WO2014185625A1 - Geopolymer mix design method - Google Patents
Geopolymer mix design method Download PDFInfo
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- WO2014185625A1 WO2014185625A1 PCT/KR2014/002103 KR2014002103W WO2014185625A1 WO 2014185625 A1 WO2014185625 A1 WO 2014185625A1 KR 2014002103 W KR2014002103 W KR 2014002103W WO 2014185625 A1 WO2014185625 A1 WO 2014185625A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Definitions
- the present invention relates to a technology for construction and geoplymers, and particularly to a method for designing a geopolymer composition that can optimize the mixing ratio of each component of the geopolymer.
- [Background Gas, 3 Geopolymer] is an inorganic binder that hardens in low silver only by chemical reaction between aluminosilicate raw material and alkali activator. Since the production of geopolymers does not require a firing process, the energy consumption required for production is much lower than that of the Forland sheet, and carbon dioxide emissions can be reduced by more than 80%.
- Geopolymer of the correct concept refers to a material having amorphous properties as being made of a raw material having pozzolanicity among the inorganic binders which are reacted with an alkali activator 3: That is, fly ash, flooring, metacarlin, and soda-lime glass in thermal power plants.
- Jill Semant, natural pozzolanics, briquettes and the like can be used as raw materials for georeamers.
- blast furnace slag is used as the main raw material, it is conceptually not a geoplasmer because CSH galls similar to the Semanite Mall are produced as the main reactants.
- geopolymers made using strong alkalis are not only consistent in quality, but also have safety problems due to the use of excess alkali, and the manufacturing cost is high. For example, if a lot of strong alkali is used, excess Nat will remain in the pore SQkltlOR, and over time, sodium will react with carbon dioxide in the air, causing eif iorescence on the surface of the geopolymer. .
- the present invention has been made to solve the above problems, and sets in advance the reference values of the factors affecting the properties of the geo «reamer, and premixes the blending ratio of the raw materials to allow the geopolymer to be produced that can satisfy this reference value.
- the purpose is to provide a geopolymer formulation design method that can be calculated.
- Geo-polymer-fold 3 ⁇ 4 'design method according to the present invention for achieving the above object, as for determining the baehapbieul of geo polymer are prepared by mixing the base material containing the Al luminometer silicate component, an alkali activator and water A raw material analysis step of selecting a basic raw material and an alkali reactivator »and analyzing the chemical composition; A basic calculation step of calculating the moles of each of Si, Al, Na and H per unit weight of the basic raw material, shallow cal activator and water; Si / A in the final geopolymer produced!
- the method of designing the blender of the geopolymer may satisfy the set values of the Si Ml ratio, the a / Al ratio and the water content ratio, which are factors which have a significant influence on the physical properties of the geopolymer. It provides a method to calculate the blending amount of geol reamer raw materials.
- the present invention is expected to contribute to the geopolymer industry by providing the most important and basic data on the properties of geopolymers.
- I is a schematic flow diagram of a geopolymer formulation design method according to an embodiment of the present invention.
- Figure 2 is a table showing the use of the geopolymer according to the Si / ratio-.
- 3 is a table showing the design data and the result data of the experiment for the present invention.
- 5 is a graph of the quantitative X-ray diffraction analysis results for the sample.
- 6 is an amorphous component analysis result of the landfill coal material of Seocheon Thermal Power Plant calculated from X-fluorescence spectroscopy and quantitative X-ray diffraction analysis.
- Figure 3 is a graph showing the compressive strength of geopolymer made under the conditions shown in Figure 3,
- 8 (a) to 8 (c) are photographs of blood-sections observed with a gaze-cell ⁇ microscope for three samples.
- 9 is a photograph taken with scanning electron micrographs of fracture surfaces of four georeamer 3 ⁇ 4 samples.
- Geopolymer blending design method for achieving the above object, to determine the blending ratio of the geopolymer produced by mixing a basic raw material containing an aluminosilicate component, an al 3 ⁇ 4 reactivator and water as, dicing material analysis step of analyzing the chemical composition by selecting the base material 7 i and the alkaline activator; Singh-ki basic raw materials. Si. Per unit weight of alkali activator and water.
- the basic raw material, alkali may satisfy the reference value of the main factor set in the target setting step in the mixture containing the basic raw material, alkali activator and water.
- the main factor for determining the characteristics of the geopolymer in the target setting step further includes a water content ratio.
- pretreatment is performed to remove unburned carbon powder from the basic raw material, and in the basic calculating step, only Si, Al are present in the amorphous part except for the crystalline part of the basic raw material. It is preferred to calculate the respective moles for, Na and H.
- the singular-base calculation step is Si, Al, Na.
- the contents of Ai 2 0 3 , Si3 ⁇ 4 ' Na 2 0, 3 ⁇ 40 contained in the basic raw materials, additives, and water, respectively, were determined, and then, Si, Al ; It is preferable to calculate the sum of the moles of Na and H.
- the front-to-acid sodium powder in the solid state is selected.
- FIG. 1 is a schematic flowchart of a geo 3 ⁇ 4 reamer formulation design method according to an embodiment of the present invention-.
- Geopolymer formulation design method is to determine the relative blending ratio of ⁇ , alkali activator and mole of the base material raw materials of the geopolymer, as shown in FIG. It comprises a pretreatment step (10), raw material analysis step (20), basic calculation step (30), target setting step (40), compounding ratio calculation step (40).
- the basic raw material of the geopolymer is composed of aluminosilicate components and is a material having pozzolanic properties.
- Materials that can be used as basic raw materials include fly ash, bottom ash, coal briquettes, etakaol inj and natural pozzolanic ash (pumice or volcanic ash) from thermal power plants. It is submerged in water and activated by an alkali activating agent.
- Alkali activator is a basic substance that reacts with coal landfill. Nath hydroxide f (NaOH). Water glass (N Si ⁇ H 2 0), Sodium aluminate powder (NaAK ⁇ ), Sodium aluminate solution (NaAi 'n3 ⁇ 40 ). Alkaline foaming agents can be used singly. You may use it in two or more plurality. In this example, two alkali activators were used.
- pre-treatment is di to the above to crush the coal methoxy ripjae a suitable particle size and to remove the non-drawn tansobun, however, the tansobun content of unburnt coal in the buried material If low, the pretreatment may be omitted.
- the flotation method 1 is one of the beneficiation methods, which utilizes the difference in hydrophobicity and hydrophilicity of the mineral surface. It is a method of selectively attaching hydrophobic mineral particles to an air bubble to separate them.
- coal-filled land with a fluid is injected into a tank, and a collecting agent and a foaming agent are injected, and when bubbles are blown, bubbles adhere to unburned carbon powder. It floats to the surface of the tank and can remove unburned carbon powder from coal landfill.
- ⁇ analyze the chemical composition of the alkali activator of the coalfill material. Identifying what is contained in the coal filler and the alkali activator is essential for the scientific design of geopolymer.
- the composition ratio of the above oxides in the raw material and the alkali activator can be determined by various methods, such as the X TM fciy flourescene spectrometer as in this embodiment Can be identified through side equipment,
- composition ratio of the above oxides is not exaggerated for the entire coal landfill material, but only for the amorphous part of the coal landfill material except for the crystalline material. This is because the presence of these materials as crystalline makes no sense in the formulation design because they do not participate in geopolymer reactions with alkalinizers.
- SK contained in coal continuum is common in crystallinity and crystalline.
- the crystalline Si3 ⁇ 4 content is determined by XRD again. Since the difference between these two values is the amorphous SI0 2 content, only these values are used for the calculation of the blender.
- the composition ratio of sodium hydroxide or alumina soda solution among al3 ⁇ 4 reactivators is already known. For example, two moles of NaOH each contain one mole of ⁇ 3 ⁇ 40 and 3 ⁇ 40.
- the basic calculation step 20 is performed based on the chemical composition analysis of the coalfill material and the alkali activator which are the basic raw materials.
- the basic calculation step (20) calculates the content of Si, Al, Na, H per unit weight of the base material.
- the content of Si, Al, Ma, fl per unit weight of the basic raw material can be easily calculated through a mathematical calculation considering the chemical formula of each oxide.
- the content means the number of moles or increase of the silicon, aluminum, sodium, and hydrogen components.
- the deformation between weight and mole number is simple with the atomic weight known, so any unit can be used.
- Do. In this embodiment calculates the number of moles of each component per unit weight coal ash merip, will be briefly described, for example, within the embedding material coal. Assuming that 40 wt% of 3 ⁇ 4 is mixed, 1 kg of coal landfill contains 400 g of Si.
- the basic calculation step (20) is based on the calculation of the number of moles of each component in the base material , Si / A!
- the molar ratio and the Na / Al molar ratio can be calculated and used later in the target setting step. This will be described later.
- the reference values for the main factors of the geopolymer to be finally prepared in the batch setting step (30) Set After determining the number of moles per unit weight of silicon, aluminum, nat, and hydrogen in the basic raw material through the basic calculation step ( ) , the reference values for the main factors of the geopolymer to be finally prepared in the batch setting step (30) Set.
- Geopolymers include Si0 4 and Ala; Oxygen atoms alternately share in the tetrahedron to form a network structure. That is, A! Is substituted for Si in a continuous SiO., Tetrahedron structure. Since Si has a tetravalent charge while Ai has a trivalent charge, a monovalent bivalent silver such as sodium (Na) or potassium (K) is further formed.
- the ratio SI / A1 and Na / Al of geopolymers are important for structural warming. It has a meaning and acts as a major factor in determining the properties of the geoplymer. here
- Si / Al ratio or Na / Al ratio means molar ratio, but the weight ratio can be used because it knows the atomic weight of silicon, aluminum and sodium.
- the present invention has been conceived based on the main themes that constitute the core concept of the geometrical structure of the geopolymer, such as Si / Ai ratio, Na / Al ratio in the geoplymer, specifically, the basic raw material, alkali activator
- a method of preliminarily setting a reference value for the above-mentioned main factors and calculating a compounding ratio of raw materials that can satisfy the reference value is chemically and mathematically developed.
- the meaning of having a Si / Al bur is complex, but if the molar ratio of Si / AI is less than 3.0, the compressive strength of the geopolymer becomes large, and if it exceeds 3,0, it has flexible elasticity. Accordingly, as shown in FIG. 2 : the use of the geopolymer may vary according to a Si / Al molar ratio as a building material, an adhesive S, a sealant, or a resin material. In this example, the Si / Al rates were set to 2.0, 2.5, 3.0, and the like.
- the Na / Al ratio is important for the stability of geopolymers . Lose. If the Na content is excessive due to the excessive use of the alkali activator, Na, which does not participate in the reaction, remains in the geopolymer and combines with carbon dioxide in the air, causing whitening of the geopolymer.
- the Na / M ratio is set to 3 ⁇ 4 above 1, such as 0.8.
- the water content has a great influence on the flow (ow) of the geopolymer and is an important factor in the working rate and the curing rate.
- the relative value of the basic raw material, alkali activator and water to satisfy this reference value The amount of lilies will be determined.
- the compounding ratio calculation step 40 calculates by the mathematical method in which proportion the base material, the alkali activator and the water should each be mixed.
- the geopolymer was blended by mixing two kinds of alkali activator and water in coal-filled materials, and the Si per unit weight of coal-filled materials and two alkali activators and water, The moles of Al, Na and H have already been calculated in the basic calculation step (20).
- Values for the ratio, a / Ai ratio and water content rate can be used to calculate the amount of coalfill, two alkali activators and water in a mathematical manner. More specifically, to know the Si, Ma, AI and the water content included in each gyeryo, because it is finally determined that the ratio to obtain the status, it is possible seeul linear equations to mathematically the matrix form, each through which The blending amount of the materials can be determined. Mathematically, each material obtained through calculation increases the applicability in the field by expressing the increase ratio.
- the water content can be modified in a certain range in consideration of workability.
- the water content can be determined in the range of approximately 20-25 increments 3 ⁇ 4. That the acceleration -I- content obtained from the L (4. Q) Hefei calculation step means that the hydrogen content in the bovine and sat geo polymer varies.
- the addition of water does not affect the Si i ratio and Na / Al ratio, which are the main factors of the geopolymer in the present invention, so that the flowability of the geopolymer is adjusted to the desired level. It is desirable to match
- the Si / Al ratio, Na / Al ratio and water content of the finally prepared geopolymer are determined in advance. In order to meet this standard, it is possible to determine the mixing ratio of the four raw materials.
- the inventors have geo replicon Murray mix design method consisting of the above-described configuration ⁇ developed to record computer programs made up of computer 3 ⁇ 4 deche form. This computer program calculates the final blended weight ratios for the four raw materials given the input data. Is displayed by
- the user inputs data on the ratio of 3: sex ratio (weight ratio) of SiO ,, Ai 2 0 3 , Na 2 0, 3 ⁇ 40 for the four raw materials: basic raw material, two alkali activators and water. Enter the Si / Al molar ratio > Na / Al molar ratio , water content of the geopolymer.
- the formula for calculating the content of Si, Al, Na, in Si3 ⁇ 4, Al 2 0 St Na, 0, 3 ⁇ 4Q, the change equation for the increase and the molar number, and the matrix for mathematically solving the compounding ratio are included.
- the computer program uses the data to mathematically calculate the blending ratio of the four raw materials (compound ratio calculation step).
- the outermost longitudinal computer displays the four blending weight ratio of the raw material ⁇ monitor.
- the present inventors developed a computer program as described above, and then analyzed the composition of the actual coal landfill material and alkali activator, the target Si / Al ratio, Na! The experiment was performed to obtain the blending ratio of the four raw materials by refraining the ratio of rain and water.
- the experimental example will be described.
- the sample used as the raw material of geopolymer in this experiment is landfill coal discharged from Seocheon thermal power plant.
- the landfill coal ash is mainly buried with seawater in the landfill due to the mixing of large-size retent ash among the bottom ash and fly ash of the thermal power plant.
- the cone and quarter sampling method was used by using a shovel after convection, and the large particles and the particles were mixed evenly, and 20 kg were taken.
- the unburned carbon was removed by the flotation method due to the high unburned carbon content.
- kerosene is used as a foaming agent to keep the air bubbles attached to the unburned carbon powder without being put out.
- the unburned carbon content of samples and flotation was analyzed by a co- analyzer (TGA 601, Leco Corp., US). Unburned carbon was removed from the sample using a rod mill (rod miii). Quantitative X- ray diffraction analysis of the sample is attracted to 7 discrete i 5 teubeop was used DIFFMC 'T0PAS 4.2 (Bruker-AXS , Gern iiy) software. Internal standard material Cakkim Fluoride (CaF 2l 99.985%, Aifa) was added 10wt% of sample weight.
