized bed boiler furnace in a dry form by mixing and burning after being put into a fluidized bed boiler furnace to be used, and utilizing combustion residues remaining after the combustion.

Shells are the shells of shellfish, and when shellfish are shipped, most of the shellfish are removed and only the contents are distributed, and shells are generated in large quantities as waste in the vicinity of shellfish collection points, etc., and are stored on the coast to pollute the coast. and causes a number of environmental problems.

Currently, it is known that 360,000 tons of oyster shells are generated annually on the coast of Korea, and in particular, shells are often generated according to oyster farming. Of these, only 10% is reused as calcium fertilizer and the rest is left on the coast, so the need for mass processing of marine waste such as oyster shells is emerging.

The chemical composition of the shell usually consists of more than 90% by weight of CaCO ₃ , and the remaining trace amounts are composed of inorganic materials such as SiO ₂ , MgO, Al ₂ O ₃ , Na ₂ O, and SO ₃ .

However, some of the organic matter and salts remaining during shellfish desorption are present in the shell, and when the shell is left unattended for a long time, problems such as odor and farm contamination due to organic matter decay and leachate generation occur.

Accordingly, various technologies for recycling shells are being developed. Among them, Patent Document 1 includes the steps of washing oyster shells to remove salt; Grinding the desalted oyster shells; A classification step of powdering the pulverized oyster shells to a predetermined particle size; A sintering step of generating quicklime (calcium oxide) by burning oyster shell powder at a temperature of 600 to 900 ° C to remove carbon dioxide; A mixing step of mixing 40 to 60 parts by weight of quicklime, 4 to 20 parts by weight of fly ash, 5 to 20 parts by weight of gypsum, and 40 to 60 parts by weight of blast furnace slag in a mixing ratio; has been

Patent Document 2 is an invention related to an inorganic coagulant containing waste gypsum, starfish powder, shell powder and clay mineral, waste gypsum powder 50 to 200 parts by weight, starfish powder 50 to 200 parts by weight, shellfish powder 50 to 100 parts by weight and 30 to 70 parts by weight of clay minerals. It provides an inorganic coagulant composition for wastewater treatment, and suggests applicability as an inorganic coagulant composition for food wastewater treatment, livestock manure wastewater treatment, and river wastewater treatment.

Patent Document 3 relates to a method for producing waste recycled feed, which includes first firing at a temperature of 1,300 to 1,500 ° C. for 20 to 30 minutes by inputting raw materials such as shellfish washed with water into a firing furnace; Putting the firstly calcined raw material into a grinder and pulverizing it; Separating the pulverized raw material powder by introducing it into a separator; Injecting the separated pulverized powder into a granular molding machine and molding it into granules using hot water as a binder; Putting the molded granular feed into the firing furnace and secondarily firing it at a temperature of 900 to 1000 ° C. for 10 to 20 minutes; After cooling the secondly calcined granular feed, reintroducing it into the calcining furnace and repeating the third calcining at a temperature of 900 to 1,000 ° C. for 10 to 20 minutes; and a step of sifting the granular feed that has been calcined for the third time by introducing it into a vibrating body.

In addition, Patent Document 4 includes the steps of heat-treating oyster shells, preparing slurry by grinding the heat-treated oyster shells, wet desulfurization by reacting the slurry with exhaust gas, and recovering precipitated desulfurized gypsum during wet desulfurization. In the heat treatment step, the oyster shells are heat-treated at 800 to 1,500 ° C. for 0.25 to 10 hours, and the waste shells are used for wet desulfurization to produce high-quality desulfurized gypsum.

Patent Document 5 proposes a shell crushing system for producing a new flue gas desulfurization raw material and a method for producing high-quality desulfurized gypsum using the same. (70 to 100 minutes at 500 to 800 ° C.) by reacting the powder with the exhaust gas to perform wet desulfurization and to recover the precipitated desulfurized gypsum during wet desulfurization, which pulverizes the shells more evenly to obtain high quality It is reported that shell powder can be provided.

