KR102641129B1 - 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 an agent for reducing hydrogen chloride generation in a fluidized bed boiler using oyster shell shells, a method for reducing hydrogen chloride generation in the furnace of a fluidized bed boiler using the same, and a binder composition using the combustion residue.
The present invention uses oyster shell powder obtained only through drying and grinding processes of discarded shells without separate washing and firing processes as a hydrogen chloride generation reducing agent for a fluidized bed boiler, and uses the hydrogen chloride generation reducing agent including the oyster shell powder as a hydrogen chloride generation reducing agent in a fluidized bed boiler. It is put into the furnace and mixed with solid fuel for combustion to reduce the generation of hydrogen chloride in the fluidized bed boiler furnace in a dry form, thereby reducing the atmospheric emission of hydrogen chloride (HCl) gas generated after combustion in the conventional fluidized bed boiler using solid fuel in the downstream process. Since it is possible to replace the method of reducing hydrogen chloride gas emissions by spraying liquid slaked lime, etc., it is possible to realize the effect of reducing the treatment costs of cave closures and reducing the operating costs of the fluidized bed boiler.

Description

Fluidized bed boiler hydrogen chloride generation reduction agent using oyster shell shells, method for reducing chlorine hydrogen generation in a 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 a fluidized bed boiler hydrogen chloride generation reduction agent using oyster shell shells, a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace using the same, and a binder composition using the combustion residue. More specifically, the pretreatment process is complicated and recycling is insufficient. Oyster shell powder obtained by drying and grinding the discarded shells without separate washing and firing processes is used as a hydrogen chloride generation reducing agent in a fluidized bed boiler, and the hydrogen chloride generation reducing agent including the oyster shell powder is used as 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 it after injection into the used fluidized bed boiler furnace, and utilizes the combustion residue remaining after the combustion.

Shells are the shells of shellfish (shellfish). When shellfish are shipped, most of them are removed and only the contents are distributed. A large amount of shells are generated as waste around shellfish collection points and are piled up on the coast, contaminating the coast. This is causing various environmental problems.

Currently, it is known that 360,000 tons of oyster shells are generated annually on the coast of Korea, and in particular, a lot of shells are generated due to oyster farming. Of these, only 10% are reused as calcium fertilizers and the rest are left abandoned on the coast, raising the need for large-scale disposal of marine waste such as oyster shells.

The chemical composition of the shell usually consists of more than 90% by weight of CaCO ₃ , and the remaining traces are made up of inorganic substances such as SiO ₂ , MgO, Al ₂ O ₃ , Na ₂ O, and SO ₃ .

However, there are some organic substances and salts that remain in the shell when the shell is desorbed, and if the shell is left for a long time, problems such as bad odor and farm contamination due to organic matter decay and leachate generation occur.

Accordingly, various technologies are being developed to recycle shells. Among these, Patent Document 1 includes the steps of washing oyster shells to remove salt; Crushing oyster shells from which salt has been removed; A classification step of powdering the pulverized oyster shells into a predetermined particle size; A calcination step of producing quicklime (calcium oxide) by burning oyster shell powder at a temperature of 600 to 900°C to remove carbon dioxide; A ground improvement type solidified material manufacturing method using cave shells comprising 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 is disclosed. It is done.

Patent Document 2 is an invention regarding an inorganic coagulant containing waste gypsum, starfish powder, shellfish shell powder, and clay minerals, comprising 50 to 200 parts by weight of waste gypsum powder, 50 to 200 parts by weight of starfish powder, and 50 to 100 parts by weight of shell powder. and 30 to 70 parts by weight of clay minerals, providing a flocculating composition for treating inorganic wastewater, and suggesting applicability as an inorganic flocculating composition for food wastewater treatment, livestock manure wastewater treatment, and river wastewater treatment.