- X-ray diffraction analysis was performed using a D8 Advance diffractomeer (Bruker ⁇ AXS, Germany) with Cu target and LynxEye position sensitive detector. Diffraction patterns were obtained with 3 ⁇ 4 cases of 5 ° to 95 ° 2 ⁇ , 0.0 ⁇ step size, 1 sec per step, and 0.3 ° divergence s! It and 2.5 "' solar slit were used. .
- X-ray stripe patterns were obtained for the sample and the standard sample (La, SRM 660b ; NiS ' f, US) in the same case.
- the chemical composition of the samples was analyzed by X-ray fluorescence spectrometer (X Ray Floiirescence Spectrometer, Shi mad zu Sequent iai XRF ] .800, Shimadzu, Japan), and the contents of amorphous silicon, aluminum, and sodium were calculated.
- A1 2 0 3 19.0 wt%, 3 ⁇ 4052 3 ⁇ 4) was used.
- metacarlin Si0 2 54.60wt, Al 2 0 3 42,71ivi3 ⁇ 4 calcined with a powder of chlorine for 2 hours at 700 t: was also used as a source of aluminum. 24 hours after mixing with water glass and sodium aluminate solution Of coking coal.
- the compounding ratio is amorphous silicon and aluminium in the sample.
- the Si / Al and Na / Ai burs of the geopolymer to be prepared were calculated by a computer program to which the present invention was applied (Table 3).
- the weight ratio of the liquid phase (free water (molar added separately) in the alkali activator) to the weight of the sample was calculated, and the actual kneading of the blend was made using a mini slump cone made in the laboratory. It was measured by. Slum .
- the inner diameter of the bottom of the cone is 38. i ⁇ , the inner diameter of the top is 19 ⁇ , and the cone height is 60.4 ⁇ .
- Geopolymer paste formulations are highly tacky, so they are thinner than cement, filled in mini slump cones, lifted off, separated, and then measured two diameters at the bottom of the floor after two minutes from the perpendicular to each other. Used. If the dough is significantly different, adjust the water content and mix again.
- the upper and lower surfaces of the cylindrical test specimens were polished with sandpaper such that the upper and lower surfaces were perpendicular to the sides and parallel to each other, and the height was 58 ⁇ .
- the microstructure of the geopolymer fracture surface was observed with a scanning electron microscope (JEOL JSM-6380, Japan). Geopolymers were formulated between November 27 and December 1, 2012, and were exposed to air buildup from 4 days after blending to see if whitening was present.
- sample means a state in which carbon is removed.
- the chemical composition of the sample (coated coal ash) is shown in the table of FIG. The sum of si3 ⁇ 4 and A1 2 0 3 content exceeds 70% and the CaO content is less than 20%, and the chemical composition corresponds to Class F fly ash classified in ASTM C618 standard.
- amorphous component analysis result of the landfill coal material of Seocheon thermal power plant calculated from X-ray fluorescence spectroscopy and quantitative X-ray diffraction analysis.
- the content of amorphous silica was 36.8wt% and the content of amorphous alumina was 12.8 3 ⁇ 4, so the amorphous Si / Al ratio was 2.44. It was decided. Therefore, to prepare a geopolymer having a Si / Al ratio of less than 2.44, a solid sodium aluminate or sodium aluminate solution or metakaolin to supply aluminum was added, and water glass and NaOH were used when the Si / Al ratio was 2.5 and 3.0 ( See table in FIG. 3).
- the compressive strength of the geopolymer made under the conditions shown in the table of FIG. 3 is shown in the graph of FIG. Compressive strength is the average of four specimens and the standard deviations are indicated.
- the Si / Al ratio of the geopolymers were mixed with 2.0 and Na / Al ratios of 0.8 (sample 20AS, 20NaAl, 20MK) using different raw material combinations, the bottom diameter of the slumped compound after the mini slump test was similar in all three samples. In the case of 20AS sample, it was measured in the range of 40 ⁇ 40 ⁇ .
- the average compressive strength was 11.2 MPa (standard deviation 0.9 MPa) for 20AS sample using sodium aluminate solution and NaOH, and 12.3 MPa (standard deviation l. OMPa) for 20NaAl sample using solid sodium aluminate and NaOH. Indicated. Considering the standard deviation, there is no significant difference between the use of sodium aluminate as a solid and the solution. Therefore, it would be advantageous to use different solid aluminates rather than solutions that are difficult to store and transport. In addition, it will be easier to commercialize in that geopolymer is made by pouring only water such as forland cement using solid aluminate.
- the average compressive strength of the 20MK sample using metakaolin instead of sodium aluminate as a source of aluminum was 9.1 MPa (standard deviation 2.0 MPa).
- the mechanical properties were slightly lower than those used.
- metakaolin is amorphous, but the short-range order is still maintained to some extent, which may be because the amount of semi-aluminum silica and alumina actually involved in the reaction was less than expected. It may be because aluminum is supplemented with meta-caline rather than sodium aluminate, so that the amount of alkali is relatively low.
- the water content was 23 wt% when the liquid alumina soda was used, but similar flowability was obtained when the water content was slightly increased to 24% when the solid aluminate was used (see the table in FIG. 3).
- metakaolin should have increased the water content to 25%, due to the large specific surface area of the metakaolin particles and the plate-like particle shape, the water ratio required for the formulation should be high, and in fact the amount of free water was highest (Table 3) may be the reason why the strength of the 20MK sample is somewhat lower among the three samples.
- the average compressive strength was 3.53MPa (standard deviation 0.8MPa).
- the 30SS-23 geopolymer sample with a Si / Al ratio of 3.0 showed an average compressive strength of 10.3 MPa (2.5 MPa for spring deviation), which was higher than 25 SS and similar to 20AS, despite the thin dough.
- the 30SS-21 sample which had the same Si / Al and Na / Al ratios but reduced the water content by 2wt3 ⁇ 4, was spread to 39 ⁇ 45 ⁇ ⁇ in the mini-sulfum test, showing a dough similar to the 25SS sample.
- the average compressive strength of the 30SS-21 sample was 17.9MPa (standard deviation 1.2MPa), which was nearly 5 times higher than 3.5MPa of the 25SS sample.
- Factors affecting the compressive strength of geopolymers are Si / Al and Na / Al ratios, the type and content of alkali metal ions, the size and distribution of unreacted Al-Si particles, and the surface reaction with geopolymer gels, water Content is known.
- the Si / Al ratio of 2.0 geopolymer showed 9 ⁇ llMPa compressive strength, while 2.5 geopolymer showed 3.5MPa and 3.0 geopolymer showed 17.9MPa. It got worse and got better.
- the reactive Si / Al ratio of the coal ash used as the raw material of the geopolymer is 2.44, two kinds of alkalis (sodium aluminate and NaOH) were added to supply aluminum from the alkali to make the geopolymer 2.0. In the case of 2.5, water glass and NaOH were added, and in the case of 3.0, two kinds of alkalis including water glass and NaOH which could supply silicon were added (see table in FIG. 3).
- the 25SS sample was able to produce a geopolymer with a Si / Al ratio of 2.5 with a small amount of alkali. That is, since the amount of aluminum supplied from the alkali 3 ⁇ 4-forming agent was small (1.9 wt% of water glass, 5.0 wt% of NaOH, see FIG. 3), semi-aluminum of coal ash was melted to participate in the geopolymer reaction.
- the three samples showed no significant difference in the degree of adhesion between the crystalline particles and alkali polymers, which were not reacted with alkali.
- High compressive strength geopolymers have low porosity and are compact, exhibiting fine microstructure.
- the amount of silica solution added to the 30SS-23, 30SS-21, and 30SS-19 samples was 15.7-16.5 3 ⁇ 4, but there was no significant difference, but 1.9 3 ⁇ 4 of the 25SS sample was much higher (Table 3). In other words, when the silica content in the alkaline solution is high, the fine microstructure appears to develop, which is consistent with the existing research results.
- the chemical composition and flow control of geopolymers is a very important technique for the commercialization of geopolymers.
- the Si / Al ratio of the geopolymer was better than the reactive Si / Al ratio of the coal ash, which resulted in better compressive strength.
- the geopolymer formulation design method according to the present invention is a Si / Al ratio, Na / Al ratio of factors that have a significant effect on the physical properties of the geopolymer in the state of pre-set, the set value of these factors It provides a method to calculate the blending quantity of the satisfying geopolymer raw materials.
- This provides a more scientific and systematic approach to geopolymer formulations, and provides an active research base for geopolymer structures and properties using specimens prepared from formulation designs according to the major factors of geopolymers.
- the scientific compounding design according to the present invention can improve the economics of the use of raw materials, it is possible to adjust the factors that may cause problems such as the stability of the whitening of the produced geopolymer.
- the present invention is expected to contribute to the revival of the geopolymer industry by providing the most important and fundamental data on the properties of geopolymers.
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Abstract
The present invention relates to a geopolymer mix design method. The geopolymer mix design method according to the present invention for determining the mixing ratio of a geopolymer prepared by mixing a basic material containing an aluminosilicate component, an alkaline activator and water comprises: a material analysis step for selecting a basic material and an alkaline activator and analyzing the chemical composition; a basic calculation step for calculating the respective number of moles of Si, Al, Na and H per unit weight of the materials; a target setting step for setting standard values with respect to main factors including the Si/Al molar ratio and the Na/Al molar ratio in the finally prepared geopolymer; and a mixing ratio calculation step for calculating, on the basis of the result calculated at the basic calculation step, the mixing ratio of respective materials so as to meet the standard values of the main factors, which are set at the target setting step, in a mixture obtained by mixing the materials.
Description
【명세서 ϊ [Specification ϊ
【발명의 명칭】 [Name of invention]
지오폴리머 배합 설계방법 Geopolymer formulation design method
【기슬분야】 【Field of Energy】
본 발명은 건축 및 토뜩 재료인 지오플리머에 관¾한 기술로서, 특히 지오폴 리머의 각 성분들의 배합비율을 최적화할 수 있는 지오플리머 배합 설계방법에 관 한 것이디- . The present invention relates to a technology for construction and geoplymers, and particularly to a method for designing a geopolymer composition that can optimize the mixing ratio of each component of the geopolymer.
【배경기슬, 3 지오폴리머는 알루미노 실리케이트 원료와 알칼리활성화제의 화학 반응만으 로 저은에서 경화되는 무기결합재 증 하나이다. 지오폴리머의 생산에는 소성 과정 이 필요 없기 때문에 포를랜드 시¾트와 비교할 때 생산에 필요한 에너지 소모량이 휠씬 적을 뿐만 아니라 이산화탄소 배출량도 80% 이상 감축할 수 있어 친환경적인 재료로 각광받고 있다ᅳ [Background Gas, 3 Geopolymer] is an inorganic binder that hardens in low silver only by chemical reaction between aluminosilicate raw material and alkali activator. Since the production of geopolymers does not require a firing process, the energy consumption required for production is much lower than that of the Forland sheet, and carbon dioxide emissions can be reduced by more than 80%.
그러나 지오폴리머에 대한 과학적 접근이 체계적으로 뒷받침되지 않은 상태 에서 당장의 산업적 활용에만 관심을 두고 현장 중심의 연구가 주도적으로 수행된 결괴■ 지오를리머 '에 대한 정확한 개념적 합의도 없이 버소성 무기결합재라는 넓은 의미로혼용되고 있다. 정확한 개념의 지오플리머는 알칼리활성화제와 반응시켜 제 3:되는 무기결합 재들 중에서 포졸란 톡성을 가지는 원료로 제조되는 것으로서 비정질 특성을 갖는 재료를 의미힌다. 즉, 화력발전소의 비산재와 바닥재, 메타카을린, 소다석회 유리
질 시맨트, 천연 포졸란, 연탄재 등이 지오 리머의 원료기- 될 수 있다. 그러나 고로슬래그를 주원료로 사용하는 경우 시맨트 광몰과 유사한 C-S-H 갤이 주요 반응 물로 생성되기 때문에 이는 개념적으로지오쁠리머에 해당하지 않는다. However, that scientific approach to geo-polymers are concerned only the industrial utilization of the right in a state that is not backed by systematic field-oriented research has been directed to perform gyeolgoe ■ Geo a dreamer 'precise conceptual agreement also buggy firing weapons without for the binder It is mixed in a broad sense. Geopolymer of the correct concept refers to a material having amorphous properties as being made of a raw material having pozzolanicity among the inorganic binders which are reacted with an alkali activator 3: That is, fly ash, flooring, metacarlin, and soda-lime glass in thermal power plants. Jill Semant, natural pozzolanics, briquettes and the like can be used as raw materials for georeamers. However, when blast furnace slag is used as the main raw material, it is conceptually not a geoplasmer because CSH galls similar to the Semanite Mall are produced as the main reactants.
상기한 바와 같이, 지오폴리머에 대한 연구가 즉각적인 현징ᅳ 적용성을 중심 으로 편향되게 이루어지고 있다. 지오폴리머 연구논문들은 대부분 원료의 화학조 성이나 성상에는 관계없이 알칼리활성화제의 몰농도를 일정하게 증가시켜 반응시 ¾ 후 압축강도의 변화를 연구하는데 촛점이 맞추어져 있다. 예컨대 지오폴리머의 원 재료인 석탄재의 경우 · 석탄의 연소조건, 석탄재에 함유된 광물의 종류와 함량, 입 자의 크기와 형태;, 석탄재의 보관상태 등에 따라 알칼리에 대한 반웅성이 매우 다 르기 때문에 , 지오폴리머의 물성은 알칼리활성화제의 농도 이외에도 많은 다양한 조건들에 의하여 결정된다. 그러나 지오풀리머의 물성, 반응성을 결정하는 인자들 에 대한 과학적 규명 없이 경험적인 토대 위에서 지오플리머를 연구하고 있다. 이렇게 경험적 배합에 기초하여 강알칼리 ᅳ 사용하여 만들어진 지오폴리머는 품질어 일정하지 않을 뿐만 아니라, 과량의 알칼리 사용으로 인해 안전문제가 있으 며, 제조단가도 상숭하.게 된다. 예¾대, 강알칼리를 많이 사용하면 과량의 나트 이 공극용액 (pore SQkltlOR) 내에 남게 되며, 시간의 경과에 따라 나트륨은 공기 중의 이산화탄소와 반웅하여 지오폴리머 표면에 백화현상 (eif iorescence)을 일으키 계 된다. As mentioned above, research on geopolymers has been biased around immediate applicability. Most geopolymers research papers focus on studying the change in compressive strength after reaction by increasing the molar concentration of alkali activator constant regardless of chemical composition or properties of raw materials. For example, in the case of coal ash, which is a raw material of geopolymer, the reaction properties against alkali are very different depending on the combustion conditions of coal, the type and content of minerals contained in coal ash, the size and shape of particles, and the storage condition of coal ash. The physical properties of geopolymers are determined by many different conditions besides the concentration of alkali activator. However, he studies geoplymers on an empirical basis without scientifically identifying the factors that determine the properties and reactivity of geoplymers. Based on the empirical formulation, geopolymers made using strong alkalis are not only consistent in quality, but also have safety problems due to the use of excess alkali, and the manufacturing cost is high. For example, if a lot of strong alkali is used, excess Nat will remain in the pore SQkltlOR, and over time, sodium will react with carbon dioxide in the air, causing eif iorescence on the surface of the geopolymer. .
