TW201927721A - Method for producing inorganic polymerized cements - Google Patents

Abstract

A method for producing an inorganic polymerized cements comprises the following steps: Step (A) obtaining an F-class fly ash and water quenching furnace stone powder. Step (B) is testing the F-class fly ash and water quenching furnace stone powder. Step (C) is to prepare the qualified F-class fly ash and water quenching furnace stone powder, of which the percentage of F-class fly ash is 20% to 80%, and the percentage of water quenching furnace stone powder is 20% to 80%. Step (D) is to mix the material of step (C) with sodium silicate and sodium hydroxide, wherein the liquid-glue ratio is 0.4-0.6, the alkali equivalent is 6-10% The alkali modulus ratio of 1.0 to 2.0. Step (E) is the 3 to 28 days of nursing operations, and carry out various tests.

Description

Method for producing inorganic polymeric cement

The present invention relates to a method for producing a green building material, and more particularly to a method for producing an inorganic polymer cement.

With the vigorous development of the economy and the increasing waste of business, in this era of high environmental awareness, how to deal with the increasing amount of business waste is a matter of urgency.

"Power plant fly ash" is a by-product of power generation from coal-fired power plants. When pulverized coal is burned by boilers, about 80% of ash will rise with gas, when the flue gas flows to the electrostatic precipitator according to the flue. Almost all the ash in the flue gas is adsorbed. This part of the coal ash is called "power plant fly ash". The domestic thermal power plant is mainly based on coal-fired power generation, with an annual production capacity of about 2 million metric tons. Contains a large amount of oxides such as SiO ₂ , Al ₂ O ₃ and Fe ₂ O ₃ , and the Environmental Protection Agency announces that it is a renewable material. How to improve the utilization rate of fly ash in power plants and solve the problem of high-yield ash slag accumulation is also an important issue that must be faced by environmental protection.

In addition, the carbon dioxide produced by the cement industry affects the global warming. According to statistics, the production of 1 ton of cement emits about 1 ton of carbon dioxide into the atmosphere, and the process of manufacturing the second raw material and the raw material of the cement, which promotes air pollution. Make the earth darker and increase the global warming effect. The global cement industry contributes about 6% to carbon dioxide emissions, which in turn contributes to a 4% global warming effect. The greenhouse gas emissions generated by cement are estimated to be about 1.35 billion tons, accounting for about 7% of total greenhouse gas emissions. Therefore, some scholars suggest using less natural resources to mine and reduce energy consumption to reduce carbon dioxide emissions. He pointed out that short-term efforts can start from "industrial ecology". Long-term goals can use industrial waste products instead of cement to reduce the use of cement to reduce dioxide. Carbon emissions.

It can be seen from this that how to effectively use business waste while reducing air pollution is an urgent need for researchers.

Accordingly, it is an object of the present invention to provide a method for producing an inorganic polymeric cement which can utilize commercial waste.

The method for producing an inorganic polymeric cement of the present invention comprises the following steps: Step (A): obtaining a Class F fire power plant fly ash and water quenching furnace stone powder. Step (B) is to test the fly ash and water quenching furnace powder of the F-class thermal power plant. Step (C) is to mix the qualified F-class thermal power plant fly ash with the water quenching furnace stone powder, wherein the percentage of fly ash in the F-class thermal power plant is 20%~80%, and the percentage of the water quenching furnace powder is 20%~ 80%. Step (D) is a step of adding the material of the step (C) to sodium carbonate and sodium hydroxide for mixing with an inorganic polymer cement, wherein the liquid-to-gel ratio is 0.4 to 0.6, and the alkali equivalent is 6% to 10%. The ratio is 1.0 to 2.0, and the inorganic polymer slurry is produced. Step (E) is carried out for 3 to 28 days of maintenance work, and various tests are performed.

Another technical means of the present invention is that in the step (D), sodium citrate and sodium hydroxide are used for adjusting the alkali-containing equivalent ratio to the alkali modulus, and the sodium citrate is a sodium citrate solution.

