KR100621119B1 - Method for solidifying solid-state fossil fuels - Google Patents

Abstract

The present invention relates to a method for solidifying a solid fossil fuel by using a solidifying agent, and only a high coking bituminous coal is used as a raw material for producing a solid, as well as a single or a mixture of solid fossil fuels such as anthracite coal and powdered coke. It can be used to maintain the durability, high temperature stability and orderability of the solid produced according to the conventional blast furnace process and to produce a solid fossil fuel solid having a high calorific value.

Fossil fuels, solids, coke, coal, strength

Description

Method for solidifying solid-state fossil fuels

1 to 5 are test data showing the results of measuring the point drop strength of the coke manufactured according to the solidification method of the present invention.

6 and 7 are photographs showing the results of the high temperature stability test of the coke prepared by the solidification method of the present invention and the conventional coke treated with the solidifying agent.

8 and 9 are photographs showing the durability test results of the coke prepared according to the solidification method of the present invention.

The present invention relates to a method for solidifying solid fossil fuels, and more particularly, when a solidifying agent configured to have a specific composition is mixed with a solid fossil fuel, as a solid fossil fuel, in addition to bituminous coal, powdered coke, anthracite, etc. Solid fossil fuels that can be used to produce solids such as coke with excellent durability, high temperature stability, high degree of orderability, and high calorific value, even if a single or mixture of solid fossil fuels is used and a simple facility without a separate gas facility is used. On how to solidify.

As a process for manufacturing molten iron which is the most basic material of steel, in the conventional process (hereinafter referred to as "blast furnace process"), a furnace is used as a facility and iron ore and coal are used as raw materials used in the furnace. Iron ore is used to produce sintered ore in the form of agglomerate of a certain size through the sintering process and coal is made into the coke in the form of agglomerate through the coke process to solidify in order to increase the formation rate of molten iron to spread heat evenly. Has come. However, in order to perform the preceding coke process for use in such a blast furnace process, a separate coke oven and a coke oven gas facility for heating the coke oven is required, which requires a lot of facility costs, and the amount of environmental pollutants generated in these facilities was also high. . In addition, in order to reduce the production cost, the fire of the blast furnace should not be turned off, and the sintering process and the coke process took much time. In addition, the iron ore that can be used in the sintering process is limited to expensive lump ore, and the production cost is high, and the coal which can be used in the coke process has a high calorific value, so that the high coking bituminous coal or petroleum relying on the whole imports It is limited to bituminous coal mixtures containing at least 50 to 60% of bituminous coal, which leads to enormous foreign currency waste. In addition, the coke generated in the amount of approximately 3 to 8% byproduct during the coke process is not easy to reuse in the steelmaking process.

According to the new process of POSCO Co., Ltd., which was developed as a way to solve the problems of the conventional blast furnace process, about 23% cheaper iron ore was used as the raw material of sintered ore as the raw material of the blast furnace process. It saves 10 ~ 15% of production cost compared to blast furnace method by using raw bituminous coal which is more than 20% cheaper than formed bituminous coal. This process uses HCI (Hot Compacted Iron) manufacturing facilities to reduce the reduced ferrite ore into sintered ore, and to form ordinary bituminous coal into coke, and to put them in the blast furnace to extract the molten iron, this process is conventional blast furnace Compared with the construction method, it is possible to turn off the blast furnace to control the game situation, the amount of operation, etc., so that the production can be freely controlled and the facility cost is also reduced by about 8%. However, coal that can be used in the above-described new construction method is still limited to bituminous coal.

In addition, in order to manufacture coke as a solid by using high coking bituminous coal as it is without going through a conventional coke process requiring expensive equipment, petroleum pitch, sweet potato, starch of potato, molasses, etc. The use of mixtures prepared by mixing in water has also been studied. However, the use of such a mixture as a solidifying agent lacks the high temperature stability of the coke produced and the cost of the solidifying agent is also expensive and is only limited in very few processes.

Coke, an example of solid fossil fuel solids, is used not only for casting, but also for metallurgical processes such as iron alloy, lead and zinc production, and kilns for making lime and magnesia, depending on the size and strength. It is also used to manufacture calcium carbide, which is a raw material, and the extra coke powder is used for industrial boiler fuel.