따라서 지오폴리머의 특성에 영향을 미치는 인자들에 대한 과학적 분석이 요 구되며, 이를 기초로 표준화된 지오플리머 배합 설계 방법이 마련될 필요가 있다.
[발명의 상세한 설명】 Therefore, scientific analysis of factors influencing the properties of geopolymers is required, and it is necessary to prepare a standardized method for designing a geopolymer blend based on this. Detailed description of the invention
【기술적 과제】 [Technical problem]
본 발명은 상기한 문제점을 해결하기 위한 것으로서, 지오 «리머의 물성에 영향을 미치는 인자들의 기준값을 미리 설정하고, 이 기준값을 만족할 수 있는 지 오폴리머가 생산될 수 있게 하는 원재료의 배합 비율을 미리 산출할 수 있는 지오 폴리머 배합설계방법을 제공하는데 그 목적이 있다. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and sets in advance the reference values of the factors affecting the properties of the geo «reamer, and premixes the blending ratio of the raw materials to allow the geopolymer to be produced that can satisfy this reference value. The purpose is to provide a geopolymer formulation design method that can be calculated.
【기슬적 해결방법】 【Esoteric Solution】
상기 목적을 달성하기 위한본 발명에 따른 지오폴리머 배¾' 설계방법은, 알 루미노 실리케이트 성분이 포함된 기본원료와, 알칼리활성화제 및 물을 혼합하여 제조되는 지오폴리머의 배합비을을 결정하기 위한 것으로서, 싱-기 기본원료와 알칼 리활성화제 » 선택하여 화학조성을 분석하는 원료분석단계; 상기 기본원료, 얕칼리 활성화제 및 물의 단위 무게당 Si, Al, Na 및 H에 대한 각각의 몰수 (moie)를 산출 하는 기본산출단계; 최종적으로 제조되는 지오폴리머 내 Si/A! 몰비 (raole ratio) 및 Na/Al 몰비를 포함하여 지오폴리머의 특성을 결정하는 주요 인자들에 대한 기준 값을 설정하는 타겟설정단계; 및 상기 기본산출단계에서 산출된 결과를 기초로, 상 기 기본원료: 알칼리활성화제 및 물을 배합한 흔합물에서 상기 타겟설정단계에서 설정된 주요 인자의 기준값을 만족시킬 수 있도특 상기 기본원료, 알칼리활성화제 및 물에 대한 각각의 배합비를 산출하는 배합비산출단계;를 포함하여 이루어진 것 에 특징이 있다. Geo-polymer-fold ¾ 'design method according to the present invention for achieving the above object, as for determining the baehapbieul of geo polymer are prepared by mixing the base material containing the Al luminometer silicate component, an alkali activator and water A raw material analysis step of selecting a basic raw material and an alkali reactivator »and analyzing the chemical composition; A basic calculation step of calculating the moles of each of Si, Al, Na and H per unit weight of the basic raw material, shallow cal activator and water; Si / A in the final geopolymer produced! A target setting step of setting reference values for key factors that determine the properties of the geopolymer, including the molar ratio and the Na / Al molar ratio; And based on the result calculated in the basic calculation step, the basic raw material : in the mixture containing the alkali activator and water, the basic raw material and alkali may satisfy the reference values of the main factors set in the target setting step. Characterized in that made, including; compounding ratio calculation step of calculating the respective compounding ratio for the activator and water.
【유리한 효과】
본 발명에 따른 지오플리머 배합 설계방법은 지오폴리머의 물성에 중요한 영 향을 미치는 인자인 Si Ml 비율, a/Al 비율 및 물함량비 * 미리 설정한 상태에서, 이 인자들의 설정값을 만족할 수 있는 지오를리머 원료들의 배합량을 산출할 수 있 는 방법을 제공한다. Advantageous Effects According to the present invention, the method of designing the blender of the geopolymer may satisfy the set values of the Si Ml ratio, the a / Al ratio and the water content ratio, which are factors which have a significant influence on the physical properties of the geopolymer. It provides a method to calculate the blending amount of geol reamer raw materials.
이에 따리- 지오폴리머 배합에 있어서 보다 과학적이고 체계적인 접근 가능성 을 제공하며 , 지오폴리머의 주요 인자들에 따른 배합설계로부터 제조된 공시체를 이용하여 지오폴리머의 구조와특성에 대한 활발한 연구 기반을 마련할수 있다ᅳ 또한, 본 발명에 따른 과학적 배합설계를 통해 원료 사용의 경제성을 도모할 수 있으며, 제조되는 지오폴리머의 백화현상 등 안정성에 문제를 즐 수 있는 요소 e ΪΪ -i- s. ¾·: 1 ΑΛ "1 . This provides a more scientific and systematic approach to geopolymer formulations and provides a foundation for active research into the structure and properties of geopolymers using specimens prepared from formulation designs according to the major factors of geopolymers. ᅳ In addition, through the scientific blending design according to the present invention, it is possible to improve the economics of using raw materials, and to enjoy stability problems such as the whitening of the produced geopolymer. E ΪΪ -i- s. ¾ ·: 1 ΑΛ "1.
본 발명은 지오폴리머의 특성에 있어서 가장 중요하면서도 기본적인 데이터 를 제공함으로써 지오폴리머 산업 부홍에 기여할수 있을 것으로 기대된다.. The present invention is expected to contribute to the geopolymer industry by providing the most important and basic data on the properties of geopolymers.
ί도면의 간단한 설명】 Brief description of the drawing]
도 i은 본 발명의 일 실시예에 따른 지오폴리머 배합 설계방법의 개략적 흐 름도이디- . I is a schematic flow diagram of a geopolymer formulation design method according to an embodiment of the present invention.
도 2는 지오폴리머의 Si/ 비율에 따른사용용도가 나타나 있는표이디-. 도 3은 본 발명에 대한 실험의 설계 데이터 및 결과 데이터가 나타나 있는 표이다, Figure 2 is a table showing the use of the geopolymer according to the Si / ratio-. 3 is a table showing the design data and the result data of the experiment for the present invention,
도 4의 시료 (매립 석탄재)의 화학조성을 나타낸 표아다. It is a table which shows the chemical composition of the sample (filled coal ash) of FIG.
도 5는 시료에 대한정량 X-선 회절 분석 결과 그래프이다.
도 6의 그래프는 X 형광분광 분석과 정량 Xᅳ선 회절 분석으로부터 계산한 서천화력발전소 매립석탄재의 비정질 성분분석 결과이다. 5 is a graph of the quantitative X-ray diffraction analysis results for the sample. 6 is an amorphous component analysis result of the landfill coal material of Seocheon Thermal Power Plant calculated from X-fluorescence spectroscopy and quantitative X-ray diffraction analysis.
도 ?은 도 3의 쬬에 나타난 조건으로 만들어진 지오폴리머의 압축강도를 나 타낸 그래프이다, Figure 3 is a graph showing the compressive strength of geopolymer made under the conditions shown in Figure 3,
도 8의 (a) 내지 (c)는 3개의 시료에 대한 주시 -전지■현미경으로 관찰한 피-단 면의 사진이다. 8 (a) to 8 (c) are photographs of blood-sections observed with a gaze-cell ■ microscope for three samples.
도 9는 4가지 지오 리머 ¾ 시료의 파단면을 주사전자현미경으로 찍은 사진 이디- . 9 is a photograph taken with scanning electron micrographs of fracture surfaces of four georeamer ¾ samples.
【발명의 실시를 위한 최선의 형태】 [Best form for implementation of the invention]
상기 목적을달성하기 위한 본발명에 따른 지오폴리머 배합 설계방법은, 알 루미노 실리케이트 성분이 포함된 기본원료와 알¾리활성화제 및 물을 흔합하여 제조되는 지오폴리머의 배합비을을 결정히-기 위한 것으로서, 싱 ·7ᅵ 기본원료와 알칼 리활성화제를 선택하여 화학조성을 분석하는 원료분석단계 ; 싱-기 기본원료. 알칼리 활성화제 및 물의 단위 무게당 Si. Al, Na 및 H에 대한 각각의 몰수 (roole)를 산출 하는 기본산출단계; 최종적으로 제조되는 지오폴리머 내 Si/A! 몰비 (mo!e ratio) 및 Na/Al 몰비를 포함하여 지오폴리머의 특성을 결정하는 주요 인자들에 대한 기준 값을 설정하는 타¾설정단계; 및 상기 기본산출단계에서 산출된 결과를 기초로, 상 기 기본원료, 알칼리활성화제 및 물을 배합한 흔합물에서 상기 타겟설정단계에서 설정된 주요 인자의 기준값을 만족시킬 수 있도특 상기 기본원료, 알칼리활성화제 및 물에 대한 각각의 배합비를 산출하는 배합버산출단계:를 포함하여 이루어진 것
에 특징어 있다. Geopolymer blending design method according to the present invention for achieving the above object, to determine the blending ratio of the geopolymer produced by mixing a basic raw material containing an aluminosilicate component, an al ¾ reactivator and water as, dicing material analysis step of analyzing the chemical composition by selecting the base material 7 i and the alkaline activator; Singh-ki basic raw materials. Si. Per unit weight of alkali activator and water. A basic calculation step of calculating the number of moles of each of Al, Na, and H; Si / A in the final geopolymer produced! A third step of setting reference values for key factors that determine the properties of the geopolymer, including the mo! E ratio and the Na / Al molar ratio; And based on the result calculated in the basic calculation step, the basic raw material, alkali may satisfy the reference value of the main factor set in the target setting step in the mixture containing the basic raw material, alkali activator and water. Comprising the step of calculating the respective compounding ratio for the activator and water: consisting of It is characterized by.
본 발명에 따르면 상기 타겟설정단계에서 상기 지오폴리머의 특성을 결정하 는 주요 인자는 물함량비를 더 포함하는 것이 바람직하다. According to the present invention, it is preferable that the main factor for determining the characteristics of the geopolymer in the target setting step further includes a water content ratio.
또한ᅳ상기 원료분석단계에서는 상기 기본원료로부터 미연탄소분을 제거하는 전처리를 수행하며 , 상기 기본산출단계에서는 상기 기본원료에서 결정질로 존재하 는 부분을 제외하고, 비정질로 존재하는 부분에 대해서만 Si, Al, Na 및 H에 대한 각각의 몰수 (mole)를 산출하는 것이 바람직히 -다. In addition, in the raw material analyzing step, pretreatment is performed to remove unburned carbon powder from the basic raw material, and in the basic calculating step, only Si, Al are present in the amorphous part except for the crystalline part of the basic raw material. It is preferred to calculate the respective moles for, Na and H.
특히, 싱-기 기본산출단계예서 Si, Al, Na. H의 함량을 산출하기 위하여, 상 기 기본원료와 첨가제 및 물에 각각 포함되어 있는 Ai203, Si¾' Na20, ¾0의 세부성 분 함량을 파악한 후, 상기 세부성분들에 포함되어 있는 Si, Al; Na, H의 몰수를 합하여 산출하는 것이 바람직하다. In particular, the singular-base calculation step is Si, Al, Na. In order to calculate the content of H, the contents of Ai 2 0 3 , Si¾ ' Na 2 0, ¾0 contained in the basic raw materials, additives, and water, respectively, were determined, and then, Si, Al ; It is preferable to calculate the sum of the moles of Na and H.
그리고 > 상기 기본산출단계에서는 상기 기본원료의 Si/Al 몰비 및 Ma/Ai 몰 비를 분석한 후, 상기 타겟설정단계어 I서는 상기 Si l 몰비 기준값을 상기 기본 ¾ 료의 SI/A1 몰비에 버하여 더 높? 도는 낮게 설정하는 것이 바람직하다. And> the basic calculation step, after the analysis of the Si / Al molar ratio of the base material and Ma / Ai molar ratio, the target setting standing phase control I member of the Si l molar ratio reference value in the SI / A1 molar ratio of the basic ¾ fee Higher? It is preferable to set the degree low.
본 발명의 일 실시예에서 > 상기 알칼리선택단계에서 알칼리활성화제로서 알 루민산소다를 선택함에 있어서, 고체 상태의 앞투미산소다 분말을 선택한다. In one embodiment of the present invention > In selecting the sodium aluminate as the alkali activator in the alkali selection step, the front-to-acid sodium powder in the solid state is selected.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
이하 첨부된 도면을 참고하여ᅳ 본 발명의 일 실시예에 따른 지오폴리머 배 합 설계방법에 대하여 더욱 상세히 설명하기로 한다.
도 1은 본 발명의 일 실시예에 따른 지오 ¾리머 배합 설계방법의 개략적 흐 름도이다-. Hereinafter, a geopolymer composition design method according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. 1 is a schematic flowchart of a geo ¾ reamer formulation design method according to an embodiment of the present invention-.
본 발명의 일 실시예에 따른지오폴리머 배합 설계방 ¾αοο)은지오폴리머의 재료언 기본원료의 ·, 알칼리활성화제 및 몰에 대한 상대적 배합비를 결정하기: 위한 것으로서, 도 ᅵ에 도시된 바와 같이, 전처리단계 (10), 원료분석단계 (20), 기본산출 단계 (30), 타겟설정단계 (40), 배합비산출단계 (40)를 구비한다. Geopolymer formulation design method according to an embodiment of the present invention (¾αοο) is to determine the relative blending ratio of · , alkali activator and mole of the base material raw materials of the geopolymer, as shown in FIG. It comprises a pretreatment step (10), raw material analysis step (20), basic calculation step (30), target setting step (40), compounding ratio calculation step (40).