As described above, various technologies for recycling shells are being developed. However, in order to recycle shells, technologies for pre-processing shells and technologies that can be produced at a lower cost than products currently used in the field are required. The cost of recycling is excessive compared to the cost of shell treatment, and the final product is economically unfavorable compared to existing products, so it is not currently commercialized.

In particular, Patent Document 4 and Patent Document 5 use shells as a boiler desulfurization agent and are used as a boiler hydrogen sulfide generation reduction agent, but the prior art is a wet desulfurization agent for a pulverized coal boiler (Pulverized Combustion) of a thermal power plant equipped with a separate desulfurization device Since it is used as a raw material, the limestone (CaCO ₃ ) component is converted to the quicklime (CaO) component through the process of washing, drying, crushing, and firing, and then mixed with water again to prepare a slurry. Because of this method, there is a problem in that the process cost is excessive.

On the other hand, in general, in a fluidized bed boiler that burns only coal 100%, hydrogen chloride gas, which is a toxic gas, is not generated, but in a fluidized bed boiler using general solid fuel and bio solid fuel, a large amount of hydrogen chloride gas is generated, and its removal is essential.

In most cases, the method of removing hydrogen chloride gas by spraying liquid slaked lime in the post-combustion process is the most commonly used method. When solid fuel containing waste synthetic resin or waste wood is burned, a large amount of hydrogen chloride gas is generated, resulting in the highest allowable emission concentration. In order to maintain phosphorus below 0.3%, liquid slaked lime is excessively sprayed. For this reason, the use of a large amount of expensive liquid slaked lime increases the operating cost of the boiler and the final remaining combustion residue is discharged in a lump form due to the moisture of the liquid slaked lime, resulting in problems such as difficult recycling.

Accordingly, the present inventors have tried to solve the conventional problems, and as a result, the discarded oyster shells, which were insufficiently recycled due to the complicated pretreatment process, were dried and pulverized to pulverized oyster shell powder having appropriate organic matter content, moisture content, and salt content. It was confirmed that hydrogen chloride gas generation can be drastically reduced from the combustion stage by mixing and burning after being put into a fluidized bed boiler furnace using solid fuel, and the oyster shell powder can be used as a hydrogen chloride reduction agent inside the fluidized bed boiler The present invention was completed by confirming the effect of reducing the operating cost of the fluidized bed boiler by omitting the pretreatment process because the oyster shells containing the components are directly injected together with the fuel.

Republic of Korea Patent No. 0464666 (2005.01.03 announcement) Korean Patent No. 1169563 (published on July 27, 2012) Republic of Korea Patent No. 0993223 (2010.11.09 announcement) Korean Patent No. 1753823 (Announced on July 5, 2017) Republic of Korea Patent No. 2109756 (Announced on May 26, 2020)

An object of the present invention is to provide an agent for reducing hydrogen chloride generation in a fluidized bed boiler, including oyster shell powder containing organic matter and chlorine components, through drying and grinding the discarded shells as they are in a state in which a separate washing and firing process is omitted. .

Another object of the present invention is to provide a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace in which oyster shell powder is put into the furnace of a fluidized bed boiler using solid fuel, mixed and burned, and carried out in a dry form.

Another object of the present invention is to provide a binder composition utilizing combustion residues obtained from the method for reducing hydrogen chloride generation in the fluidized bed boiler furnace.

In order to achieve the above object, the present invention provides a fluidized bed boiler hydrogen chloride generation reducer using oyster shell powder pulverized to a calcium carbonate component of 90% or more and a particle size of 5 mm or less.

The fluidized bed boiler hydrogen chloride generation reducer of the present invention may further include 5 to 1,000 parts by weight of limestone powder based on 100 parts by weight of the oyster shell powder.

The oyster shell powder preferably has an organic content of 0.1 to 10% by weight, and preferably has a water content of 0.01 to 5% by weight.

In addition, the oyster shell powder preferably has a salt content of 0.01 to 3% by weight.