Currently, the bituminous coal used as the main coke raw material is all depended on imports. Considering the domestic situation of bituminous coal import value of $ 38.9 billion in 2004, all the bituminous coal can be manufactured as coke without generating by-products such as bunker. There is an urgent need for a solidification method for using other solid fossil fuels such as anthracite coal and powdered coke as a raw material for coke production.

Therefore, the present inventors have conducted a study to solve such a conventional problem, when the solidified fossil fuel is solidified by adding a solidifying agent which is composed of a specific composition and solidifies the solid fossil fuel quickly, In addition, it is possible to use either a single or a mixture of solid fossil fuels such as anthracite coal and powdered coke, and to maintain the durability, high temperature stability and water repellency of the conventional solid body even without the conventional process requiring expensive facility cost, and to generate high calorific value. It has been found that the solid body of the solid fossil fuel having can be prepared and the present invention has been completed.

It is an object of the present invention to provide a solidification method of a solid fossil fuel that can produce a high-strength solid body using all solid fossil fuels, including anthracite coal and powdered coke, as raw materials.

In order to achieve the above object, the present invention is a method of solidifying a solid fossil fuel by using a solidifying agent, wherein 3 to 10 parts by weight of a solidifying agent is added to and mixed with 100 parts by weight of one or more solid fossil fuels. First step; A second step of molding the mixture prepared in the first step; And a third step of preparing the solidified body by heating the molded product prepared in the second step at a temperature of 100 to 300 ° C., wherein the solidifying agent is 25 to 35% by weight emulsified asphalt, 0.05 to emulsifier for asphalt, based on the total weight. It is characterized by containing 0.20% by weight, hydrochloric acid 0.1-0.3% by weight, calcium chloride 0.01-0.05% by weight, oleic acid 0.01-0.05% by weight, surfactant 0.005-0.030% by weight and the balance.

Hereinafter, the present invention will be described in more detail.

In the present invention, the solidified body of the solid fossil fuel is prepared by adding a solidifying agent as a binder to facilitate the solidification of the solid fossil fuel.

In the present invention, the solid fossil fuel excludes liquid and gaseous fossil fuels such as petroleum and natural gas among fossil fuels, and may be used without limitation as long as it is mainly a coal itself or a fuel mainly composed of coal. Bituminous coal, anthracite coal or a mixture of two or more of these fuels is most preferred.

On the other hand, the solidifying agent serves to transform the solid fossil fuel in the form of a powder, it is configured to contain an emulsified asphalt, asphalt emulsifier, hydrochloric acid, calcium chloride, oleic acid, surfactants and water.

Among these components, emulsified asphalt is used to increase the elasticity and stability of the mixed particles and serve as surface waterproofing. Nonionic emulsified asphalt is also possible. desirable. If it is contained in an amount of less than 25% by weight may have a problem of lack of high temperature stability due to the decrease in elasticity between particles, and when contained in an amount of more than 35% by weight is prematurely burned or the porosity of fossil fuel is reduced Since there may be a problem, it is contained in an amount of 25 to 35% by weight based on the total weight of the solidifying agent. More preferably, it is contained in the quantity of 28.0-30.0 weight%.

Emulsifiers for asphalt have good degradability due to high emulsification and are used as mixing asphalt emulsions, and any of cationic or nonionic emulsifiers can be used. If it is contained in an amount of less than 0.05% by weight may have a problem that can not emulsify asphalt, etc. If it is contained in an amount of more than 0.20% by weight, there may be a problem that increases the product cost and rather decreases the emulsification function, It is contained in an amount of 0.05 to 0.20% by weight based on the total weight of the solidifying agent. More preferably, it is contained in the amount of 0.10 to 0.15 weight%.

Hydrochloric acid is mixed with emulsifiers for asphalt to perform dispersion and decomposition and is used for mixed purification. If it is contained in an amount of less than 0.1% by weight, there may be a problem that the dispersion and decomposition is not smooth, if contained in an amount of more than 0.3% by weight, there may be a problem that an environmental inhibitory factor occurs, the total weight of the solidifying agent It is contained in the amount of 0.1 to 0.3% by weight relative to the. More preferably, it is contained in 0.20 to 0.25 weight%.