Patent Document 3 relates to a method for manufacturing waste shell recycled feed, which includes the steps of putting raw materials such as washed shellfish into a firing furnace and performing primary firing at a temperature of 1,300 to 1,500°C for 20 to 30 minutes; Grinding the first fired raw material by putting it into a grinder; Separating the pulverized raw material powder by inputting it into a separator; Injecting the separated fine powder into a granulator and forming it into granules using high temperature water as a binder; Injecting the molded granular feed into the firing furnace and performing secondary firing at a temperature of 900 to 1000°C for 10 to 20 minutes; Cooling the second-fired granular feed and then reintroducing it into the kiln and repeating third-fire at a temperature of 900 to 1,000°C for 10 to 20 minutes; And it is performed by putting the thirdly fired granular feed into a vibrating sieve and sieving it.

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

Patent Document 5 proposes a new shell crushing system for producing flue gas desulfurization raw materials and a method for producing high-quality desulfurized gypsum using the same. Specifically, the shells are washed, dried (35 to 60 minutes at 250 to 350 ° C.), crushed, sorted, and fired. (70 to 100 minutes at 500 to 800°C), which is carried out in a wet desulfurization step by reacting the powder with exhaust gas and a step of recovering the desulfurized gypsum precipitated during wet desulfurization, thereby pulverizing the shell more evenly and producing high quality product. 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, technology to pre-process the shells and produce them cheaper than products currently used in the field is required. However, excessive costs are incurred during pre-treatment processes such as washing, drying, grinding, and high-temperature firing, and during product manufacturing, resulting in waste. The recycling cost is excessive compared to the shell processing cost, 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 to reduce the generation of boiler hydrogen sulfide, but the prior art uses a wet desulfurization agent for a pulverized combustion boiler in a thermal power plant equipped with a separate desulfurization device. Since it is used as a drying agent, the limestone (CaCO ₃ ) component is converted to quicklime (CaO) component through washing, drying, grinding, and firing processes, and then mixed with water to produce a slurry, and this slurry is reacted with exhaust gas to perform wet desulfurization. Because this method is used, there is a problem that the process cost is excessive.

Meanwhile, in general, fluidized bed boilers that burn 100% of coal do not generate hydrogen chloride gas, which is a toxic gas, but in fluidized bed boilers that use 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 most commonly used. When burning solid fuel containing waste synthetic resin or waste wood, a large amount of hydrogen chloride gas is generated, so the maximum allowable emission concentration is high. In order to maintain phosphorus below 0.3%, liquid slaked lime is excessively sprayed. For this reason, the use of large amounts of expensive liquid slaked lime increases the operating cost of the boiler, and the final remaining combustion residues are discharged in lumps due to the moisture in the liquid slaked lime, making recycling difficult.

Accordingly, as a result of the present inventors' efforts to solve the existing problems, the pre-treatment process was complicated and recycling was insufficient. The discarded oyster shells were dried and pulverized to obtain pulverized oyster shell powder with appropriate organic content, moisture content, and salt content. It was confirmed that the generation of hydrogen chloride gas can be dramatically reduced from the combustion stage by mixing and burning after putting it into the fluidized bed boiler furnace using solid fuel. It was confirmed that the oyster shell powder can be used as a hydrogen chloride generation reduction agent inside the fluidized bed boiler and as an organic matter and chlorine agent. The present invention was completed by confirming the effect of reducing operating costs of the fluidized bed boiler by omitting the pretreatment process because the oyster shells containing the ingredients are directly added together with the fuel.

Republic of Korea Patent No. 0464666 (announced on January 3, 2005) Republic of Korea Patent No. 1169563 (announced on July 27, 2012) Republic of Korea Patent No. 0993223 (announced on November 9, 2010) Republic of Korea Patent No. 1753823 (announced on July 5, 2017) Republic of Korea Patent No. 2109756 (announced on May 26, 2020)

The purpose of the present invention is to provide a fluidized bed boiler hydrogen chloride generation reduction agent containing oyster shell powder containing organic matter and chlorine components by drying and grinding the discarded shells while omitting separate washing and firing processes. .