In the method for reducing hydrogen chloride generation in a fluidized bed boiler furnace according to the present invention, the hydrogen chloride generation reducing agent and solid fuel are introduced into the furnace of a fluidized bed boiler, and then mixed and burned to reduce hydrogen chloride generation in a dry form, and the fluidized bed boiler hydrogen chloride generation reduction agent With respect to 100 parts by weight, it is preferable to add 100 to 2,000 parts by weight of the solid fuel.

The solid fuel may use any one or a mixture of two or more selected from general solid fuel (SRF, Solid Refuse Fuel) and bio solid fuel (BIO-SRF, Biomass-Solid Refuse Fuel).

In addition, the present invention provides a binder composition including combustion residues remaining after mixing and burning a hydrogen chloride reducing agent and a solid fuel in a fluidized bed boiler through a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace. At this time, the combustion residue has a CaO content of 10 to 50% by weight and a Cl ^- content in the range of 0.5 to 25% by weight.

The binder composition of the present invention may further include 10 to 4,000 parts by weight of cement based on 100 parts by weight of the combustion residue, and may further include 10 to 4,000 parts by weight of slag based on 100 parts by weight of the combustion residue.

According to the present invention, in the present invention, discarded shells are dried and pulverized oyster shell powder, which has undergone only a crushing process, is put into a fluidized bed boiler furnace to reduce the generation of hydrogen chloride. By confirming the effect, it can be used as a hydrogen chloride generation reducing agent for a fluidized bed boiler using pulverized oyster shells.

In addition, the fluidized bed boiler hydrogen chloride generation reducer using the pulverized oyster shells of the present invention is put into the fluidized bed boiler furnace and mixed with solid fuel for combustion to reduce hydrogen chloride generation in the fluidized bed boiler furnace in a dry form, thereby reducing the generation of hydrogen chloride in the fluidized bed boiler using conventional solid fuel In order to reduce the air emission of hydrogen chloride (HCl) gas generated after combustion in the post-process, it is possible to replace the method of reducing hydrogen chloride gas emission by spraying liquid slaked lime, etc.

Therefore, it is possible to reduce the operating cost of the fluidized bed boiler, and there is an effect of recycling a large amount of oyster shells.

1 is a schematic diagram of an apparatus for measuring the amount of hydrogen chloride gas generated by mixing and burning oyster shells and solid fuel according to the method for reducing hydrogen chloride generation in a fluidized bed boiler furnace of the present invention;
FIG. 2 is an exterior photograph of the actually built device of FIG. 1 .

Hereinafter, the present invention will be described in detail.

The present invention provides a fluidized bed boiler hydrogen chloride reducing agent containing oyster shell powder pulverized to a particle size of 5 mm or less and having a calcium carbonate component of 90% or less.

The present invention can be used as a hydrogen chloride generation reducer for a fluidized bed boiler through only drying and grinding processes without separate washing and firing pretreatment processes.

This is because solid fuel containing a large amount of chlorine is used as the fuel for the fluidized bed boiler, so even if some chlorine is present in the oyster shell, which is a hydrogen chloride reducing agent, it does not cause boiler operation problems, and organic matter is completely burned together with the fuel inside the boiler. Because.

Therefore, oyster shells, which are used as a hydrogen chloride gas reduction agent for fluidized bed boilers using solid fuel, can be used without separating the coated yarn, washing or firing even if it contains a large amount of salt or organic matter, or contains some water and plastic coated yarn for oyster farming. There are advantages to being able to.

Therefore, the oyster shell powder of the present invention may have an organic content of 0.1 to 10% by weight, a water content of 0.01 to 5% by weight and a salt content of 0.01 to 3% by weight.

The principle of hydrogen chloride reduction by mixed combustion of solid fuel and oyster shells in a fluidized bed boiler is that oyster shells, whose main component is calcium carbonate (CaCO ₃ ), are decarboxylated (CaO + CO ₂ ) at a temperature of about 800 ° C and converted to CaO components. The transferred CaO component reacts directly with the hydrogen chloride (HCl) component generated during solid fuel combustion in the furnace to be converted to calcium chloride component and contained in the combustion residue.

Equation 1) CaO + 2HCl → CaCl ₂ + H ₂ O

Therefore, in the oyster shell used as a hydrogen chloride generation reducer for a fluidized bed boiler of the present invention, it is preferable that the calcium carbonate component is 90% or more and the particle diameter is 5 mm or less.