본 발명에서는 우선 지오폴리머의 기본원료와 알칼리활성화제를 선택하고, 이들의 화학조성을 분석하는 원료분석단계 αω를 수행한다, In the present invention, first select the basic raw material and alkali activator of the geopolymer, and performs the raw material analysis step αω to analyze their chemical composition,
지오폴리머의 기본원료는 알루미노 실리케이트 성분으로 이루어지며, 포졸란 특성을 가지는 물질이다. 기본원료로 사용가능한 물질은 화력발전소의 비산재 (fly ash)나 바닥재 (bottom ash) , 연탄계, 에타카을린 ( etakaol inj , 천연 포졸란재 (부 석 (pumice)이나 화산재) 등이 있다. 이들은 모두 잠채수경성을 가지며 알칼리활성 화제에 의하여 활성화된다. 본 발명에서는 기본원료를 석탄데립재로 상정하여 설 명하기로한다-. The basic raw material of the geopolymer is composed of aluminosilicate components and is a material having pozzolanic properties. Materials that can be used as basic raw materials include fly ash, bottom ash, coal briquettes, etakaol inj and natural pozzolanic ash (pumice or volcanic ash) from thermal power plants. It is submerged in water and activated by an alkali activating agent.
알칼리활성화제는 석탄매립재와 반웅하는 염기성 물질로세 수산화나트 f (NaOH).. 물유리 (N Si ᅳ H20), 알루민산소다 분말 (NaAK^), 알루민산소다 용 액 (NaAi ' n¾0) 등이 있다. 알칼리 ¾성화제는 단수로 사용할 수도 있지만. 2개 이상의 복수로 사용할 수도 있다. 본 실시예에서는 2개의 알칼리활성화제를 사용 하였다.
기본원료와 알칼리활성화제를 선택한 후에는 기본원료에 대한 전처리를 수행 한다, 전처리란 석탄메립재를 적당한 입도로 분쇄하고 미연탄소분을 제거하기 위 한 것이디, 다만, 석탄매립재에 미연탄소분 함량이 낮은 경우 전처리를 생략해도 무방하다. 미연탄소분을 제거하기 위한 방법은 다양한테, 예컨대 부유선 ¾¾ 법 (froth flotation)을 사용할 수 있다、 부유선1 법은 선광법의 하나로서 광물 표 면의 소수성과 친수성의 차이를 이용, 공기거 -(air bubble)에 선택적으로 소수성 광물 입자를 부착시켜 분리하는 방법이다ᅳ 즉, 유체와 함께 석탄매립쟤를 수조에 수용한 후 포집제와 기포제를 주입하고, 기포를 블어 넣으면 기포가 미연탄소분에 부착되어 수조의 표면으로 부유되어 석탄매립재로부터 미연탄소분을 제거할 수 있 다ᅳ Alkali activator is a basic substance that reacts with coal landfill. Nath hydroxide f (NaOH). Water glass (N Si ᅳ H 2 0), Sodium aluminate powder (NaAK ^), Sodium aluminate solution (NaAi 'n¾0 ). Alkaline foaming agents can be used singly. You may use it in two or more plurality. In this example, two alkali activators were used. After selecting the base material with an alkaline activator performs pre-processing for the main raw material, pre-treatment is di to the above to crush the coal methoxy ripjae a suitable particle size and to remove the non-drawn tansobun, however, the tansobun content of unburnt coal in the buried material If low, the pretreatment may be omitted. There are various methods for removing unburned carbon dust, such as the flotation of the flotation. The flotation method 1 is one of the beneficiation methods, which utilizes the difference in hydrophobicity and hydrophilicity of the mineral surface. It is a method of selectively attaching hydrophobic mineral particles to an air bubble to separate them. That is, coal-filled land with a fluid is injected into a tank, and a collecting agent and a foaming agent are injected, and when bubbles are blown, bubbles adhere to unburned carbon powder. It floats to the surface of the tank and can remove unburned carbon powder from coal landfill.
전처리가 끝나면 석탄매립재의■ 알칼리활성화제의 화학조성을 분석한다, 석 탄메립재와 알칼리활성화제에 포함된 성분이 무엇인지를 파악하는 것은 지오플리머 의 과학쩍 배합 설계에 있어서 반드시 요구되는 사항이다. 화학조성 분석은 후술 할 기본산출단계에서 기본원료와 알칼리활성화제의 Si, Al, Na. H의 몰버를 파악하 는 과정과 연결된다. 기본원료와 알칼리활성화제의 Si, Al, Na. H는 순수한 원자 형태로 존재하는 것이 아니라 Si¾, Α1-,¾, Ν 0, 0와 같이 산화물 형태로 존재하 므로 원료분석단계 (Κ))에서는 이 산화물의 조성비율을 먼저 파악하여야 한다、 기 본원료와 알칼리활성화제 내 위 산화물들의 조성비율은 다양한 방법으로 파악될 수 있으며, 본 실시예와 같이 X—선형광분석기 (X™fciy flourescene Spectrometer) 등 계
측장비를 통해 파악가능하다, After the pretreatment, ■ analyze the chemical composition of the alkali activator of the coalfill material. Identifying what is contained in the coal filler and the alkali activator is essential for the scientific design of geopolymer. Chemical composition analysis of the basic raw material and alkali activator Si, Al, Na. This is linked to the process of identifying the H's mobilizer. Si, Al, Na. Of basic raw material and alkali activator. Since H does not exist in pure atomic form but in oxide form such as Si¾, Α1-, ¾, Ν 0, 0, the composition ratio of this oxide must be determined first in the raw material analysis step (Κ ) . The composition ratio of the above oxides in the raw material and the alkali activator can be determined by various methods, such as the X ™ fciy flourescene spectrometer as in this embodiment Can be identified through side equipment,
중요한 점은, 석탄메립재 전체에 대해서 위 산화물의 조성비를 과악하는 것 이 아니라, 석탄매립재 증에서 결정질을 제외한 버정질 부분에 대해서만 파악한다 는 것이다. 위 물질들이 결정질로 존재하면 알칼리 «성화제와의 지오폴리머 반웅 에 참여하지 않기 때&에 배합설계에서 의미가 없기 때문이다. Importantly, the composition ratio of the above oxides is not exaggerated for the entire coal landfill material, but only for the amorphous part of the coal landfill material except for the crystalline material. This is because the presence of these materials as crystalline makes no sense in the formulation design because they do not participate in geopolymer reactions with alkalinizers.
예컨대, 석탄계속에 함유된 SK)2는 버정질과 결정질이 흔재되어 있는데 , XRF 로 전체 Si()2 함량을 분석한후에 다시 XRD로 결정질 Si¾ 함량을 결정한다. 이 두 값의 차이가 비정질 SI02함량어므로 이 값만 배합버 계산에 사용한다. 그리고 알¾리활성화제들 중 수산화나트륨이나 알루민산 소다용액 등은 이 미 그 조성비 이 알려져 있다. 예컨대, 2몰의 NaOH는 각각 1몰의 Ν¾0외ᅳ ¾0가 포 함되어 있다, For example, SK) 2 contained in coal continuum is common in crystallinity and crystalline. After analyzing the total Si () 2 content by XRF, the crystalline Si¾ content is determined by XRD again. Since the difference between these two values is the amorphous SI0 2 content, only these values are used for the calculation of the blender. And the composition ratio of sodium hydroxide or alumina soda solution among al¾ reactivators is already known. For example, two moles of NaOH each contain one mole of Ν¾0 and ¾0.
상기한 바와 같이, 기본원료인 석탄매립재와 알칼리활성화제에 대한 화학조 성 분석을 기초로 기본산출단계 (20)를 수행한다. 기본산출단계 (20)에서는 기본원 료의 단위 무게당 Si, Al, Na, H의 함량을산출한다. As described above, the basic calculation step 20 is performed based on the chemical composition analysis of the coalfill material and the alkali activator which are the basic raw materials. In the basic calculation step (20) calculates the content of Si, Al, Na, H per unit weight of the base material.
원료분석단계 (10)에서 산화물의 조성비을에 대해서 과악어 완료된 상태이므 로, 각 산화물의 화학식을 고려하여 수학적 계산을 통해 기본원료의 단위 무게당 Si, Al, Ma, fl의 함량을 쉽게 산출할수 있다ᅳ 여기서, 함량이라는 것은 규소, 알 루미늄, 나트륨, 수소 성분의 몰수 또는 증량을 의미한다. 원자량을 알고 있는 상 태에서 중량과 몰수 사이의 변형은 얘우 간단하므로 어떤 단위를 사용하여도 무방
하다. 본 실시예에서는 석탄메립재의 단위 무게당 각 성분의 몰수를 산출한다, 간단하게 예를 들어 설명한다, 석탄매립재 내 . 는 40중량 ¾의 비을로 혼 합되어 있다고 가정하면, 석탄매립재 1kg에는 400g의 Si 가 포함된 것이며, Si의 Since the composition of the oxide in the raw material analysis step (10) is a complete crocodile for the state, the content of Si, Al, Ma, fl per unit weight of the basic raw material can be easily calculated through a mathematical calculation considering the chemical formula of each oxide. ᅳ Here, the content means the number of moles or increase of the silicon, aluminum, sodium, and hydrogen components. The deformation between weight and mole number is simple with the atomic weight known, so any unit can be used. Do. In this embodiment calculates the number of moles of each component per unit weight coal ash merip, will be briefly described, for example, within the embedding material coal. Assuming that 40 wt% of ¾ is mixed, 1 kg of coal landfill contains 400 g of Si.
¾자량은 14이고 산소의 원자량은 8(산소분자를 형성했으므로 16)이므로, Si¾ 내 Since the molecular weight of ¾ is 14 and the atomic weight of oxygen is 8 (16 because it formed oxygen molecules),
Si의 증량은 400x(W/30)= 86.6g 정도가 된다. 어¾ 규소의 원자량인 14로 나누 어 몰수로 환산하면 13.2몰이 된다. 즉, 석탄매립재 1kg에 포함된 규소의 몰수는 13.2가 된다. The increase of Si is about 400x (W / 30) = 86.6g. Divide by 14, the atomic weight of ¾ silicon, to 13.2 moles. That is, the number of moles of silicon contained in 1 kg of coal landfill is 13.2.
또한, 기본산출단계 (20)에서는 기본원료 내 각 성분들의 몰수를 산출한 것을 기초로, 석탄매립재의 단위 무게당 Si/A! 몰비와, Na/Al 몰비를 산출하여 추후 타 겟설정단계에서 이용할수 있다. 이에 대해서는뒤에서 설명하기로 한다. In addition, the basic calculation step (20) is based on the calculation of the number of moles of each component in the base material , Si / A! The molar ratio and the Na / Al molar ratio can be calculated and used later in the target setting step. This will be described later.
기본산출단계 ( ))를 통해 기본원료 내 규소, 알루미늄, 나트 · 및 수소의 단 위 무게당 몰수를 파악한 후에는 타갯설정단계 (30)에서 최종적으로 제조하고자 하 는 지오폴리머의 주요 인자에 대한 기준값을 설정한다. After determining the number of moles per unit weight of silicon, aluminum, nat, and hydrogen in the basic raw material through the basic calculation step ( ) , the reference values for the main factors of the geopolymer to be finally prepared in the batch setting step (30) Set.
지오폴리머는 Si04와 Ala; 사면체에 산소 원자가 교대로 공유하여 네트워크 구조를 형성한다. 즉, 연속되는 SiO.,사면체 구조에서 Si를 A!이 치환하는 형태이 다. 그리고 Si는 4가의 전하를 가지는 반면, Ai은 3가의 전하를 가지므로, 나트 륨 (Na)이나칼륨 (K)과 같은 1가 양이은이 추가적으로 결합되는 구조를 형성한다. Geopolymers include Si0 4 and Ala; Oxygen atoms alternately share in the tetrahedron to form a network structure. That is, A! Is substituted for Si in a continuous SiO., Tetrahedron structure. Since Si has a tetravalent charge while Ai has a trivalent charge, a monovalent bivalent silver such as sodium (Na) or potassium (K) is further formed.
이에 지오폴리머의 SI/A1 비을과、 Na/Al 비율은 구조적으로 데우 중요한
의미를 가지며, 지오플리머외 물성을 결정하는데 주요 인자로 작용한다. 여기서The ratio SI / A1 and Na / Al of geopolymers are important for structural warming. It has a meaning and acts as a major factor in determining the properties of the geoplymer. here
Si/Al 비율이나 Na/Al 비율은 몰비를 의미하지만, 실리콘, 알루미늄, 나트륨의 원 자량을 알고 있으므로중량비를사용할수도 있다ᅳ Si / Al ratio or Na / Al ratio means molar ratio, but the weight ratio can be used because it knows the atomic weight of silicon, aluminum and sodium.
종래기술에서도 설명한 바와 같이, 기존의 연구는 알칼리활성화제의 다변화 에 따른 강도의 변회ᅵ나 알칼리 ¾성화제의 농도 변화에 하른 압축강도 특성에 대해 서만 편향적으로 이루어져 왔다. 이에 본 발명은 지오플리머 내 Si/Ai 비율, Na/Al 비을과 같이 지오폴리머의 회 -학적 구조의 핵심 개념을 이루는 주요 인자들을 기본 테마로 하여 착안 되었으며, 구체적으로는 기본원료, 알칼리활성화제 및 물을 배합함에 있어서 상기한 주요 인자들에 대한 기준값을 미리 설정하고 이 기준값을 만족할 수 있는 원료들의 배합비율을 화학적, 수학적으로 산출하는 방법을 개발하 였다. As described in the prior art, the existing studies have been biased only for the characteristics of compressive strength depending on the variation of strength according to the diversification of alkali activator or the concentration of alkali ¾ agent. Accordingly, the present invention has been conceived based on the main themes that constitute the core concept of the geometrical structure of the geopolymer, such as Si / Ai ratio, Na / Al ratio in the geoplymer, specifically, the basic raw material, alkali activator In the formulation of water, a method of preliminarily setting a reference value for the above-mentioned main factors and calculating a compounding ratio of raw materials that can satisfy the reference value is chemically and mathematically developed.
Si/Al 버을어 가지는 의미는 복합적이지만, 예컨대 Si/AI의 몰비자 3.0 이하 이면 지오폴리머의 압축강도가 커지고 , 3,0을 초과하면 f lexible한 탄성을 가지 :게 된다. 이에 , 도 2에 도시된 바와 같이 : Si/Al 몰비에 따라 건축재료, 접착재 S, 실런트나 레진 재료 등으로 지오폴리머의 용도가 달라질 수 있다. 본 실시예에서 Si/Al 버율은 2.0, 2.5, 3.0등으로설정하였다. The meaning of having a Si / Al bur is complex, but if the molar ratio of Si / AI is less than 3.0, the compressive strength of the geopolymer becomes large, and if it exceeds 3,0, it has flexible elasticity. Accordingly, as shown in FIG. 2 : the use of the geopolymer may vary according to a Si / Al molar ratio as a building material, an adhesive S, a sealant, or a resin material. In this example, the Si / Al rates were set to 2.0, 2.5, 3.0, and the like.