Another object of the present invention is to provide a method for reducing the generation of hydrogen chloride in a fluidized bed boiler furnace, which is performed in a dry manner by adding oyster shell powder into the furnace of a fluidized bed boiler using solid fuel and mixing and combustion.

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 reduction agent using oyster shell powder pulverized to a particle size of 5 mm or less and containing more than 90% by weight of calcium carbonate.

The fluidized bed boiler hydrogen chloride generation reduction agent 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 a moisture content of 0.01 to 5% by weight.

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

The method for reducing hydrogen chloride generation in a fluidized bed boiler furnace according to the present invention involves putting the hydrogen chloride generation reducing agent and solid fuel into the furnace of a fluidized bed boiler, and then performing mixed combustion to reduce hydrogen chloride in a dry form. For 100 parts by weight, it is preferable to add 100 to 2,000 parts by weight of the solid fuel.

The solid fuel may be 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 containing combustion residues remaining after mixed combustion of a hydrogen chloride generation reducing agent and 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, oyster shells, which are underutilized due to the complexity of the pretreatment process of washing and firing the shells, are dried and crushed oyster shell powder that has only undergone a grinding process is introduced into the fluidized bed boiler furnace to reduce the generation of hydrogen chloride. By confirming the effect, pulverized oyster shells can be used as a reducing agent for hydrogen chloride generation in a fluidized bed boiler.

In addition, the fluidized bed boiler hydrogen chloride generation reduction agent using pulverized oyster shell 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 fluidized bed boiler using conventional solid fuel. In order to reduce atmospheric emissions of hydrogen chloride (HCl) gas generated after combustion, it is possible to replace the method of reducing hydrogen chloride gas emissions by spraying liquid slaked lime, etc. in the later process.

Therefore, the operating cost of the fluidized bed boiler can be reduced and large quantities of oyster shells can be recycled.

Figure 1 is a schematic diagram of a device 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 the fluidized bed boiler furnace of the present invention,
FIG. 2 is a photograph of the exterior of the actually constructed device of FIG. 1.

Hereinafter, the present invention will be described in detail.

The present invention provides a fluidized bed boiler hydrogen chloride generation reduction agent containing oyster shell powder with a calcium carbonate content of 90% by weight or more and a particle size of 5 mm or less.

The present invention can be used as a hydrogen chloride generation reduction agent in 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 fluidized bed boiler fuel, so even if some chlorine is present in the oyster shell, which is a hydrogen chloride generation reducer, it does not cause boiler operation problems, and organic matter is also completely burned along with the fuel inside the boiler. Because.

Therefore, oyster shell shells, which are used as a hydrogen chloride gas reduction agent in fluidized bed boilers using solid fuel, can be used without separating the coated sand, washing, or firing even if they contain a large amount of salt or organic matter or contain some moisture and plastic coating sand for oyster farming. There is an advantage to being able to do this.

Therefore, the oyster shell powder of the present invention may have an organic content of 0.1 to 10% by weight, a moisture 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 through mixed combustion of solid fuel and oyster shell in a fluidized bed boiler is that oyster shell, which is mainly composed of calcium carbonate (CaCO ₃ ), is decarboxylated (CaO + CO ₂ ) at a temperature of about 800°C and converted to CaO component. The CaO component transferred in this way directly reacts with the hydrogen chloride (HCl) component generated during combustion of solid fuel in the furnace and is transferred to calcium chloride component, which is contained in the combustion residue.

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

Therefore, it is preferable that the oyster shell used as a hydrogen chloride generation reduction agent in the fluidized bed boiler of the present invention is crushed to have a calcium carbonate component of 90% by weight or more and a particle size of 5 mm or less.