Another technical means of the present invention is that in the step (B), the physical properties of the fly ash of the F-class thermal power plant are tested, and XRD and XRF analysis are performed.

Still another technical means of the present invention is to prepare an inorganic polymer slurry having a base equivalent of 6%, 8%, and 10% in the step (D).

Another technical means of the present invention is to prepare an inorganic polymer slurry having an alkali modulus ratio of 1.0, 1.5, 2.0 in the step (D).

Another technical means of the present invention lies in the step (D) Medium is an inorganic polymer slurry having a liquid to rubber ratio of 0.4, 0.5, and 0.6.

Still another technical means of the present invention is that in the step (E), the maintenance operation is performed for 3 days, 7 days, and 28 days.

Another technical means of the present invention is that in the step (C), the proportions of the water quenching furnace powder/F-class thermal power plant fly ash are 20/80, 40/60, 60/40, 80/20, respectively.

Another technical means of the present invention is that in the step (E), a compression test, a coagulation time test, and a dry shrink test are performed.

According to still another technical means of the present invention, in the step (C), the fly ash and the water quenching furnace powder of the F-class thermal power plant are required to be ground to a fineness requirement of at least 4000 (cm ² /g) or more.

The beneficial effect of the invention is that the activity of the fly ash of the power plant is enhanced by the alkali activation treatment technology, and the ability of the fly ash cementation of the power plant is stimulated to be made into an inorganic polymer green cement, which is used as a reference for future engineering design.

1 to 3 are columnar statistical diagrams illustrating the effect of alkali equivalent on the setting time of the fly ash inorganic polymer in a preferred embodiment of the method for producing an inorganic polymeric cement of the present invention; FIGS. 4 to 6 Is a columnar statistical diagram illustrating the effect of alkali equivalent on the compressive strength of the fly ash inorganic polymer in the preferred embodiment; Figures 7 to 9 are columnar charts illustrating the base in the preferred embodiment. The effect of equivalent on the water absorption of the fly ash inorganic polymer in the power plant; Figures 10 to 12 are all columnar statistical diagrams, showing the effect of alkali equivalent on the dry shrinkage of the fly ash inorganic polymer in the preferred embodiment; Is a crystal phase diagram, indicating that in the preferred embodiment, AE = 6%, Ms = 2.0, W / B = 0.4, the crystal phase structure of the ratio S20F80; Figure 14 is a crystal phase diagram, illustrating the preferred implementation In the example, AE=6%, Ms=2.0, W/B=0.4, and the crystal phase structure of the S40F60 ratio; FIG. 15 is a crystal phase diagram showing that in the preferred embodiment, AE=6%, Ms=2.0 , W / B = 0.4, the ratio of the crystal phase structure of S60F40; Figure 16 is a crystal phase diagram, illustrating AE = 6% in the preferred embodiment, Ms=2.0, W/B=0.4, the crystal phase structure of the ratio S80F20; FIG. 17 is a crystal phase diagram showing that in the preferred embodiment, AE=8%, Ms=2.0, W/B=0.4, The crystal phase structure of S20F80; FIG. 18 is a crystal phase diagram showing the crystal phase structure of AE=8%, Ms=2.0, W/B=0.4, and ratio S40F60 in the preferred embodiment; FIG. The crystal phase diagram illustrates the crystal phase structure of AE=8%, Ms=2.0, W/B=0.4, and the ratio of S60F40 in the preferred embodiment; FIG. 20 is a crystal phase diagram illustrating the preferred embodiment. , AE = 8%, Ms = 2.0, W / B = 0.4, the crystal phase structure of the ratio S80F20; Figure 21 is a crystal phase diagram, indicating that in the preferred embodiment, AE = 10%, Ms = 2.0, W /B=0.4, the crystal phase structure of the ratio S20F80; FIG. 22 is a crystal phase diagram showing the crystal phase of the SF=10%, Ms=2.0, W/B=0.4, and the ratio of S40F60 in the preferred embodiment. Figure 23 is a crystal phase diagram showing the crystal phase structure of AE = 10%, Ms = 2.0, W / B = 0.4, and the ratio of S60F40 in the preferred embodiment; and Figure 24 is a crystal phase diagram, In the preferred embodiment, AE=10%, Ms=2.0, W/B=0.4, and the crystal phase structure of S80F20.