그리고 Na/Al 비율은 지오폴리머의 안정성에 있어서 중요한 의미를 가.진다. 알칼리활성화제의 과다 사용으로 인해 Na의 양이 과다해지면, 반웅에 참여하지 않 은 Na가 지오폴리머에 잔존하면서 공기중의 이산화탄소와 결합하여 지오폴리머에 대한 백화현상을 일으 ᅵ기 때문이다. 화학 구조를 고려할 때 이론적인 Na/Al 비율 The Na / Al ratio is important for the stability of geopolymers . Lose. If the Na content is excessive due to the excessive use of the alkali activator, Na, which does not participate in the reaction, remains in the geopolymer and combines with carbon dioxide in the air, causing whitening of the geopolymer. Theoretical Na / Al Ratio Considering Chemical Structure
II
은 1이 되어야 하지만, 본 발명자의 실험적 고찰에 의하면 ᅳ과 A1이 1:1 비율인 경우에도 백화현상이 나타나는 것을 확인하였다. 이에 본 실시예에서는 Na/M 비을 을 1 이하의 ¾위, 예컨대 0.8 등으로설정하였다. 또한, 물 함량은 지오폴리머의 흐름성 ( ow)에 큰 영향을 미치며, 작업 율 이나 경화속도에 있어서도 중요한 인자가 된다、 II Should be 1, but experimental results of the inventors confirmed that bleaching occurs even when A and A1 are in a 1: 1 ratio. In this example, the Na / M ratio is set to ¾ above 1, such as 0.8. In addition, the water content has a great influence on the flow (ow) of the geopolymer and is an important factor in the working rate and the curing rate.
이에 본 발명에서는 타겟설정단계 (30)에서 Si/Al 비 Na/Al 비율 및 지오 플리머 배합시 물 함량에 대한 기준값을 설정한 후, 이 기준값을 만족할 수 있도록 기본원료, 알칼리활성화제 및 물의 상대적 백합량을 결정하게 된다. Therefore, in the present invention, after setting the reference value for the water content during the Si / Al ratio Na / Al ratio and geo-polymer blending in the target setting step ( 30), the relative value of the basic raw material, alkali activator and water to satisfy this reference value The amount of lilies will be determined.
지오폴리머의 주요 인자에 대한 결정이 완료되면, 배합비산출단계 (40)에서는 기본원료, 알칼리활성화제 및 물이 각각 어느 비율로 흔합되어야 하는지를 수학적 방법에 의하여 산출한다. 뒤의 실험예에서 설명하겠지만, 본 실시예에서는 석탄메립재 2종의 알칼리 활성화제 및 물을 흔합하여 지오폴리머를 배합하였으며, 석탄메립재와 2종의 알칼 리활성화제 및 물의 단위 무게당 Si, Al, Na, H의 몰수는 기본산출단계 (20)에서 이 미 산출되었다. When the determination of the main factors of the geopolymer is completed, the compounding ratio calculation step 40 calculates by the mathematical method in which proportion the base material, the alkali activator and the water should each be mixed. As will be described later in the experimental example, in this embodiment, the geopolymer was blended by mixing two kinds of alkali activator and water in coal-filled materials, and the Si per unit weight of coal-filled materials and two alkali activators and water, The moles of Al, Na and H have already been calculated in the basic calculation step (20).
배합비산출단계 (40)에서는 기본산출단계 (20)에서 산출한 석탄매립겨ᅵ, 2종의 알칼리활성화제 및 물의 단위 무게당 Si: Al, Na. H의 몰수애 대한 값괴 ·, 타겟설정 단계 (30)에서 선택한 S.i/A! 비율, a/Ai 비율 및 물함량 버율에 대한 값을 이용하 여 수학적 방식으로 석탄메립재, 2종의 알카리활성화제 및 물의 배합량을 계산할 수 있디- .
좀 더 구체적으로 설명하면, 각 계료에 포함된 Si, Ma, A I 그리고 물의 함량 을 알고 있고, 최종적으로 구하고자 하는 비율들이 정해진 상태이므로, 수학적 매 트릭스 형태로 선형방정식을 세을 수 있으며, 이를 통해 각 재료들의 배합량을 결 정할 수 있다. 수학적으로 계산을 통해 얻어지는 각 재료들은 증량 비율로 나타 내는 것이 현장에서의 적용성을 증대시킨다. In the compounding ratio calculation step (40), the coal landfill bran calculated in the basic calculation step (20), two alkali activators and Si : Al, Na. Ingot for H confiscation · Si / A! Selected in target setting step (30) Values for the ratio, a / Ai ratio and water content rate can be used to calculate the amount of coalfill, two alkali activators and water in a mathematical manner. More specifically, to know the Si, Ma, AI and the water content included in each gyeryo, because it is finally determined that the ratio to obtain the status, it is possible seeul linear equations to mathematically the matrix form, each through which The blending amount of the materials can be determined. Mathematically, each material obtained through calculation increases the applicability in the field by expressing the increase ratio.
상기한 바와 같이, 각 재료들의 중량 비율을 정한 후에는 물 함량에 대해서 는 일부 조정할수 있다. 즉, 배합비산출단계 (40)에서 구해진 물 함량을 이용하여 실제 반죽하여 반죽 질기를 확인한 후, 작업성을 고려하여 물의 함량을 일정 범위 에서 수정할수 있다. 물 함량은 대략 20-25 증량 ¾의 범위에서 결정할수 있다. 패합비산출단계 (4.Q)에서 구해진 -I- 함량을 가감한다는 것은 지오폴리머 내 수소와 삳소의 함량이 변한다는 것을 의미한다. 그러나, 물을 첨가한다고 하여도 본 발명에서 지오폴리머의 주요 인자로 삼았던 Si i 비율과 Na/Al 비율에는 영향 을 미치지 않으므로, 지오플리머의 흐름성을 조절하여 작업성과 경화시간을 원하는 수준으로 맞추는 것이 바람직하다ᅳ As described above, after determining the weight ratio of each material, some adjustments can be made to the water content. That is, after confirming the actual dough kneading by using the water content obtained in the compounding ratio calculation step 40, the water content can be modified in a certain range in consideration of workability. The water content can be determined in the range of approximately 20-25 increments ¾. That the acceleration -I- content obtained from the L (4. Q) Hefei calculation step means that the hydrogen content in the bovine and sat geo polymer varies. However, the addition of water does not affect the Si i ratio and Na / Al ratio, which are the main factors of the geopolymer in the present invention, so that the flowability of the geopolymer is adjusted to the desired level. It is desirable to match
이상에서 설명한 바와 같이, 본 발명에서는 최종적으로 제조되는 지오폴리머 의 Si/Al 비율, Na/Al 비율 및 물 함량을 미리 결정하고. 이 기준값을 맞출 수 있 도톡 4가지 원료의 배합비을을 결정할 수 있다. As described above, in the present invention, the Si / Al ratio, Na / Al ratio and water content of the finally prepared geopolymer are determined in advance. In order to meet this standard, it is possible to determine the mixing ratio of the four raw materials.
본 발명자는 상기한 구성으로 이루어진 지오플리머 배합 설계방법을 ■ 퓨터 프로그¾으로 구성하여 컴퓨터 기록데체 형태로 개발하였다. 이 컴퓨터 프로그램 에서는 입력 데이터가 주어지면 4가지 원료에 대한 최종적인 배합중량비를 산출하
여 디스플레이힌'다 , The inventors have geo replicon Murray mix design method consisting of the above-described configuration ■ developed to record computer programs made up of computer ¾ deche form. This computer program calculates the final blended weight ratios for the four raw materials given the input data. Is displayed by
즉, 사용자는 기본원료와 2종의 알칼리활성화제 및 물의 4가지 원료에 대한 각각의 SiO,, Ai203, Na20, ¾0의 3:성비 (중량비)에 대한 데이터를 입력하고, 제조하 고자 하는 지오폴리머의 Si/Al 몰 비율 > Na/Al 몰 비율, 물 함량에 데이터를 입력 한다. In other words, the user inputs data on the ratio of 3: sex ratio (weight ratio) of SiO ,, Ai 2 0 3 , Na 2 0, ¾0 for the four raw materials: basic raw material, two alkali activators and water. Enter the Si / Al molar ratio > Na / Al molar ratio , water content of the geopolymer.
컴퓨터 프로그램에서는 Si¾, Al20St Na,0, ¾Q에서 Si, Al , Na, 의 함량을 구하는 관계식과 증량과 몰에 대한 변화식이 수톡되어 있고, 배합비를 수학적으로 풀기 위한 메트릭스기ᅳ 수록되어 있다. ¾퓨터 프로그 ¾에서는 데이터를 이용하여 메트릭스를 수학적으로 ¾어 4가지 원료의 배합비를 산출한다 (배합비산출단계). 최 종적으로 컴퓨터에서는 4가지 원료의 배합 중량비 ■ 모니터에 디스플레이한다. 본 발명자는 상기한바와 같이 컴퓨터 프로그램을 개발한 후, 실제 석탄매립 재와 알칼리활성화제의 조성을 분석한후, 타겟이 되는 Si/Al 비율, Na ! 비을 및 물 함량을 쵸절하여 4가지 원료의 배합비율을 구하는 실험을 수행하였다. 이하, 실험예에 대하여 설명하기로 한다ᅳ In the computer program, the formula for calculating the content of Si, Al, Na, in Si¾, Al 2 0 St Na, 0, ¾Q, the change equation for the increase and the molar number, and the matrix for mathematically solving the compounding ratio are included. . The computer program uses the data to mathematically calculate the blending ratio of the four raw materials (compound ratio calculation step). In the outermost longitudinal computer displays the four blending weight ratio of the raw material ■ monitor. The present inventors developed a computer program as described above, and then analyzed the composition of the actual coal landfill material and alkali activator, the target Si / Al ratio, Na! The experiment was performed to obtain the blending ratio of the four raw materials by refraining the ratio of rain and water. Hereinafter, the experimental example will be described.
본 실험에서는 서천화력발전소 매립 석탄재에서 알칼리와 반응할 수 있는 반 웅성 알루미늄과 규소의 양을 측정, 계산하였디-. 또한 제조하고자 하는 지오폴리 머의 화학조성과 원료흔합물의 흐름성을 조절할 수 있도록 배합비를 계산하여 지오 ¾리머 제조가능한지를 알아보았디-. 지오 - 리머의 Si/Al 버를 2,0, 2.5 및 3.0으로
변화시켜 다양한 종류의 알칼리활성화제를 사용하였을 때 지오플리머의 압축강도와 미세구조의 관계를 실험하였다. In this experiment, we measured and calculated the amounts of semi-male aluminum and silicon that could react with alkali in buried coal ash at Seocheon Thermal Power Plant. In addition, the composition ratio was calculated to control the chemical composition of the geopolymer to be prepared and the flowability of the raw material mixture. Geo-reamer Si / Al burs to 2,0, 2.5 and 3.0 The relationship between the compressive strength and the microstructure of geoplymer was tested when various alkali activators were used.
1. 실험방법 1. Experimental method
본 실험에서 지오폴리머의 원료로사용한 시료는 서천화력발전소에서 배출되 는 매립 석탄재이다. 메립 석탄재는 주로 화력발전소의 바닥재와 비산재 중 입도 가 큰 잔사회 (r ect ash)가소¾ 흔합되어 메립지에 해수와 함께 매립된 것이다-. 시료는 수집된 후 3일 동안 자연 건조시 ¾ 후 삽을 이용한 콘앤쿼터 샘풀 ¾ 법 (cone~and~quarter sampling)을 적용하여 큰 입자와 미립자가 고르게 섞이도톡 한 후 20kg을 취하였다. 공업분석 결과 시료의 미연탄소 함량이 높아 부유선별법으 로 미연탄소를 제거하였다. 미연탄소분 입자 표면의 소수성을 증가시켜 거품에 선 택적으로 부착시키는 목적으로 사용하는 포집제 (caiiector)로는 등유 (kerosene)를, 미연탄소분 입자가 부착된 공기거품이 꺼지지 않고 유지되도록 넣어주는 기포 제 (irother)로는 송유 (pine oil)를 사용하였디-, The sample used as the raw material of geopolymer in this experiment is landfill coal discharged from Seocheon thermal power plant. The landfill coal ash is mainly buried with seawater in the landfill due to the mixing of large-size retent ash among the bottom ash and fly ash of the thermal power plant. After the samples were collected and dried naturally for 3 days, the cone and quarter sampling method was used by using a shovel after convection, and the large particles and the particles were mixed evenly, and 20 kg were taken. As a result of industrial analysis, the unburned carbon was removed by the flotation method due to the high unburned carbon content. As a collector used to increase the hydrophobicity of the surface of unburned carbon powder and selectively attach it to the foam, kerosene is used as a foaming agent to keep the air bubbles attached to the unburned carbon powder without being put out. irother) I used pine oil-,
시료와 부유선별 산물언 미연탄소 함량은 공¾분석기 (TGA 601, Leco Corp. , US)로 분석하였다. 미연탄소가 제거된 시료는 로드밀 (rod miii)로 입자크기가 100 이하가 되도특 분쇄하여 실험에 사용하였디-. 시료의 정량 X-선회절분석은 리트5 트법에 7ᅵ반한 DIFFMC' T0PAS 4.2 (Bruker-AXS, Gern iiy)소프트웨어를 사용하였다. 내부표준 물질로는 Cakkim
Fluoride (CaF2l 99.985%, Aifa)를 시료 무게의 10wt% 첨가하였다. X~선 회절 분석 은 Cu target과 LynxEye position sensitive detector가 부착된 D8 Advance diffractome er (Bruker~AXS, Germany)롤 이용하여 수행하였다. 회절 패턴은 5° ~ 95° 2Θ 구간, 0.0Γ step size, step 당 1 sec의 ¾건으로 얻었으며, 0.3° 발산 술¾ (divergence s!it)과 2.5"' 솔러슬릿 (soller slit)이 사용되었다. The unburned carbon content of samples and flotation was analyzed by a co- analyzer (TGA 601, Leco Corp., US). Unburned carbon was removed from the sample using a rod mill (rod miii). Quantitative X- ray diffraction analysis of the sample is attracted to 7 discrete i 5 teubeop was used DIFFMC 'T0PAS 4.2 (Bruker-AXS , Gern iiy) software. Internal standard material Cakkim Fluoride (CaF 2l 99.985%, Aifa) was added 10wt% of sample weight. X-ray diffraction analysis was performed using a D8 Advance diffractomeer (Bruker ~ AXS, Germany) with Cu target and LynxEye position sensitive detector. Diffraction patterns were obtained with ¾ cases of 5 ° to 95 ° 2Θ, 0.0Γ step size, 1 sec per step, and 0.3 ° divergence s! It and 2.5 "' solar slit were used. .