More preferably, the grain size of the oyster shell is 0.005 to 5 mm. At this time, if the oyster shell is crushed to less than 0.005mm, the hydrogen chloride reduction efficiency is improved, but the grinding cost is excessively increased, and the oyster shell is not pulverized, whereas if the oyster shell is used in the form of coarse grains exceeding 5mm, the hydrogen chloride reduction reaction inside the boiler The longer the time, the lower the efficiency.

The fluidized bed boiler hydrogen chloride generation reducer of the present invention preferably further includes 5 to 1,000 parts by weight of limestone powder based on 100 parts by weight of the oyster shell powder. It is preferable to use it when the supply itself of the hydrogen chloride generation reducing agent using is unstable or the cost is excessive due to long-distance transportation.

The limestone powder may have a particle size of 5 mm or less and a purity of 80% or more and are generally distributed on the market.

When the limestone powder is less than 5 parts by weight relative to 100 parts by weight of the oyster shell powder, the effect is insignificant, and when it exceeds 1,000 parts by weight, the oyster shell mixing ratio is relatively reduced, greatly reducing the recycling rate of the oyster shell.

The fluidized bed boiler hydrogen chloride generation reducer of the present invention is generated in large quantities as a by-product in marine aquaculture in the case of shellfish shells, and is stored on the coast to pollute coastal fisheries and cause various environmental problems such as making management of public waters difficult, Since oysters produce the most shells among shellfish, the biggest problem has been pointed out in the coastal environment of the south and west coasts.

In addition, in the present invention, the discarded shells are dried and crushed to utilize the crushed oyster shells, which are insufficiently utilized due to the complicated pretreatment process of washing and firing the shells.

In addition, the shell is made into a hydrogen chloride gas reducing agent through a simple pretreatment process without separate washing and firing processes, and is mixed with solid fuel and burned inside the fluidized bed boiler to remove hydrogen chloride (HCl) generated during fuel combustion and at the same time In addition to reducing the cost of processing and purchasing expensive liquid slaked lime, various effects such as resource saving through waste recycling and prevention of coastal environment pollution can be expected.

The present invention provides a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace in which 100 to 2,000 parts by weight of solid fuel is put into the furnace of a fluidized bed boiler and then mixed and burned in a dry form with respect to 100 parts by weight of the fluidized bed boiler hydrogen chloride generation reducing agent including oyster shell powder. do.

It is preferable to input 100 to 2,000 parts by weight of solid fuel with respect to 100 parts by weight of the fluidized bed boiler hydrogen chloride generation reducer. At this time, if it is less than 100 parts by weight, the power generation efficiency is rapidly reduced due to the lack of fuel component and the amount of heat generated is low.

The solid fuel is preferably any one selected from general solid fuel (SRF, Solid Refuse Fuel) and bio-solid fuel (BIO-SRF, Biomass-Solid Refuse Fuel), or a mixture of two or more.

1 is a schematic diagram of an apparatus for measuring the amount of hydrogen chloride gas generated by mixing and burning oyster shells and solid fuel according to the method for reducing hydrogen chloride generation in a fluidized bed boiler furnace of the present invention, and FIG. 2 is an external photograph of the actually constructed apparatus of FIG.

As a result of measuring the amount of hydrogen chloride gas generated from the device, as a result of measuring the exhaust gas of the combustion residue after mixing and burning 70% by weight of wood chip solid fuel and 30% by weight of oyster shell powder in an electric furnace as solid fuel, oyster shell powder was used without mixing The reduction result can be confirmed by reducing the hydrogen chloride concentration to 1/15 level compared to the case.

In addition, as solid fuel, 70% by weight of wood chip solid fuel and 30% by weight of oyster shell powder were mixed and burned in an electric furnace, and the CaO content of the combustion residue increased about 2 times and the free-CaO content increased about 8 times. By this, it can be confirmed that some of the oyster shell powder reacts with hydrogen chloride and exists as a pure quicklime (CaO) component.