Calcium chloride has a freeze protection function of the mixture and is used to increase the density to prevent cracking and to promote absorption. If it is contained in an amount of less than 0.01% by weight it may not be smoothly accommodated with water, there is a problem that the freezing prevention effect is weak, and when contained in an amount of more than 0.05% by weight anhydride is generated a large amount of solidifying agent Since there may be a difficult problem, it is contained in an amount of 0.01 to 0.05% by weight relative to the total weight of the solidifying agent. More preferably, it is contained in the quantity of 0.02-0.03 weight%.

Oleic acid is used as an emulsifier as a type of fatty acid surfactant, and the other material is well absorbed by the mixed particles, penetrates into the mixed particles inner surface to improve the waterproofing and reduce the solidification phenomenon at the freezing temperature. If it is contained in an amount of less than 0.01% by weight may have a problem that the waterproofness is lowered, if it is contained in an amount of more than 0.05% by weight may cause a problem to form a float, 0.01 ~ 0.05 relative to the total weight of the solidifying agent It is contained in an amount of% by weight. More preferably, it is contained in the quantity of 0.02-0.03 weight%.

Surfactants increase foamability, activate dispersing power and improve product productivity as emulsifiers, more preferably using one or two or more mixtures of cationic or amphoteric surfactants. If it is contained in an amount of less than 0.005% by weight relative to the total weight of the composition there may be a problem that the surface tension occurs in the emulsifier does not emulsify, and when contained in an amount of more than 0.030% by weight the product cost is increased It may be present in an amount of 0.005 to 0.030% by weight based on the total weight of the solidifying agent. More preferably, it is contained in the amount of 0.01 to 0.02 weight%.

Water is contained to accommodate the adaptation of the water content to occupy the remaining amount except the above components. If too little water is contained, there may be a problem that the emulsion dispersion does not occur properly. If too much water is present, there may be a problem that the adhesion between the mixture particles, water resistance and strength is reduced, so that the water content is also adjusted to a suitable range shall. Most preferably in an amount of about 70% by weight relative to the total weight of the solidifying agent.

Since the solidifying agent prepared according to this composition is a liquid, it is easy to uniformly mix in the mixing process mixed with the solid fossil fuel powder, which is the coke raw material, so that the variation in the strength of the product is very small, and thus the process and quality control are easy. In addition, since the liquid phase is almost burned away in the curing process during the production process, even if the produced solid is used as a fuel and a reducing agent, the amount of ash is not increased, so that no additional slag is generated during steel operation. However, when the liquid solidifying agent is used in an amount of less than 3 parts by weight with respect to 100 parts by weight of solid fossil fuel, there may be a problem in the solidification and strength of the fossil fuel, when used in an amount of more than 10 parts by weight Since there may be a problem that the porosity of the solid is lowered, there is a lack of sufficient calorific value and combustibility, and the product cost is high, it is preferably used in an amount of 3 to 10 parts by weight. More preferably, it is used in the quantity of 7-8 weight part.

When the solid fossil fuel and the solidifying agent is prepared with such a component composition, these may be mixed, and then molded using a molding machine according to a conventional method, and the molded body may be heated at a temperature of 100 to 300 ° C. to prepare a solid such as coke. . When the solidified body is manufactured according to the solidification method, the curing speed is shortened, and thus the solidified body is produced at a high speed, and a product having excellent structural durability, high temperature stability, and high degree of orderability at a high temperature can be manufactured. Preferably, the calorific value of the solid produced according to the present invention is about 6,200 to 7,500 kcal / kg.

Hereinafter, the present invention will be described in detail with reference to Examples of the preparation of the solidifying agent, followed by Examples and Comparative Examples, but the present invention is not limited only to these examples.