시료의 정량툰석 및 기기 인자의 표준화 (fundaraen l parameter)를 위해서 동일한 2:건으로 본 시료와 표준시료 (La , SRM 660b ; NiS'f, US)에 대하여 각각 X- 선 희절 패턴을 얻었디-. 시료의 화학조성은 X-선 형광분광 분석기 (X Ray Floiirescence Spectrometer , Shi mad zu Sequent iai XRF ].800, Shimadzu, Japan)로 분석하였으며, 비정질 규소와 알루미늄, 나트튬의 함량을 계산하였다. For the standardization of the quantitative tunite and instrumental parameters of the sample, two X-ray stripe patterns were obtained for the sample and the standard sample (La, SRM 660b ; NiS ' f, US) in the same case. The chemical composition of the samples was analyzed by X-ray fluorescence spectrometer (X Ray Floiirescence Spectrometer, Shi mad zu Sequent iai XRF ] .800, Shimadzu, Japan), and the contents of amorphous silicon, aluminum, and sodium were calculated.
¾칼리활성화제로는 가성소다 (NaOH, Sodium hydroxide, Wako pure chemical, 순도 9?.0wt% 이상) , 물유리 (N¾Si03 ' ¾0, Kanto chemical , Si02 35~38wt%, Naa0 Caustic soda (NaOH, Sodium hydroxide, Wako pure chemical, purity 9 ~ .0wt% or more), water glass (N¾Si0 3 '¾0, Kanto chemical, Si0 2 35 ~ 38wt%, Na a 0
17~19wt¾) , 알루민산소다 분말 (NaAK , Junsei chemical, Na20 35.0-39.0wt¾, 婦 3 17 ~ 19wt¾), Sodium aluminate powder (NaAK, Junsei chemical, Na 2 0 35.0-39.0wt¾, 婦3
52.0-56.0 t¾), 알루민산소다 용액 (NaAi¾ · n¾(), (주)에이텍정밀화헉ᅳ, Na30 20.0wt%: 52.0-56.0 t¾), Sodium aluminate solution (NaAi¾ n¾ (), ATEC Co., Ltd.), Na 3 0 20.0wt% :
A1203 19.0wt%, ¾052 ¾)을사용하였다. 알루민산소다 외에 알루미늄의 공급원으로 카을린 분말을 700t:에서 2시간 동안 소성한 메타카을린 (Si02 54.60wt , Al203 42,71ivi¾ 도 사용하였다. NaOH는 증 류수와 혼합하고, 경우에 따라 물유리, 알루민산소다 용액과 섞어 24시간이 경과된
후석탄재의-흔합하였디 . A1 2 0 3 19.0 wt%, ¾052 ¾) was used. In addition to sodium aluminate, metacarlin (Si0 2 54.60wt, Al 2 0 3 42,71ivi¾) calcined with a powder of chlorine for 2 hours at 700 t: was also used as a source of aluminum. 24 hours after mixing with water glass and sodium aluminate solution Of coking coal.
배합비는 시료의 비정질 규소.와 알루머늄. 나트륨의 양과, 알칼리활성화제ᅳ 물 및 메타카을린에서의 규소 , 알루미늄, 나트륨의 양 . 제조하고자 하는 지오폴리 머의 Si/Al 및 Na/Ai 버를 고려하여 본 발명이 적용된 컴퓨터 프로그램에 의하여 계산하였다 (도 3의 표). The compounding ratio is amorphous silicon and aluminium in the sample. The amount of sodium and the amount of silicon, aluminum and sodium in alkali activators and water and metacarlin. The Si / Al and Na / Ai burs of the geopolymer to be prepared were calculated by a computer program to which the present invention was applied (Table 3).
시료의 무게에 대한 액상 (알칼리활성화제에 함유된 물괴- free water (별도로 첨가되는 몰))의 무게비를 계산하였고, 배합물의 실제 반죽질기는 실험실예서 제작 한 미니 슬럼프콘 (mini slump cone)을 사용하여 측정하였다. 슬럼.프콘 하단의 내경 은 38. i醒, 상단의 내경은 19誦이며, 콘의 높이는 60.4腦이다. The weight ratio of the liquid phase (free water (molar added separately) in the alkali activator) to the weight of the sample was calculated, and the actual kneading of the blend was made using a mini slump cone made in the laboratory. It was measured by. Slum . The inner diameter of the bottom of the cone is 38. i 醒, the inner diameter of the top is 19 誦, and the cone height is 60.4 腦.
지오폴리머 페이스트 배합물은 점착성이 높기 때문에 시멘트보다 묽게 배합 하여 미니 슬럼프콘에 채워 넣고 콘을 들어 을려 분리한 후 분 뒤 바닥에 퍼진 하 단의 지름을, 서로 수직이 되는 방향에서 2개 측정하여 기준으로 사용하였다. 반죽 질기가크게 다른 경우, 물함량을 조절하여 다시 배합하였다 ·. Geopolymer paste formulations are highly tacky, so they are thinner than cement, filled in mini slump cones, lifted off, separated, and then measured two diameters at the bottom of the floor after two minutes from the perpendicular to each other. Used. If the dough is significantly different, adjust the water content and mix again.
시료와 알칼리 등의 흔합몰은 시멘트믹서를 사용하여 저속에서 1분, 고속에 서 1분 동안 흔합한 후 상하로 진동하는 진동기 위에서 2분간 진동시켜 혼합물 안 에 잡혀있는 공기가 빠지도록 하였다. 배합몰은 직경 29腿 높이 60删의 실린더형 몰드에 붓고 뚜¾을 닫아 밀봉한 후 습도가 조절되지 않는 오븐에서 은도 70r로 72시간 양셉한 후 싱은에 꺼내어 하루가 지난 뒤 몰드에서 탈형하였디-, 양생을 시 작한지 120시간째에 공시체 4개의 압축강도를 iiS F 2405 규격에 따라 측정하고 평 균 압축강도와표준편차를 계산하였다,
압축강도 측정을 위해 실린더형 시험체의 상, 하면이 옆면에 수직하고 서로 평행하도특, 또한 높이가 58ι腿가 되도록 사포로 연마하였다. 지오폴리머 파단면의 미세구조는 주사전자현미경 (JEOL JSM-6380, Japan)으로 관찰하였다. 지오폴리머는 2012년 11월 27일부터 12월 1일 사이에 배합되었고, 배합 후 4일 이후부터 공기 증 에 노출시켜 백화현상이 나타나는지 관찰하였다. Mixing moles such as samples and alkali were mixed for 1 minute at a low speed and 1 minute at a high speed using a cement mixer, and then vibrated for 2 minutes on a vibrator that vibrated up and down to remove air trapped in the mixture. The compounding mall was poured into a cylindrical mold having a diameter of 29 腿 and a height of 60 删, closed with a seal, sealed for 72 hours with 70 R of silver in an uncontrolled humidity oven, taken out of Xingeun, and demolded from the mold after one day. -120 hours after the start of curing, the compressive strengths of the four specimens were measured according to the iiS F 2405 standard and the average compressive strength and standard deviation were calculated. In order to measure the compressive strength, the upper and lower surfaces of the cylindrical test specimens were polished with sandpaper such that the upper and lower surfaces were perpendicular to the sides and parallel to each other, and the height was 58 腿. The microstructure of the geopolymer fracture surface was observed with a scanning electron microscope (JEOL JSM-6380, Japan). Geopolymers were formulated between November 27 and December 1, 2012, and were exposed to air buildup from 4 days after blending to see if whitening was present.
2. 실험결과 및 고찰 2. Experimental Results and Discussion
공업분석 결과 시료의 미연탄소 함량은 13.94%로 높게 나타났다. 부유선별법 으로 미연탄소를 제거한 시료에서는 탄소가 검출되지 않았다. 이하에서 "매립 석 탄재" 또는 "시료 "는 탄소를 제거한 상태를 의미한다. 도 4의 표에 시료 (매립 석 탄재)의 화학조성을 나타내었다. si¾와 A1203 함량의 합이 70%를 초과하고 CaO 함 량이 20% 이하로 나타나, 화학조성으로는 ASTM C618규격에서 분류하는 Class F fly ash에 해당함을 알수 있다. Industrial analysis showed that the unburned carbon content of the sample was 13.94%. No carbon was detected in samples from unburned carbon by flotation. Hereinafter, "buried coal ash" or "sample" means a state in which carbon is removed. The chemical composition of the sample (coated coal ash) is shown in the table of FIG. The sum of si¾ and A1 2 0 3 content exceeds 70% and the CaO content is less than 20%, and the chemical composition corresponds to Class F fly ash classified in ASTM C618 standard.
정량 X-선 회절 분석 결과 시료에 함유된 결정질은 물라이트가 22.6 %로 가 장 높았으며 석영과 마그헤마이트가 각각 8.5w«, 5.6 %로 나타났다 (도 5의 그래 프). As a result of quantitative X-ray diffraction analysis, the crystalline content contained in the sample was the highest in mullite (22.6%) and quartz and maghemite in 8.5w «and 5.6%, respectively (graph 5).
도 6의 그래프는 X-선 형광분광 분석과 정량 X-선 회절 분석으로부터 계산한 서천화력발전소 매립석탄재의 비정질 성분분석 결과이다. 비정질 실리카의 함량은 36.8wt%, 비정질 알루미나의 함량은 12.8 ¾로 나타나 비정질 Si/Al 비는 2.44로
결정되었다. 따라서 Si /Al 비가 2.44보다 낮은 지오폴리머를 제조하기 위해서는 알루미늄을 공급해 줄 고체 알루민산소다나 알루민산소다용액 또는 메타카올린을 첨가하고, Si/Al 비가 2.5와 3.0인 경우 물유리와 NaOH를 사용하였다 (도 3의 표 참 조) . 6 is an amorphous component analysis result of the landfill coal material of Seocheon thermal power plant calculated from X-ray fluorescence spectroscopy and quantitative X-ray diffraction analysis. The content of amorphous silica was 36.8wt% and the content of amorphous alumina was 12.8 ¾, so the amorphous Si / Al ratio was 2.44. It was decided. Therefore, to prepare a geopolymer having a Si / Al ratio of less than 2.44, a solid sodium aluminate or sodium aluminate solution or metakaolin to supply aluminum was added, and water glass and NaOH were used when the Si / Al ratio was 2.5 and 3.0 ( See table in FIG. 3).
도 3의 표에 나타난 조건으로 만들어진 지오폴리 머의 압축강도를 도 7의 그 래프에 나타내었다. 압축강도는 4개 공시체의 평균값이고 표준편차를 함께 표시하 였다. 서로 다른 원료의 조합으로 지오폴리머의 Si/Al 비를 2.0, Na/Al 비가 0.8 이 되도록 배합한 경우 (시료 20AS, 20NaAl , 20MK) , 미니 슬럼프 테스트 후 슬럼프 된 배합물의 하단 직경은 세 시료에서 유사하였으며 20AS시료의 경우 40~40讓 범위 로 측정되었다. The compressive strength of the geopolymer made under the conditions shown in the table of FIG. 3 is shown in the graph of FIG. Compressive strength is the average of four specimens and the standard deviations are indicated. When the Si / Al ratio of the geopolymers were mixed with 2.0 and Na / Al ratios of 0.8 (sample 20AS, 20NaAl, 20MK) using different raw material combinations, the bottom diameter of the slumped compound after the mini slump test was similar in all three samples. In the case of 20AS sample, it was measured in the range of 40 ~ 40 讓.
알루민산소다 용액과 NaOH를 사용한 20AS 시료의 경우 평균 압축강도는 11.2MPa (표준편차 0.9MPa) , 고체 알루민산소다와 NaOH를 사용한 20NaAl 시료는 12.3MPa (표준편차 l . OMPa) 의 평균 압축강도를 나타내었다. 표준편차를 고려한다 면 알루민산소다를 고체로 사용하는 경우와 용액으로 사용하는 경우 의미 있는 차이 는 없다고 판단된다. 따라서 보관과 운반이 까다로운 용액보다는 고체 알루민산소 다를 사용하는 것이 유리할 것으로 생각된다. 또한 고체 알루민산소다를 사용하여 포를랜드 시멘트와 같이 물만 부어 지오폴리머가 만들어진다는 점에서 상용화가 보 다 용이할 것 이다 . The average compressive strength was 11.2 MPa (standard deviation 0.9 MPa) for 20AS sample using sodium aluminate solution and NaOH, and 12.3 MPa (standard deviation l. OMPa) for 20NaAl sample using solid sodium aluminate and NaOH. Indicated. Considering the standard deviation, there is no significant difference between the use of sodium aluminate as a solid and the solution. Therefore, it would be advantageous to use different solid aluminates rather than solutions that are difficult to store and transport. In addition, it will be easier to commercialize in that geopolymer is made by pouring only water such as forland cement using solid aluminate.
한편, 알루미늄의 공급원으로 알루민산소다 대신 메타카올린을 사용한 20MK 시료의 경우 평균 압축강도는 9.1MPa (표준편차 2.0MPa)로 나타나, 알루민산소다를
사용한 경우보다 다소 낮은 기 계적 특성을 나타내었다. X-선회절분석에서는 메타카 올린이 비정질이지만 단주기 질서 (short-range order)는 여전히 어느 정도 유지되 기 때문에 실제로 반웅에 참여한 반웅성 실리카와 알루미나의 양이 예상보다 적었 기 때문일 수 있다. 알루미늄을 알루민산소다가 아닌 메타카을린으로 보충하여 상 대적으로 알칼리의 양이 적 게 배합된 때문일 수도 있을 것 이다 . 액상의 알루민산 소다를 사용한 경우는 물함량이 23wt%였지만 고체 알루민산소다를 사용하는 경우 물함량을 다소 증가시켜 24 %로 맞추었을 때 비슷한 흐름성을 얻을 수 있었다 (도 3의 표 참고) . On the other hand, the average compressive strength of the 20MK sample using metakaolin instead of sodium aluminate as a source of aluminum was 9.1 MPa (standard deviation 2.0 MPa). The mechanical properties were slightly lower than those used. In the X-ray diffraction analysis, metakaolin is amorphous, but the short-range order is still maintained to some extent, which may be because the amount of semi-aluminum silica and alumina actually involved in the reaction was less than expected. It may be because aluminum is supplemented with meta-caline rather than sodium aluminate, so that the amount of alkali is relatively low. The water content was 23 wt% when the liquid alumina soda was used, but similar flowability was obtained when the water content was slightly increased to 24% when the solid aluminate was used (see the table in FIG. 3).