A preferred embodiment of the method for producing an inorganic polymeric cement of the present invention comprises the following steps.

Step (A) Obtain a fly ash from a Class F thermal power plant. "Fly ash" is a by-product of power generation from coal-fired thermal power plants. When pulverized coal is burned by a boiler, about 80% of the ash will rise with the gas. When the flue gas flows to the electrostatic precipitator according to the flue. Almost all the ash in the flue gas is adsorbed. This part of the coal ash is called fly ash, while the other part of the ash is coarser and heavier. It falls directly to the boiler. The bottom is called "bottom ash". The fly ash collected by the dust collection equipment shall be of a quality in accordance with CNS 3036 [Buyland cement concrete fly ash and natural or sputum burnt sputum] or CNS 11271 [Butel fly ash cement fly ash] According to the regulations, the composition and quality of fly ash are greatly affected by the burning process of coal source or power plant. Fly ash is divided into two types, C and F. Those who use lignite or sub-bituminous coal to burn collectors are classified as C, in addition to having activity as A certain degree of cementation, CaO content may be higher than 10%; and the use of anthracite or bituminous coal combustion to obtain F, which only has a sputum activity. At present, the fly ash produced by the Taiwan Power Company's thermal power plant is mostly Class F.

Among them, the physical properties of fly ash include (1) fineness, (2) 岚 activity index, (3) high pressure steamer expansion rate (health), and (4) loss on ignition (LOI). Among them, in terms of fineness, according to CNS 3036, the fly ash fineness wet screening method, the percentage of retention of No. 325 sieve, the maximum value is 34%; the larger the residence rate, the coarser the fly ash, the carbon content The bigger it is. The smaller the particles, the larger the specific surface area of the fly ash, and the higher the activity index. In terms of activity index, it refers to the ratio of the strength of fly ash and Putlan cement mortar tested to 28 days according to CNS 3036 to the control group (pure Portland cement mortar sample). CNS stipulates that the minimum value is 75%; the greater the activity index of the sputum, the better the reaction ability of fly ash and calcium hydroxide, and the better the quality of concrete. In terms of strength, CNS 3036 stipulates that the maximum expansion ratio of fly ash concrete in the autoclave is 0.8% to prevent abnormal expansion or contraction of concrete. In terms of loss on ignition, when the pulverized coal is burning, a small amount of coarser carbon particles are not completely burned and are caught as the fly ash floats upward. These carbon particles will still burn and lose weight at high temperatures. , called the loss on ignition. The higher the loss on ignition, the higher the carbon content in the fly ash; the higher the water demand of the concrete, the lower the effect on the chemical admixture. The fly ash according to CNS 3036, F and C fly ash. No more than 6%.

Gypsum powder is an industrial by-product manufactured by the production of steel. It is obtained by hot-melting blast furnace slag by water spray cooling granulation treatment and grinding into fine powder. The classification of hearthstone can be divided into two types: gas-cooled hearthstone and water-hardened hearthstone depending on the cooling method. The former is to place the blast furnace slag in a cold manner, so that it can be slowly cooled, and has enough time to complete the crystallization, so that it has a hard and dense structure, high stability, and due to its small glassy composition, The cementation function is not good, and it is generally used as a raw material for cement manufacturing. The water quenching furnace stone is sprayed with water to rapidly cool it, and a large amount of incompletely crystallized glass is produced. The microstructure is relatively messy and the activity is high. After proper grinding and treatment, the cement has the same cement property. Since the steel production raw materials are similar to the chemical composition of the cement raw materials, the ratio of the composition of the hearth powder to the cement clinker is slightly different, and the remaining components are very similar. The particle shape of the blast furnace clinker is polygonal like a gravel. It can be used as a supplementary material for cement. After fine grinding, it can directly replace the cement. If the grinding is finer, the contact area with water is larger, and the reactivity is more. good. The finer the clinker clinker is, the more the area of contact with water increases. For the same water-cement ratio, the proportion of adsorbed water increases. Of course, the free water is reduced, the viscosity is relatively increased, and the bleeding and precipitation are inhibited. Function, but workability is slightly reduced due to the increase in internal shear. In terms of strength, the hydration "reaction field" is increased by the increase in fineness, so that the initial good strength quality can be provided, but the reduction rate of hydration heat is relatively reduced. Usually, the fineness of the whetstone clinker is required to be at least 4,000 (cm ² /g) or more. However, the mechanical grinding process involves cost, and if the grinding fineness exceeds 6000 (cm ² /g), it can become high. The grouting material at the price point belongs to the site improvement material. That is, the tiny grit powder particles can be effectively filled between the cement particles to make the slurry structure more compact.