Production Examples 1 to 3 Solidifying Agent

Emulsified asphalt (AP-3; Korea Emulsion, Korea), Asphalt emulsifier (Farmin ST-7; Kao Corp., Japan), Hydrochloric acid, Calcium chloride, Oleic acid, Surfactant (NP-8; Youngchang Chemical, South Korea) and water to quantify each component to the content of the following Table 1 and then physically combined using a homogenizer (Homogenizers) and the like. Specifically, emulsified asphalt It was heated to 130 ℃ and other components were heated to 80 ℃ to emulsify and disperse to the physical bond to prepare a solidifying agent of Preparation Examples 1-3.

Ingredient (% by weight) Production Example One 2 3 Emulsified asphalt 29.6259 25.000 35.000 Emulsifiers for Asphalt 0.1367 0.1185 0.1578 Hydrochloric acid 0.2279 0.1975 0.2630 Calcium chloride 0.0285 0.0247 0.0329 Oleic acid 0.0253 0.0219 0.0292 Surfactants 0.0141 0.0122 0.0163 water Remaining amount Remaining amount Remaining amount

<Examples 1 to 3 and Comparative Examples 1 to 6> coke production

After the powdered coke is put into an input hopper installed in a conventional coke forming facility line, the powder is transferred to a storage hopper and weighed, and the solidifying agent prepared in Preparation Examples 1 to 3 in a tubelaid mixer is mixed with the composition shown in Table 2 below. The product was discharged by molding at a pressure of 5 kg / ㎠ in a molding machine and then heated to a temperature of 100 ~ 300 ℃ in the stabilization device to produce a molded coke. At this time, the hardening | curing agent was added with respect to 100 weight part of powdered coke.

Ingredients (parts by weight) Example Comparative example One 2 3 One 2 3 4 5 6 Solidifying agent Preparation Example 1 7 - - 2 - - 12 - - Preparation Example 2 - 7 - - 2 - - 12 - Preparation Example 3 - - 7 - - 2 - - 12 Solid fossil fuel Buncokes (POSCO products) 100 100 100 100 100 100 100 100 100

Test Example 1 Measurement of Coke Quality

The main component content, compressive strength, porosity and calorific value of the coke prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were measured according to a conventional measuring method, and the results are shown in Table 3 below.

quality Example Comparative example One 2 3 One 2 3 4 5 6 Main ingredients (Unit: wt%) Moisture content 0.37 0.36 0.39 0.28 0.33 0.42 0.37 0.32 0.37 Volatility 1.61 1.76 2.50 0.82 0.96 1.36 1.52 1.38 1.52 Ash 12.15 12.19 9.77 11.13 12.14 11.89 12.03 12.13 12.03 Fixed carbon 86.24 86.06 87.34 85.58 85.06 86.16 86.82 86.85 86.82 Performance Compressive strength (㎏ / ㎠) 72.5 77.2 45.3 42.3 42.4 44.1 79.2 80.1 83.52 Porosity (%) 32.3 34.9 33.7 41.1 42.5 42.8 26.4 28.1 23.3 Calorific Value (kcal / ㎏) 6,899 6,894 6,834 6,444 6,325 6,338 5,942 6,097 6,102

Compared with the volatile matter of 0.5-2.0% by weight, 10-13% by weight of ash, 80-89% by weight of fixed carbon, and calorific value of 6500-7200 kcal / kg In view, the main components of the coke of Examples 1 to 3 prepared by using powdered coke as the raw material for coke production and adding 7 parts by weight of a hardener were similar, and the calorific value was also close. Meanwhile, in Comparative Examples 1 to 3 in which a small amount of a hardener was added and Comparative Examples 4 to 6 in which an excessive amount of a hardener were added, the contents of moisture content, volatile matter, ash and fixed carbon in the main components of coke were similar to those of the related art. However, in Comparative Examples 1 to 3, in which a small amount of a hardener was added, the porosity was improved, but the compressive strength and calorific value were lowered. Was improved, but porosity and calorific value were lowered.

Examples 4 to 12 Preparation of Coke

According to the composition and content of the following Table 4, a solidifying agent and a solid fossil fuel single or a mixture was homogeneously mixed in the same manner as in Examples 1 to 3 to produce coke. At this time, the solidifying agent was added based on 100 parts by weight of the solid fossil fuel.