According to the method for reducing hydrogen chloride generation in the fluidized bed boiler furnace of the present invention, the oyster shell powder of the present invention is introduced into the existing fluidized bed boiler furnace and directly mixed and burned the oyster shells and solid fuel to significantly reduce the generation of hydrogen chloride gas from the combustion stage. By confirming, since the oyster shells are useful as a hydrogen chloride reducing agent inside the fluidized bed boiler, and the oyster shells containing organic matter and chlorine are directly injected together with the fuel, the pretreatment process is omitted, thereby reducing the process cost.

Furthermore, the present invention provides a binder composition including combustion residues remaining after mixing and burning a hydrogen chloride reducing agent and a solid fuel in a fluidized bed boiler through a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace.

The combustion residue remaining in the fluidized bed boiler by the hydrogen chloride generation reduction method has a CaO content of 10 to 50% by weight and a Cl ^- content in the range of 0.5 to 25% by weight. This is because the limestone component of oyster shells is deoxidized and reacts with hydrogen chloride to be present in the form of CaCl ₂ or some quicklime (CaO).

When the combustion residue is used together with cement and slag, strength can be further greatly improved.

Therefore, the binder composition of the present invention may further include 10 to 4,000 parts by weight of cement based on 100 parts by weight of the combustion residue.

The cement is preferably any one of general Portland cement, early-strength Portland cement, semi- early-strength cement, blast furnace slag cement, and fly ash cement, or a mixture of two or more. When the amount of the cement is less than 10 parts by weight, the effect is insignificant, and when it exceeds 4,000 parts by weight, the strength is greatly improved, but the amount of combustion residues is relatively reduced and the cost is excessively increased.

In addition, the binder composition of the present invention may further include 10 to 4,000 parts by weight of slag based on 100 parts by weight of the combustion residue.

The slag is in the form of fine powder or dust selected from the group consisting of blast furnace slag, converter and electric furnace reduction slag, converter and electric furnace oxidation slag, ferronickel slag, ladle slag, KR slag, coal gasification composite slag, stainless slag, and lead slag Any one or a mixture of two or more is preferred.

The slag is stimulated and accelerated by the components of CaO and CaCl ₂ of the combustion residue to destroy the amorphous state and cause a hydration reaction so that it can be hardened. When the slag is less than 10 parts by weight, the effect is insignificant. Conversely, when the amount exceeds 4,000 parts by weight, the amount of combustion residues is relatively greatly reduced, resulting in a large amount of slag that has not reacted due to lack of stimulant and accelerator components, so that the strength is rather large. It is lowered.

As described above, the combustion residue generated after the hydrogen chloride generation reduction process of the fluidized bed boiler according to the present invention has a high chlorine content, so it cannot be used for ready-mixed concrete used with reinforcing bars, but it is useful as a binder at various construction sites such as unreinforced concrete or soft ground reinforcement. is high

Preferred examples and comparative examples of the present invention will be described below. In addition, the following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the present invention.

<Comparative example>

After burning 100% of wood chip solid fuel as fuel at 850 °C in an electric furnace, exhaust gas was measured and combustion residues were analyzed.

<Example>

As fuel, 70% by weight of wood chip solid fuel and 30% by weight of oyster shell powder were burned in an electric furnace at 850 ° C., and then exhaust gas was measured and combustion residues were analyzed.

The oyster shell powder was obtained through a crushing process by drying the discarded oyster shells as they were, and the crushed oyster shells contained 92.3% by weight of calcium carbonate component and had an average particle diameter of 430 μm.

<Experimental Example 1> Exhaust gas measurement

As a result of measuring the exhaust gas after burning 100% of the wood chip solid fuel as the comparative example, the hydrogen chloride concentration was 4,923 ppm, exceeding the maximum allowable concentration of 3,000 ppm.

On the other hand, in the case of the examples, the hydrogen chloride concentration was measured at 312 ppm, reduced to about 1/15 level compared to the comparative example, and could be maintained at about 1/10 level of the highest allowable concentration of 3,000 ppm.