Inorganic polymer is a kind of framework structure and chemical composition similar to zeolite (Zeolite). French scientist Joseph Davidovits used hydrothermal synthesis to synthesize aluminosilicate minerals rich in antimony and aluminum. A framework structure of approximately zeolite (Zeolite) is synthesized in a high alkali solution environment, wherein metakaolin is most representative, and aluminosilicate mineral is amorphous or semi-crystalline. The three-dimensional alumino-silicate composite material is mainly prepared by dissolving elements such as bismuth and aluminum in mineral powder in a highly alkaline solution environment, and then bonding with oxygen ions to form a closed frame-like structure. This material is referred to as "Geopolymer" in Taiwan.

The inorganic polymer is mainly composed of a mineral material rich in yttrium aluminum oxide and a basic activator, and can be polymerized under normal temperature environment, hardened after drying and dehydrating, and has high strength, hard solid fastness and high temperature resistance. , chemical corrosion resistance and low thermal conductivity, in addition to The material's manufacturing process consumes less energy than ordinary Portland cement, which reduces carbon dioxide emissions, making inorganic polymers a new type of green energy material with forward-looking development. The raw materials for the production of inorganic polymeric materials are quite extensive, and any mineral containing aluminum and cerium elements can be used as a raw material. The inorganic polymer is usually prepared by mixing three kinds of added materials: (1) lnactive Filler; (2) inorganic polymer (Geopolymer Liquor); (3) active additive (Active Filler) And the liquid contains an alkali metal citrate solution and an aqueous alkali metal hydroxide solution. Inorganic polymers are usually made by mixing three added materials, respectively:

1. Aluminium silicate materials: In the current domestic research, aluminosilicate materials are classified into natural minerals, mostly kaolin and metakaolin; while wastes are more common in furnaces, fly ash, reservoir sludge, etc. In the case of kaolin, the pretreatment can be completed at 500~900 °C, while the Portland cement calcination temperature needs 1450~1550 °C. Compared with mineral materials of inorganic polymers, it is convenient to obtain, so the current research can also be used. Industrial waste furnaces can also be used to make the furnace waste resources.

2. Sodium citrate solution: At present, the sodium citrate solution on the market differs depending on the concentration of the solution. The liquid sodium citrate solution is more common. Some studies have pointed out that the concentration of sodium citrate solution itself and the inorganic polymer There is no significant proportional relationship between the compressive strengths, and the addition of sodium citrate solution can supplement the Si ⁴⁺ in the polymerization reaction, ^thereby exciting the cementation of the inorganic polymer and increasing the compressive strength.

3. Alkali metal solution: The types of alkali metal solutions are mostly divided into NaOH or KOH solutions, which are divided into powder type and liquid type. For research purposes, it is proposed that metal oxides are easily dissociated in water to produce metals. Under the action of ions and hydroxide ions and aluminosilicate raw materials, the structure of minerals will be gradually eroded by OH-destruction from the outside to the inside, and the aluminosilicate monomer anions will be precipitated from the structure, followed by Si ⁴⁺ Al ³⁺ is a centrally linked peripheral hydroxyl group, wherein the hydroxyl group is one of the functional groups having a condensation function, which promotes the reaction and can be repolymerized.