Ingredients (parts by weight) Example 4 5 6 7 8 9 10 11 12 Solidifying agent Preparation Example 1 7 7 7 7 7 7 7 7 7 Solid fossil fuel Bunk coke 50 40 30 50 40 30 - - - hard coal 50 60 70 - - - 50 100 - Bituminous coal - - - 50 60 70 50 - 100

Test Example 2 Measurement of Coke Quality

The main component content and calorific value of the coke prepared in Examples 4 to 12 were measured according to a conventional measuring method, and the results are shown in Table 5 below.

quality Example 4 5 6 7 8 9 10 11 12 Main ingredients (Unit: wt%) Initial Weight Moisture (IM) 1.19 1.25 2.69 3.28 1.47 0.88 2.19 3.34 2.13 Volatile Powder (VM; Volatile Meter Dry Basis) 3.56 3.94 4.62 17.37 14.77 19.56 15.00 7.60 28.11 Ash 15.11 13.82 12.85 5.34 9.66 9.69 11.62 14.17 7.05 Fixed Carbon (FC) 81.32 82.24 82.53 77.30 75.57 70.75 73.38 78.23 64.84 Performance Calorific Value (kcal / ㎏) 6,528 6,515 6,490 7,085 7,133 7,233 6,950 6,260 7,492

The calorific value of Example 12 prepared according to the solidification method of the present invention using bituminous coal as a raw material for coke production was 7,492 kcal / kg, which was significantly higher than the calorific value of coke produced according to the conventional blast furnace method. In addition, the calorific value of Examples 7 to 10 using the powdered coke or anthracite and a mixture of bituminous coal as raw materials was also excellent. The calorific value of Example 11, which had an approximate value of kcal / kg and only anthracite coal, was also 6,200 kcal / kg or more. Indicated.

Test Example 3 Measurement of Coke Quality

The test results measured after one day of age by applying the point drop strength of the coke manufactured in Examples 1, 4, 7, 11 and 12 to the Geotechnical Engineering Laboratory of the University of Seoul are shown in Table 6 below. Specific test results of each example are shown in FIGS. 1 to 5, respectively.

Dotted Drop Strength Is (50) Weak Surface Strength Ratio Ia (50) γ _t Point load Point load level Perpendicular option Q _u Q _umax unit kgf / ㎠ kgf / ㎠ kgf / ㎠ g / cm 3 kg / ㎠ kg / ㎠ kg / ㎠ kg / ㎠ Example 1 2.83 3.7 1.57 1.31 1.04 62.3 81.3 34.6 81.3 Example 4 1.47 3.56 1.07 2.42 1.28 32.4 78.4 23.6 78.4 Example 7 1.81 5.14 1.12 2.85 1.16 39.7 113.2 24.7 113.2 Example 11 2.41 4.08 1.50 1.69 1.40 53.1 89.7 32.9 89.7 Example 12 3.66 5.45 0.76 1.49 1.08 80.6 119.8 16.8 119.8

As can be seen in Table 6 and Figures 1 to 5, the strength of the molded body produced according to the solidification method of the present invention is good and shows a high 119.8kgf / ㎠, high temperature stability and durability according to the conventional blast furnace method It is superior to the existing products manufactured, and it is possible to produce products equivalent to or higher than the coke produced in the existing coke process.

Test Example 4 High Temperature Stability Test of Coke

The sample coal (1) manufactured by molding the coke of Example 10 and the sample coal (2; manufactured by POSCO Co., Ltd.) manufactured by molding the coke produced in the existing coke process were subjected to temperature in a conventional high temperature stability test apparatus. After 1 hour and 30 minutes of adjusting to 1,152 ° C., the coke state and 30 minutes after 1 minute and 1,152 ° C. of temperature were lowered to 770 ° C. and then the coke state was observed after 30 minutes, respectively. Indicated. As can be seen from FIG. 6 and FIG. 7, the coke produced according to the solidification method of the present invention did not deform in shape even at a high temperature of 1,152 ° C.