메타카올린을 첨가한 경우 물함량을 25 %로 증가시켰어야 했는데, 이는 메 타카올린 입자의 큰 비표면적과 판상형의 입자형 태 때문에 배합에 필요한 물비가 높아야 하고 , 실제로 free water의 양이 가장 높아 (도 3의 표) 20MK 시료의 강도가 세 개의 시료 중 다소 낮게 나타난 이유가 될 수 있을 것 이다. The addition of metakaolin should have increased the water content to 25%, due to the large specific surface area of the metakaolin particles and the plate-like particle shape, the water ratio required for the formulation should be high, and in fact the amount of free water was highest ( Table 3) may be the reason why the strength of the 20MK sample is somewhat lower among the three samples.
이 세 가지 경우는 목적하는 지오폴리머의 화학조성을 만족시키기 위해 다양 한 원료의 배합이 가능하다는 것과, 사용하는 알칼리의 종류, 점도 , 첨가물에 따라 흐름성을 조절해야 한다는 것을 보여준다. 메타카올린을 사용한 20MK 시료의 경우 물함량은 25wt%로 가장 높았지만 L/S( l iquid/soI id) 비율은 가장 적 었고, 그럼에도 불구하고 미니 슬럼프 테스트에서는 비슷한 반죽질기를 보였기 때문이다. 주사전자 현미경으로 관찰한 파단면에서 세 시료는 비슷한 미세구조를 보였다 (도 8 참조) . 도 8에 나타난 미세구조는 공통적으로 조직 이 다소 느슨하며 큰 기공이 관찰 되고 서로 연결되어 있기도 하였다. 압축강도의 차이에 따른 미세구조의 차이는 관
찰되지 않았는데, Duxson 등은 지오폴리머의 미세구조는 압축강도보다 영 률 (Young' s modulus)과 밀접한 관계가 있음을 보인 바 있다 . 본 실험에서는 지오 폴리머의 영률을 측정하지 않았으므로 미세구조와 영률사이의 관계는 알 수 없으 나, 본 실험조건에서는 석탄재를 알루민산소다와 NaOH로 활성화시키는 경우 압축강 도가 증가되더 라도 미세구조에 큰 변화를 가져오지 않음을 알 수 있었다. These three cases show that various raw materials can be blended to satisfy the chemical composition of the desired geopolymer, and the flow must be controlled according to the type of alkali, viscosity and additives used. In case of 20MK sample using metakaolin, the water content was the highest as 25wt%, but the L / S ratio was the smallest. Nevertheless, the mini slump test showed similar dough kneading. The three samples showed similar microstructures at the fracture surface observed with the scanning electron microscope (see FIG. 8). The microstructure shown in FIG. 8 has a slightly loose structure and large pores are observed and connected to each other. Differences in microstructure due to differences in compressive strength Duxson et al. Have shown that geopolymer microstructures are more closely related to Young's modulus than compressive strength. Since the Young's modulus of the geopolymer was not measured in this experiment, the relationship between the microstructure and the Young's modulus was not known.In this experimental condition, when the coal ash was activated with sodium aluminate and NaOH, even though the compressive strength increased, It did not make a difference.
물유리와 NaOH를 사용하여 Si /Al=2.5 인 지오폴리머로 제조한 시료 25SS는 미니 술럼프 테스트에서 40~43腿 크기로 퍼져, Si/Al=2.0인 앞의 세 경우와 비슷한 반죽질기를 보였지만, 평균 압축강도는 3.53MPa (표준편차 0.8MPa)로 낮게 나타났 다. Si /Al 비가 3.0인 지오폴리머 시료 30SS-23은 반죽질기가 묽은데도 불구하고 25SS보다 높고 20AS와 유사한 10.3MPa (표춘편차 2.5MPa)의 평균 압축강도를 나타 내었다. Sample 25SS made of geopolymer with Si / Al = 2.5 using water glass and NaOH spread out to 40 ~ 43 腿 in mini-sulfum test and showed a similar dough kneader as the previous three cases with Si / Al = 2.0. The average compressive strength was 3.53MPa (standard deviation 0.8MPa). The 30SS-23 geopolymer sample with a Si / Al ratio of 3.0 showed an average compressive strength of 10.3 MPa (2.5 MPa for spring deviation), which was higher than 25 SS and similar to 20AS, despite the thin dough.
30SS-23 시료와 Si/Al , Na/Al 비는 동일하되 물함량만 2wt¾ 줄인 30SS-21 시 료의 경우 미니 술럼프 테스트에서 39~45ι腿 크기로 퍼져 25SS 시료와 비슷한 반죽 질기를 나타내었다. 30SS-21 시료의 평균 압축강도는 17.9MPa (표준편차 1.2MPa) 로, 25SS 시료의 3.5MPa의 5배에 가까이 증가된 강도를 나타내었다. 지오폴리머의 압축강도에 영향을 주는 인자는 Si /Al과 Na/Al 비 , 알칼리 금속이온의 종류와 함 량, 반웅하지 않은 Al-Si 입자의 크기와 분포 및 지오폴리머 겔과의 표면반응, 물 함량 등으로 알려져 있다. 다양한 인자가 영향을 주기 때문에, 일률적으로 Si /Al 비가 얼마일 때 강도가 높다고 말하기는 어 렵지 만, 메타카을린으로 만든 지오폴리 머의 경우 Si /Al=1.8~2.5 Na/Al=0.9~1.3 일 때 압축강도가 최 대를 나타낸다고 알려
져 있다. The 30SS-21 sample, which had the same Si / Al and Na / Al ratios but reduced the water content by 2wt¾, was spread to 39 ~ 45ι 腿 in the mini-sulfum test, showing a dough similar to the 25SS sample. The average compressive strength of the 30SS-21 sample was 17.9MPa (standard deviation 1.2MPa), which was nearly 5 times higher than 3.5MPa of the 25SS sample. Factors affecting the compressive strength of geopolymers are Si / Al and Na / Al ratios, the type and content of alkali metal ions, the size and distribution of unreacted Al-Si particles, and the surface reaction with geopolymer gels, water Content is known. It is difficult to say that the strength is high at some Si / Al ratio, because various factors affect it, but in the case of geopolymers made of metacarlin, Si /Al=1.8~2.5 Na / Al = 0.9 ~ 1.3 Is the maximum compressive strength when Lost
실리카와 알루미나라는 단순한 화학조성의 메타카올린으로부터 제조한 지오 폴리머에서는 Si/Al과 Na/Al 비에 따른 지오폴리머의 강도특성의 경향이 잘 연구된 반면, 화학조성과 광물함량, 입자의 크기와 형 태가 다양하고 불균질한 석탄재에서 는 일반화하기가 어렵다. Geopolymers prepared from metakaolins of simple chemical compositions, such as silica and alumina, have been well studied in terms of the strength characteristics of geopolymers according to Si / Al and Na / Al ratios, while chemical composition, mineral content, particle size and shape It is difficult to generalize in various types of heterogeneous coal ash.
본 실험에서는 Si/Al 비가 2.0인 지오폴리머에서 대체로 9~llMPa의 압축강도 를 보인 반면 2.5인 지오폴리머에서는 3.5MPa, 3.0인 지오폴리머에서는 17.9MPa을 나타내 Si/Al 비가 증가함에 따라 기 계적 특성 이 나빠졌다가 더욱 좋아진 것으로 나타났다. 이 결과를 지오폴리머의 성분과 반웅에 사용된 알칼리활성화제의 종류 와 특성 이라는 면에서 검토해 볼 필요가 있다. 지오폴리머의 원료로 사용한 석탄 재의 반응성 Si/Al 비가 2.44이기 때문에 , 2.0인 지오폴리머를 만들기 위해 알루미 늄을 알칼리에서 공급하기 위해 두 종류의 알칼리 (알루민산소다와 NaOH)를 첨가하 였다. 2.5의 경우 물유리와 NaOH를, 3.0인 경우는 규소를 공급할 수 있는 물유리와 NaOH 두 종류의 알칼리를 첨가하였다 (도 3의 표 참조) . In this experiment, the Si / Al ratio of 2.0 geopolymer showed 9 ~ llMPa compressive strength, while 2.5 geopolymer showed 3.5MPa and 3.0 geopolymer showed 17.9MPa. It got worse and got better. These results need to be examined in terms of the components and characteristics of geopolymer components and alkali activators used in reaction. Since the reactive Si / Al ratio of the coal ash used as the raw material of the geopolymer is 2.44, two kinds of alkalis (sodium aluminate and NaOH) were added to supply aluminum from the alkali to make the geopolymer 2.0. In the case of 2.5, water glass and NaOH were added, and in the case of 3.0, two kinds of alkalis including water glass and NaOH which could supply silicon were added (see table in FIG. 3).
먼저 25SS 시료는 적은 양의 알칼리를 사용하고도 Si/Al 비 인 2.5인 지오폴 리머를 만들 수 있었다 . 즉 알칼리 ¾성화제로부터 공급되는 알루미늄의 양이 적었 기 때문에 (물유리 1.9wt%, NaOH 5.0wt%, 도 3 참조), 석탄재의 반웅성 알루미늄이 용융되어 지오폴리머 반응에 참여하여야 하였다. First, the 25SS sample was able to produce a geopolymer with a Si / Al ratio of 2.5 with a small amount of alkali. That is, since the amount of aluminum supplied from the alkali ¾-forming agent was small (1.9 wt% of water glass, 5.0 wt% of NaOH, see FIG. 3), semi-aluminum of coal ash was melted to participate in the geopolymer reaction.
알루미늄이 지오폴리머 반응에 얼마나 참여할 수 있는가는 지오폴리머 겔 형 성에 매우 결정적 인 역할을 한다고 알려져 있다. 화력발전소 비산재에서 알루미늄
이 알칼리에 용융되는 속도는 메타카올린에서보다 느리몌 알칼리의 종류와 농도에 도 좌우된다. 25SS 시료는 알칼리의 사용량이 적었고 석탄재로부터 층분한 양의 알루미늄이 용출되지 못한 것으로 판단된다. 따라서 지오폴리머의 Si/Al 비는 석탄 재의 반응성 Si/Al 비보다낮거나높아야 할 것이다. How much aluminum can participate in geopolymer reactions is known to play a crucial role in the formation of geopolymer gels. Aluminum from thermal power plant fly ash The rate of melting in this alkali is also slower than in metakaolin, depending on the type and concentration of alkali. The 25SS sample was found to be low in alkali and did not dissolve a sufficient amount of aluminum from the coal ash. Therefore, the Si / Al ratio of geopolymer should be lower or higher than the reactive Si / Al ratio of coal ash.
한편, Si/Al=3.0인 지오폴리머의 압축강도는 물함량이 감소함에 따라 증가 (도 7참조)한 것은 예측되었으며, 기^의 연구결과와도 일치하였다. On the other hand, the compressive strength of the geopolymer with Si / Al = 3.0 was predicted to increase as the water content decreased (see Fig. 7), which is consistent with the results of previous studies.
그리고 주사전자현미경으로 지오폴리머 겔의 파단면을 관찰한 결과, Si/Al=2.5인 시료 (도 9의 (a))와 Si/Al=3.0인 세 개의 시료 (도 9의 (b)~(d))에서 흥미로운 차이가 발견되었다. 압축강도 3.5MPa를 나타낸 25SS 시료 (도 9의 (a))의 표면형상은 Si/Al=2.0으로 9~12MPa의 압축강도를 나타낸 20AS, 20NaAl , 20MK 시 료 (Fig. 4)의 표면형상과 매우 유사하였다. 반면 도 9의 (b), (c), (d)에서는 알 칼리와 반응하지 않은 입자들이 관찰되었고, 지오폴리머 겔 부분은 Si/Al=2.0과 2.5인 시료와 비교해서 미립의 지오폴리머 겔이 서로 잘 연결되어 보였다. As a result of observing the fracture surface of the geopolymer gel with a scanning electron microscope, three samples having a Si / Al = 2.5 (FIG. 9 (a)) and three samples having a Si / Al = 3.0 (FIG. 9 (b) ~ ( In d)) an interesting difference was found. The surface shape of the 25SS sample (FIG. 9 (a)) exhibiting compressive strength of 3.5 MPa was Si / Al = 2.0 and the surface geometry of 20AS, 20NaAl, 20MK sample (Fig. 4) exhibiting compressive strength of 9-12 MPa. Very similar. On the other hand, in Fig. 9 (b), (c), (d) was observed particles that do not react with alkali, the geopolymer gel portion of the fine geopolymer gel compared to the sample of Si / Al = 2.0 and 2.5 It seemed to be well connected to each other.
또한 이 세 시료는 알칼리와 반웅하지 않은 결정질 입자들과 지오폴리머 겔 과의 점착 정도에서 큰 차이를 보이지 않았다. 높은 압축강도의 지오폴리머는 공 극률이 낮고 치밀하여, 미립의 미세구조를 나타낸다. 30SS-23, 30SS-21, 30SS-19 시료의 실리카 용액 첨가량은 15.7~16.5 ¾로 큰 차이는 없지만 25SS 시료의 1.9 ¾는 보다 훨씬 높았다 (도 3의 표). 즉 알칼리 용액 중의 실리카 함량이 높은 경우 미립의 미세구조가 발달하는 것으로 보이며, 이는 기존의 연구결과와도 일치 하였다.
지오폴리머의 화학조성과 흐름성 조절은 지오폴리머 상용화에 있어 매우 중 요한 기술이다 . 이는 본 실험에서와 같이 석탄재의 정량적 화학조성을 알고, 목표 로 하는 지오폴리머의 화학조성을 달성하도록 배합비를 계산할 수 있어야 가능하 다. 화학조성에 따라 용도가 달라지고, 지오폴리머의 배합시 적은 물함량의 차이 가 큰 흐름성의 차이를 나타내기 때문이다. 예를 들어 Si/Al 비는 동일하지만 물 함량이 2wt% 차이가 남에 따라 배합물의 반죽질기는 크게 달라졌다. In addition, the three samples showed no significant difference in the degree of adhesion between the crystalline particles and alkali polymers, which were not reacted with alkali. High compressive strength geopolymers have low porosity and are compact, exhibiting fine microstructure. The amount of silica solution added to the 30SS-23, 30SS-21, and 30SS-19 samples was 15.7-16.5 ¾, but there was no significant difference, but 1.9 ¾ of the 25SS sample was much higher (Table 3). In other words, when the silica content in the alkaline solution is high, the fine microstructure appears to develop, which is consistent with the existing research results. The chemical composition and flow control of geopolymers is a very important technique for the commercialization of geopolymers. It is possible to know the quantitative chemical composition of coal ash and calculate the compounding ratio to achieve the chemical composition of the target geopolymer as in this experiment. This is because the use varies depending on the chemical composition, and the difference in water content in the mixing of the geopolymer shows a large flow difference. For example, the dough kneading of the blends varied greatly with the same Si / Al ratio but with a 2 wt% difference in water content.