More preferably, the particle size of the oyster shell is 0.005 to 5 mm. At this time, if the oyster shells are crushed to less than 0.005mm, the hydrogen chloride reduction efficiency improves, but the grinding cost increases excessively and the oyster shells are not crushed, or if the oyster shells are used in the form of coarse granules exceeding 5mm, the hydrogen chloride reduction reaction inside the boiler As time increases, efficiency decreases.

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

The limestone powder can be any product that has a particle size of 5 mm or less and a purity of 80% or more that is generally distributed on the market.

If the amount of the limestone powder is less than 5 parts by weight per 100 parts by weight of oyster shell powder, the effect is minimal, and if it exceeds 1,000 parts by weight, the mixing rate of oyster shell shells is relatively reduced and the recycling rate of oyster shell shells is greatly reduced.

The fluidized bed boiler hydrogen chloride generation reduction agent of the present invention is generated in large quantities as a by-product in marine fish aquaculture in the case of shellfish shells, and causes various environmental problems such as contaminating coastal fishing grounds and making management of public waters difficult when stored on the coast. Because 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, oyster shells, which are underutilized due to the complicated pretreatment process of washing and firing the shells, are dried and pulverized and the pulverized oyster shells are utilized.

In addition, the shells are made into a hydrogen chloride gas reduction agent through a simple pretreatment process, omitting separate washing and firing processes, and are mixed and burned with solid fuel inside the fluidized bed boiler to remove hydrogen chloride (HCl) generated during fuel combustion and at the same time remove the shells. In addition to reducing processing costs and the cost of purchasing expensive liquid slaked lime, various effects can be expected, such as resource saving through waste recycling and prevention of coastal environment pollution.

The present invention provides a method for reducing hydrogen chloride generation in a fluidized bed boiler furnace, which is performed in a dry form by injecting 100 to 2,000 parts by weight of solid fuel into the furnace of a fluidized bed boiler and then mixing and burning for 100 parts by weight of a fluidized bed boiler hydrogen chloride generation reduction agent containing oyster shell powder. do.

It is preferable to add 100 to 2,000 parts by weight of solid fuel for 100 parts by weight of the fluidized bed boiler hydrogen chloride generation reduction agent. At this time, if it is less than 100 parts by weight, the power generation efficiency is drastically reduced due to low heat generation due to a lack of fuel components, and if it exceeds 2,000 parts by weight, the amount of oyster shell powder input is relatively reduced, significantly reducing the effect of reducing hydrogen chloride generation.

The solid fuel is preferably 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).

Figure 1 is a schematic diagram of a device 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 Figure 2 is a photograph of the exterior of the actually built device of Figure 1.

As a result of measuring the amount of hydrogen chloride gas generated from the above device, the exhaust gas of the combustion residue was measured after mixing 70% by weight of wood chip solid fuel and 30% by weight of oyster shell powder as solid fuel in an electric furnace. The reduction result can be confirmed by reducing the hydrogen chloride concentration to 1/15th of the case.

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

According to the above method of reducing hydrogen chloride generation in the fluidized bed boiler furnace of the present invention, the oyster shell powder of the present invention is put into the existing fluidized bed boiler furnace and the oyster shell shell and solid fuel are directly mixed and burned to dramatically reduce the generation of hydrogen chloride gas from the combustion stage. By confirming, the oyster shell is useful as a hydrogen chloride generation reducer inside the fluidized bed boiler, and since the oyster shell containing organic matter and chlorine components is directly input together with the fuel, the pretreatment process is omitted, thereby realizing a process cost reduction effect.

Furthermore, the present invention provides a binder composition containing combustion residues remaining after mixed combustion of a hydrogen chloride generation reducing agent and 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 method for reducing hydrogen chloride generation 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 the oyster shell exists in the form of CaCl ₂ produced by deoxidation and reaction with hydrogen chloride, or in the form of some quicklime (CaO).