Test Example 5 Durability Test of Coke

The coke molded body 11 of Example 1 was put into a normal electric furnace, and the external behavior was observed at 1,000 ° C and 1,200 ° C while the temperature was raised, and the results are shown in FIGS. 8 and 9. As can be seen from Figures 8 and 9, the coke produced according to the solidification method of the present invention did not show the collapse of the product, such as differentiation and cracking, even at a high temperature of 1200 ℃ maintained the original structure as it is. Therefore, it can be expected that there will be no behavior that impedes breathability in the furnace due to the differentiation phenomenon.

Apparatus that can be used to perform the solidification method of the present invention can use a conventional coke forming line, a mixer for mixing the fossil fuel and the solidifying agent, except the complicated unnecessary equipment, a molding machine for molding into a desired shape, As a pretreatment for use as a product, a line having only minimal equipment such as a stabilization device for heating the product may be manufactured and used.

Mixed coal briquettes mixed with two or more solid fossil fuels produced according to the solidification method of the present invention can be customized to produce a product that meets the various needs of the user by adjusting the calorific value, the combustion time, etc. Can be. Since the strength of the product can be freely adjusted in the range of 30 to 80㎏ / ㎠, it is possible to flexibly cope with the quality control according to the demand of the consumer, and the size of the product is variably adjustable in the range of 25 to 200㎜, It can be produced in various ways.

The solidified bodies produced according to the solidification method of the present invention are steel mills, steel mills, thermal power plants, cogeneration plants, kilns of cement manufacturers, glass factories, nonferrous metals manufacturers, foundries, tire plants, fuel for facility agriculture, household fuels and incinerators, etc. It is supplied and can be used widely.

In the present invention, only the coke is manufactured as an example of the solidified body, but the present invention is not limited thereto, and the solidified fossil fuel and the material for solidifying the same are not limited so long as they are prepared using the solidifying agent used in the present invention. do.

As can be seen from the above, the solidification method according to the present invention is a method of solidifying by adding a solidifying agent for solidifying a solid fossil fuel rapidly, a solid raw material of solid fossil fuels such as anthracite coal, powdered coke, etc. Alternatively, any mixture may be used to maintain the durability, high temperature stability and orderability of a conventional solid produced using only high coking bituminous coal and to prepare a solid fossil fuel having a high calorific value.

In addition, the solidification method according to the present invention may use an existing factory, and may use a simple factory established by removing complex unnecessary equipment. Production costs are also reduced by approximately 32% compared to the blast furnace process and about 17-22% compared to the new POSCO process.

When using the solidification method according to the present invention to produce a mixed coal briquettes by blending a more various types of solid fossil raw coal in the future it is expected that it will be able to satisfy the needs for the quality of various consumers, the optimum according to the order specifications of the consumer Customized coal briquettes can be manufactured and supplied.

In addition, the revitalization of mining areas, which have been stagnant for a long time, can contribute to national balanced development and regional economic development.

Claims (5)

In the method of solidifying a solid fossil fuel using a solidifying agent, A first step of adding 3 to 10 parts by weight of a hardener based on 100 parts by weight of one or more solid fossil fuels; A second step of molding the mixture prepared in the first step; And The molded article prepared in the second step of 100 ~ 300 ℃ It consists of a third step of producing a solid by heating at a temperature, The solidifying agent is 25 to 35% by weight emulsion asphalt, 0.05 to 0.20% by weight emulsifier for asphalt, 0.1 to 0.3% by weight hydrochloric acid, 0.01 to 0.05% by weight calcium chloride, 0.01 to 0.05% by weight oleic acid, surfactant 0.005 ~ A method of solidifying fossil fuels, characterized in that it contains 0.030% by weight and the remaining water. The method of claim 1, wherein the solid fossil fuel is coal or a coal-based fuel. The method of claim 2, wherein the solid fossil fuel is powdered coke, bituminous coal, or anthracite coal. The solidifying method of claim 1, wherein the surfactant is one or two or more surfactants selected from the group consisting of cationic surfactants and amphoteric surfactants. The solidification method of claim 1, wherein the calorific value of the solidified body is about 6,200 to 7,500 kcal / kg.

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