또한 본 연구에서 제조한 모든 지오폴리머에서는 공기에 노출된 이후 현재까 지 백화현상이 나타나지 않았는데, 이것 역시 지오폴리머 시스템의 정량적 화학조 성을 제어할 수 있기 때문이었다. In addition, all geopolymers produced in this study did not show bleaching until now after exposure to air, because they can control the quantitative chemical composition of geopolymer systems.
3. 결론 3. Conclusion
서천화력발전소 매 립 석 탄재를 정량적으로 분석하여 반웅성 규소와 알루미늄 의 양을 계산하고, 이로부터 Si/Al 비가 2.0, 2.5, 3.0인 지오폴리머를 다양한 원 료와 배합으로 제조하였다 . Quantitative analysis of the landfill coal material at Seocheon Thermal Power Plant was used to calculate the amounts of semiungsung silicon and aluminum. From this, geopolymers with Si / Al ratios of 2.0, 2.5 and 3.0 were prepared from various raw materials.
석탄재를 정량적으로 평가함으로써 다양한 Si/Al 비를 갖는 지오폴리머를, 다양한 원료의 배합비로 제조하는 것이 가능하였다 . By quantitatively evaluating the coal ash, it was possible to produce geopolymers having various Si / Al ratios at various blending ratios.
지오폴리머의 Si/Al 비는 석탄재의 반응성 Si/Al 비보다 낮거나 높게 설계했 을 때 더 나은 압축강도가 발현되었다. The Si / Al ratio of the geopolymer was better than the reactive Si / Al ratio of the coal ash, which resulted in better compressive strength.
과량의 알칼리를 사용하는 비효율적 비 경제적 인 경험적 배합에서 벗어나 적 정량의 알칼리 활성화제를 사용함으로서 백화현상을 방지할 수 있었다.
덧붙여, 본 실험결과로부터 알루민산소다와 물유리를 활성화제로 사용한 경 우 지오폴리마의 미세구조 특성이 다르다는 것을 알 수 있었다. 알칼리 용액 중 실리카의 함량이 높을수록 지오폴리머 겔의 미세구조는 미립으로 형성되었다. 높은 압축강도를 나타내는 시료에서는 공극의 크기가 작고 미립의 미세구조가 더 나은 연결성을보임을 알수 있었다. 이상에서 설명한 바와 같이, 본 발명에 따른 지오폴리머 배합설계방법은 지 오폴리머의 물성에 중요한 영향을 미치는 인자인 Si/Al 비율, Na/Al 비율올 미리 설정한 상태에서, 이 인자들의 설정값을 만족할 수 있는 지오폴리머 원료들의 배합 량을 산출할수 있는 방법을 제공한다. Whitening could be prevented by using an appropriate amount of alkali activator, free from inefficient, inexpensive empirical formulations using excess alkali. In addition, the results showed that the microstructural properties of geopolymers differed when sodium aluminate and water glass were used as activators. The higher the silica content in the alkaline solution, the finer the microstructure of the geopolymer gel was formed. In the samples showing high compressive strength, the pore size was small and the fine microstructure showed better connectivity. As described above, the geopolymer formulation design method according to the present invention is a Si / Al ratio, Na / Al ratio of factors that have a significant effect on the physical properties of the geopolymer in the state of pre-set, the set value of these factors It provides a method to calculate the blending quantity of the satisfying geopolymer raw materials.
이에 따라 지오폴리머 배합에 있어서 보다 과학적이고 체계적인 접근 가능성 을 제공하며, 지오폴리머의 주요 인자들에 따른 배합설계로부터 제조된 공시체를 이용하여 지오폴리머의 구조와특성에 대한 활발한 연구 기반을 마련할수 있다. 또한, 본 발명에 따른 과학적 배합설계를 통해 원료사용의 경제성을 도모할 수 있으며, 제조되는 지오폴리머의 백화현상 등 안정성에 문제를 줄 수 있는 요소 들을 조절할수 있다. This provides a more scientific and systematic approach to geopolymer formulations, and provides an active research base for geopolymer structures and properties using specimens prepared from formulation designs according to the major factors of geopolymers. In addition, through the scientific compounding design according to the present invention can improve the economics of the use of raw materials, it is possible to adjust the factors that may cause problems such as the stability of the whitening of the produced geopolymer.
본 발명은 지오폴리머의 특성에 있어서 가장 중요하면서도 기본적인 데이터 를 제공함으로써 지오폴리머 산업 부흥에 기여할수 있을 것으로 기대된다. The present invention is expected to contribute to the revival of the geopolymer industry by providing the most important and fundamental data on the properties of geopolymers.
본 발명은 첨부된 도면에 도시된 일 실시예를 참고로 설명되었으나 이는 예 시적인 것에 불과하몌 당해 기술분야에서 통상의 지식을 가진 자라면 이로부터 다
양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 수 있을 것이다. 따라 서, 본 발명의 진정한 보호 범위는 첨부된 청구 범위에 의해서만 정해져야 할 것이 다.
Although the present invention has been described with reference to an embodiment shown in the accompanying drawings, this is merely exemplary, and will be understood by those skilled in the art. It will be appreciated that various modifications and other equivalent embodiments are possible. Accordingly, the true scope of protection of the invention should be defined only by the appended claims.
Claims
【청구항 1】 [Claim 1]
알투미노실리케이트 성분이 포함된 기본원료와, 알칼리활성화제 및 물을 흔 합하여 제조되는 지오폴리머의 배합비율을 결정하기 위한것으로서, To determine the blending ratio of the base material containing the altuminosilicate component, and the geopolymer produced by mixing an alkali activator and water,
상기 기본원료와 알칼리활성화제를 선택하여 화학조성을 분석하는 원료분석 단계; Raw material analysis step of analyzing the chemical composition by selecting the base material and alkali activator;
상기 기본원료, 알칼리활성화제 및 물의 단위 무게당 Si, Al, Na 및 H에 대 한각각의 몰수 (mole)를산출하는 기본산출단계; A basic calculation step of calculating the number of moles ( mole ) of Si, Al, Na and H per unit weight of the basic raw material, alkali activator and water;
최종적으로 제조되는 지오폴리머 내 Si/Al 몰비 (mole ratio) 및 Na/Al 몰비 를 포함하여 지오폴리머의 특성을 결정하는 주요 인자들에 대한 기준값을 설정하는 타겟설정단계; 및 A target setting step of setting reference values for the main factors for determining the properties of the geopolymer, including the Si / Al mole ratio and Na / Al molar ratio in the finally prepared geopolymer; And
상기 기본산출단계에서 산출된 결과를 기초로, 상기 기본원료, 알칼리활성화 제 및 물을 배합한 흔합물에서 상기 타겟설정단계에서 설정된 주요 인자의 기준값 을 만족시킬 수 있도록 상기 기본원료, 알칼리활성화제 및 물에 대한 각각의 배합 비를 산출하는 배합비산출단계 ;를 포함하여 이루어진 것을 특징으로 하는 지오폴리 머 배합설계방법. On the basis of the result calculated in the basic calculation step, the basic raw material, alkali activator and so as to satisfy the reference value of the main factor set in the target setting step in the mixture of the basic raw material, alkali activator and water Geopolymer blending design method comprising a; formulated ratio calculation step of calculating the respective blending ratio for water.
【청구항 2】 [Claim 2]
제 1항에 있어서, The method of claim 1,
상기 타겟설정단계에서 상기 지오풀리머의 특성을 결정하는 주요 인자는 물 함량비를 더 포함하는 것을 특징으로 하는 지오폴리머 배합 설계방법.
In the target setting step, the main factor for determining the characteristics of the geopolymer, geopolymer blend design method characterized in that it further comprises a water content ratio.
【청구항 3] [Claim 3]
제 1항에 있어서, The method of claim 1,
상기 원료분석단계에서는 상기 기본원료로부터 미연탄소분을 제거하는 전처 리를수행하는 것을특징으로 하는 지오폴리머 배합설계방법. And wherein said raw material analysis step performs pre-treatment to remove unburned carbon powder from said basic raw material.
【청구항 4】 [Claim 4]
제 1항에 있어서, The method of claim 1,
상기 기본산출단계에서는 상기 기본원료에서 결정질로 존재하는 부분을 제외 하고, 비정질로 존재하는 부분에 대해서만 Si, Al, Na 및 H에 대한 각각의 몰 수 (mole)를 산출하는 것을 특징으로 하는 지오폴리머 배합방법. In the basic calculation step, except for the crystalline portion of the base material, the geopolymer, characterized in that for each of the mole (Sile) for Si, Al, Na and H only for the portion present in the amorphous Formulation method.
【청구항 5】 [Claim 5]
제 1항에 있어서, The method of claim 1,
상기 기본산출단계에서 Si, Al, Na, H의 함량을산출하기 위하여, 상기 기본 원료와 첨가제 및 물에 각각 포함되어 있는 Al2¾, Si02, Na20, ¾0의 세부성분 함량 을 측정한 후, 상기 세부성분들에 포함되어 있는 각각의 Si, Al, Na, H의 몰수를 산출하는 것을 특징으로 하는 지오폴리머 배합설계방법 . In order to calculate the content of Si, Al, Na, H in the basic calculation step, by measuring the content of the specific components of Al 2 ¾, Si0 2 , Na 2 0, ¾0 contained in the basic raw materials, additives and water, respectively Then, geopolymer blend design method characterized in that for calculating the number of moles of each of the Si, Al, Na, H contained in the detail components.
【청구항 6】 [Claim 6]
거 U항에 있어서, In U,
상기 가본산출단계에서는 상기 기본원료의 Si/Al 몰비 및 Na/Al 몰비를 분석 하는 것을 특징으로 하는 지오폴리머 배합 설계방법 .
In the calculation step, geopolymer blend design method characterized in that the analysis of the Si / Al molar ratio and Na / Al molar ratio of the base material.
【청구항 7】 [Claim 7]
제 6항에 있어서, The method of claim 6,
상기 타겟설정단계에서는 상기 Si/Al 몰비 기준값을 상기 기본원료의 Si/Al 몰비에 비하여 더 높게 또는 낮게 설정하는 것을 특징으로 하는 지오폴리머 배합 설계방법. In the target setting step, geopolymer formulation design method characterized in that the reference value of the Si / Al molar ratio is set higher or lower than the Si / Al molar ratio of the base material.
【청구항 8】 [Claim 8]
제 1항에 있어서, The method of claim 1,
상기 원료분석단계에서 알칼리활성화제로서 알루민산소다를 선택함에 있어 서, 고체 상태의 알루미산소다 분말을 선택하는 것을 특징으로 하는 지오폴리머 배 합설계방법. In selecting the sodium aluminate as the alkali activator in the raw material analysis step, geopolymer formulation design method characterized in that for selecting a solid state sodium aluminate powder.
【청구항 9】 [Claim 9]
알루미노실리케이트 성분이 포함된 기본원료와, 알칼리활성화제, 첨가제 및 물을혼합하여 제조되는 지오폴리머의 배합비율을 결정하기 위한 것으로서, As to determine the blending ratio of the base material containing the aluminosilicate component, and the geopolymer produced by mixing the alkali activator, additives and water,
최종적으로 제조되는 지오폴리머 내 Si/Al 몰비 (mole ratio), Na/Al 몰비 및 물 중량비를 포함하여 지오폴리머의 특성을 결정하는 주요 인자들에 대한 기준값을 설정하여 입력하는타겟설정단계 ; A target setting step of setting and inputting reference values for the main factors for determining the properties of the geopolymer, including the Si / Al mole ratio, Na / Al mole ratio, and water weight ratio in the finally prepared geopolymer;
상기 기본원료, 알칼리활성화제, 첨가제 및 물의 단위 무게당 Si, Al, Na및 H의 몰수 (mole)에 대한총 16개의 데이터를 산출하는 기본산출단계; 및 A basic calculation step of calculating a total of 16 data on the number of moles of Si, Al, Na, and H per unit weight of the basic raw material, alkali activator, additive, and water; And
상기 기본산출단계에서 산출된 결과를 기초로, 상기 기본원료, 알칼리활성화 제, 첨가제 및 물을 배합한 흔합물에서 상기 타겟설정단계에서 설정된 주요 인자의
기준값을 만족시킬 수 있도록 상기 기본원료 , 알칼리활성화제, 첨가제 및 물에 대 한 각각의 배합비를 산출하는 배합비산출단계 ;를 포함하여 이루어진 것을 특징으로 하는 지오폴리머 배합 설계방법 . On the basis of the results calculated in the basic calculation step, in the mixture of the base material, alkali activator, additives and water of the main factor set in the target setting step Geopolymer blending design method comprising a; formulated ratio calculation step of calculating the respective blending ratio for the base material, alkali activator, additives and water so as to satisfy the reference value.
【청구항 10】 제 9항에 있어서, [Claim 10] The method of claim 9,
상기 기본산출단계는 , 상기 기본산출단계에서 Si , Al , Na, H의 함량을 산출하기 위하여 , 상기 기본 원료와 첨가제 및 물에 각각 포함되어 있는 A1203, Si02, Na20, H20의 세부성분 함량 에 대한 16개의 데이터를 입력하면, 상기 세부성분들에 포함되어 있는 Si , Αί , Na, H의 몰수를 수학적 방법으로 산출히 "는 것을 특징으로 하는 지오폴리머 배합 설계방 법 . The basic calculation step, in order to calculate the content of Si, Al, Na, H in the basic calculation step, A1 2 0 3 , Si0 2 , Na 2 0, H contained in the basic raw materials, additives and water, respectively Entering 16 data on the subcomponent content of 2 0, the number of moles of Si, Αί, Na, H contained in the subcomponents is calculated by mathematical method. .
【청구항 11】 알루미노 실리케이트 성분이 포함된 기본원료와, 알칼리활성화제, 첨가제 및 물을 흔합하여 제조되는 지오풀리머의 배합비율을 결정하기 위한 컴퓨터 프로그램 이 수록된 기록매체로서 , 청구항 9 또는 청구항 10에 기재된 지오폴리머 배합 설계방법이 컴퓨터에서 수행될 수 있는 프로그램 형태로 수록되어 있는 것을 특징으로 하는 지오풀리머 설 계방법 기록매체 .
Claim 11 A recording medium containing a computer program for determining a blending ratio of a basic raw material containing an aluminosilicate component and a geoplymer prepared by mixing an alkali activator, an additive, and water, according to claim 9 or 10. The geopolymer blending design method described in the document is described in the form of a program that can be executed on a computer.
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