When the combustion residues are used together with cement and slag, the strength can be further 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 one of general Portland cement, early steel Portland cement, semi-early steel cement, blast furnace slag cement, and fly ash cement, or a mixture of two or more. If the amount of the cement is less than 10 parts by weight, the effect is minimal. Conversely, if the amount exceeds 4,000 parts by weight, the strength is greatly improved, but the amount of combustion residues mixed in is relatively reduced and the cost increases excessively.

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 soft slag. It is preferable that it is one or a mixture of two or more.

The slag may be stimulated and promoted by the CaO and CaCl ₂ components of the combustion residue, thereby destroying its amorphous nature and causing a hydration reaction to harden. If the amount of slag is less than 10 parts by weight, the effect is minimal, and on the contrary, if it exceeds 4,000 parts by weight, the amount of combustion residues is relatively greatly reduced, resulting in the presence of a large amount of slag that has not reacted due to a lack of stimulant and accelerator components, which increases the strength. It deteriorates.

As described above, the combustion residue generated after the hydrogen chloride generation reduction process in the fluidized bed boiler according to the present invention has a high chlorine content, so it cannot be used in ready-mix concrete used with rebar, but it can be used as a binder in various construction sites such as for strengthening plain concrete or soft ground. is high.

Preferred examples and comparative examples of the present invention will be described below. Additionally, 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>

100% wood chip solid fuel was burned at 850°C in an electric furnace, then 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 at 850°C in an electric furnace, then the exhaust gas was measured and combustion residues were analyzed.

The oyster shell powder was obtained by drying discarded oyster shells as is and grinding them, and the pulverized oyster shells contained 92.3% by weight of calcium carbonate and had an average particle diameter of 430㎛.

<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 example, the hydrogen chloride concentration was measured at 312 ppm, reduced to about 1/15 compared to the comparative example, and maintained at about 1/10 of the maximum allowable concentration of 3,000 ppm.

<Experimental Example 2> Analysis of combustion residues

The chemical composition and free-CaO content results of combustion residues generated after combustion according to the comparative examples and examples are shown in Table 1 below .

From the results in Table 1, in the case of the combustion residue 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 residue generated in the Example, the CaO component content was about 35%. It was confirmed that the % increased by about two times, and the Cl ^- component content increased by about three times to about 15%.

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

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

<Experimental Example 3> Compressive strength measurement as a binder of combustion residues

To evaluate the usability of the combustion residues according to the comparative examples and examples above as a binder, the compressive strength was measured, and the results are shown in Table 2 below. The wave mixture ratio was 68% and it was produced in paste form.

From the results in Table 2, the compressive strength of the example in which oyster shell powder was mixed and burned was significantly increased compared to the comparative example in which only wood chip solid fuel was 100% burned. From the above results, it is judged that self-hardening was stronger because the Free-CaO and CaCl ₂ contents were higher.

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

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

Claims (10)

Contains oyster shell powder with a calcium carbonate content of 90% by weight or more and a particle size of 5 mm or less,
The oyster shell powder goes through only a drying and grinding process with the discarded shells without the separate washing and firing process,
Salt content 0.01 to 3% by weight,
Moisture content 0.01 to 5 weight and
A fluidized bed boiler hydrogen chloride generation reduction agent using oyster shells, which is characterized in that it reduces hydrogen chloride gas generation from the combustion stage by putting it into the fluidized bed boiler furnace using solid fuel even if it contains 0.1 to 10% by weight of organic matter. The fluidized bed boiler hydrogen chloride generation reduction agent using oyster shell 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. delete delete delete delete delete It is a binder composition containing a fluidized bed boiler hydrogen chloride generation reduction agent using the shell shell of paragraph 1 or 2 and combustion residue remaining after mixed combustion with solid fuel in the fluidized bed boiler furnace,
The oyster shell powder reacts with the hydrogen chloride component generated during combustion of solid fuel and is fixed to the combustion residue, so that the combustion residue contains a CaO content of 10 to 50% by weight and a Cl ^- content of 0.5 to 25% by weight. A binder composition. 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.