<Experimental Example 2> Analysis of combustion residues

Table 1 below shows the chemical composition and Free-CaO content of the combustion residues generated after combustion in the Comparative Examples and Examples.

From the results of Table 1, in the case of the combustion residues generated in the comparative example, the CaO component content was about 18%, and the Cl ^- component content was about 5%, but in the case of the combustion residues generated in the examples, the CaO component content was about 35%. It was confirmed that the % was increased by about 2 times, and the Cl ^- component content was increased by about 3 times to about 15%.

The above results mean that the oyster shell powder reacts with the hydrogen chloride component generated during the combustion of wood chip solid fuel and is fixed to the combustion residue without discharging hydrogen chloride gas into the atmosphere. In other words, it is interpreted that the hydrogen chloride generated during the combustion of wood chip solid fuel and the oyster shell powder caused a chemical reaction.

In addition, by confirming the result that the Free-CaO content increased by about 8 times in the Example compared to the Comparative Example, it was confirmed that some of the oyster shell powder reacted with hydrogen chloride to exist as a pure quicklime (CaO) component.

<Experimental Example 3> Measurement of compressive strength as a binder of combustion residues

In order to evaluate the usability of the combustion residues according to the Comparative Examples and Examples as a binder, the compressive strength was measured, and the results are shown in Table 2 below. The water binder ratio was 68% and was produced in the form of a paste.

From the results in Table 2, the compressive strength of the example in which the oyster shell fine powder was mixed and burned was greatly increased compared to the comparative example in which only wood chip solid fuel was burned 100%. From the above results, it is determined that the free-CaO and CaCl ₂ content is higher, and the self-hardening property is stronger.

In particular, when the content of high Free-CaO and CaCl ₂ is high, it is very effective in accelerating the hydration reaction of cement and activating latent hydraulic properties of blast furnace slag to hydrate it, so it can be confirmed that it shows higher strength at all ages.

Although the present invention has been described in detail only with respect to the specific embodiments described above, it is obvious to those skilled in the art that various changes and modifications are possible within the scope of the technical idea of the present invention, and it is natural that such changes and modifications fall within the scope of the appended claims.

Claims (10)

A fluidized bed boiler hydrogen chloride reducing agent containing oyster shell powder with a calcium carbonate component of 90% or more and a particle size of 5 mm or less. The fluidized bed boiler hydrogen chloride generation reducer according to claim 1, further comprising 5 to 1,000 parts by weight of limestone powder based on 100 parts by weight of the oyster shell powder. The fluidized bed boiler hydrogen chloride reducing agent according to claim 1, wherein the oyster shell powder contains 0.1 to 10% by weight of organic matter. The fluidized bed boiler hydrogen chloride reducing agent according to claim 1, wherein the oyster shell powder contains a water content of 0.01 to 5% by weight. The fluidized bed boiler hydrogen chloride reducing agent according to claim 1, wherein the oyster shell powder contains 0.01 to 3% by weight of salt. With respect to 100 parts by weight of the fluidized bed boiler hydrogen chloride generation reducer according to any one of claims 1 to 5, 100 to 2,000 parts by weight of solid fuel is put into the furnace of the fluidized bed boiler and then mixed and burned in a fluidized bed boiler furnace performed in a dry form. Hydrogen chloride reduction method. The fluidized bed boiler according to claim 6, wherein the solid fuel is any one selected from general solid fuel (SRF, Solid Refuse Fuel) and bio-solid fuel (BIO-SRF, Biomass-Solid Refuse Fuel) or a mixture of two or more Hydrogen chloride reduction method. A binder composition including the hydrogen chloride generation reducer according to any one of claims 1 to 5 and combustion residues remaining after mixed combustion with solid fuel in a fluidized bed boiler furnace,
A binder composition, characterized in that the combustion residue contains 10 to 50% by weight of CaO and 0.5 to 25% by weight of Cl ⁻ content. The binder composition according to claim 8, further comprising 10 to 4,000 parts by weight of cement based on 100 parts by weight of the combustion residue. The binder composition according to claim 9, further comprising 10 to 4,000 parts by weight of slag based on 100 parts by weight of the combustion residue.

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