The inorganic polymer is produced by mixing aluminum strontium-rich minerals rich in aluminum and strontium with a highly alkaline solution to achieve polymerization. The relationship between the inorganic polymer process and strength development is divided into the following four stages:

1. Dissolution: The aluminosilicate-rich mineral is mixed with an alkaline activator to dissolve.

2. Diffusion: The aluminum and antimony elements are precipitated from the surface of the mineral particles, and begin to diffuse from the surface of the particles to the interstices of the particles, and slowly begin to generate polymerization to produce strength.

3. Polymerization: The polymerization reaction between the alkali metal citrate solution and the aluminum and strontium elements and the dehydration reaction stage, the polymerization reaction is more intense, and the strength is rapidly developed.

4. Hardening: In the hardening stage, the colloid begins to harden after removing excess water in the overall structure, and its strength development gradually becomes gentle with the polymerization reaction.

The above-mentioned inorganic polymer reaction process can be divided into the following four processes in the microscopic direction:

1. The aluminosilicate mineral material is dissolved in a highly alkaline solution.

2. The OH ^- destroyed aluminosilicate material structure in the high alkali solution separates Si ⁴⁺ and Al ³⁺ and bonds with oxygen ions to form a tetrahedral structure of SiO ₄ and AlO ₄ .

3. SiO ₄ and AlO ₄ continue to react, and form a Si-O-Si (Al) framework structure by sharing oxygen atoms.

4. The gel phase is gradually consolidated and hardened, and the remaining moisture is removed to form an inorganic polymer.

The alkali-activated binder absorbs aluminum silicate materials such as fly ash, metakaolin, ground blast furnace slag (GGBFS), kaolin clay, rice husk, etc., and most of them contain a large amount of SiO ₂ and Al ₂ O ₃ , and It is easy to produce a polymerization reaction when it is made into contact with an alkaline solution, and in the inorganic polymer precursor, the tetrahedral peripheral structure of SiO ₄ and AlO ₄ is a structure with OH ^- in the inorganic polymer precursor, and is hard. In the solid-state process, due to the polymerization reaction, the two are bonded to each other, and the excess H ⁺ and OH ^{- are} eliminated, and then H ₂ O is formed by mutual bonding, thereby generating a dehydration reaction.

When the lead structure is dehydrated, it will be polycondensed and hardened to form an inorganic polymer, which is the "polycondensation process of polymerization". After the aluminosilicate mineral is mixed with the alkali activator and sodium citrate (solid or liquid) An inorganic polymer colloid is produced which is then reacted with the remaining aluminosilicate mineral and finally hardened to form a structurally intact inorganic polymer. However, there must be sufficient pores in the structure to provide water-soluble alkali metal ions such as Na ⁺ or K ^{+ to} enter and balance the overall charge. The chemical reaction process of inorganic polymerization is the chemical reaction between various aluminosilicates and strong alkali citrate solutions.

The inorganic polymer is represented by Polysialate under the chemical nomenclature of Si and Al. The empirical formula of Polysialate is as follows: Mn-[-(SiO ₂ )Z-AlO ₂ ] n . w H ₂ O, wherein M = alkali metal cation (eg K ⁺ , Na ⁺ , Ca ²⁺ )

n=degree of polycondensation

z=1, 2, 3 or more, (mainly polymeric structural unit Si: Al atom molar ratio)

w=crystalline water content

When the atomic molar ratio of Si:Al≦3:1 in the framework of the inorganic polymer precursor, the structural form also changes with the Mo:Al atom molar ratio, which changes its basic structure. Divided into three structural types, single-dimensional yttrium aluminum polymer Poly (sialate), two-dimensional yttrium aluminum polymer Poly (sialate-siloxo), yttrium aluminum polymer Poly (sialate-disiloxo), its structure is shown in Table 1 .

As the Si:Al molar ratio increases, the compressive strength is higher, but when the Si:Al ratio is too high, too much SiO ₄ will not be fully bonded to AlO ₄ except for the source of Si ⁴⁺ . In addition to the acid salt material, the sodium citrate solution can also provide Si ⁴⁺ , but when the sodium citrate solution is added too much, the precipitation of Si ^{4+ is} relatively increased, so that it is easy to cause more bubbles in the inorganic polymerization process, and the slurry is made. The compressive strength of the body is reduced and becomes brittle.

Table 1. Mo/E ratio of each Si/Al atom of inorganic polymer

In addition, regarding the reaction mechanism of alkali activation, the alkali activation technology utilizes high alkali characteristics. Generally, NaOH and KOH are commonly used in high alkali solution, and most of the alkali activators are mainly sodium citrate solution to improve the work. The purpose of material activity. Since the alkali activation technology utilizes a highly alkaline solution to catalyze the cement material and thereby generate an alkali activation reaction, that is, the structure in which the cemented material is bonded by the high alkaline solution is broken, and the Ca ^{2+ is} dissociated to cause an alkali activation reaction. The base equivalent used is generally lower than the alkalinity required for the inorganic polymer. The pH of the alkali activator is 11.5, which can be used as the activation threshold, which can provide sufficient alkalinity to destroy the Ca ^{2+ of the} cement to cause dissociation to produce an alkali activation reaction. The reaction mechanism of the alkali activator is mainly to use its high alkali characteristic to increase the alkaline concentration in the environment, destroy the vitreous crystal on the surface of the material, and thereby achieve the purpose of rapid reaction with the alkali activator ions, and the alkali activator The reaction of the material is divided into two phases:

1. The high pH base activator is used to destroy the bond of the multi-calcium aluminosilicate mineral material, thereby converting it into bismuth, aluminum and calcium ions to facilitate the reaction.

2. The anion or anion group (SiO ₄ , AlO ₄ ) which is re-bonded in the alkali activator and the Ca ²⁺ dissolved in the polycalcium aluminate mineral form a base activation reaction and form a CSH colloid. Hydration product.

During the first-stage reaction process described above, the pH of the activator will affect the formation of some hydration products at the initial stage. During the reaction at this stage, the pH of the alkali activator is set to 11.5 as the acceleration. A threshold value for the alkali activation reaction defines a standard to provide sufficient energy to dissolve and destroy the bond between bismuth and aluminum oxide and to dissolve Ca ²⁺ , and the pH of the general alkali activator is above this threshold. However, the main control of the hydration product formation reaction is the second-stage reaction. The formation of the hydration product depends on the type of anion or anion group eluted by the alkali activator, such as tetrahedral structure such as SiO ₄ or AlO ₄ , so the type of activator The difference in the product will be determined, which is also the main stage affecting the development of intensity.

As for the influence factors of the alkali activator,

1. Sodium hydroxide (NaOH): Sodium hydroxide has enough energy to destroy Ca-O, Mg-O or even Si-O and Al-O bonding. Its pH is about 13.87, which is the first among many activators. The reaction at the stage is the best. However, it is not precipitated in solution because it is a highly soluble product, Ca(OH) ₂ . Although there are other hydration products such as low C/S ratios of CSH, C ₄ AH ₁₃ and C ₂ ASH ₈ , the proportion is far less than that of the product Ca(OH) ₂ , even if its solubility is much lower than Ca (OH) ₂ also does not provide strength as appropriate.

2. Sodium citrate (Na ₂ SiO ₃ ): Sodium hydroxide has the highest pH value among all the alkali activators, and sodium citrate has a secondary pH of about 12.89. Although the pH of sodium citrate is lower than that of sodium hydroxide, the OH ^- ion can destroy the bonding of Ca-O, Si-O and Al-O after contact with ash particles. In addition, the SiO ₄ ^2- high concentration anion group dissociated from the C ²⁺ colloid dissolved on the surface of the ash particles and the sodium citrate itself is one of the indispensable elements. The alkali-activated hydration heat curve shows that the peak curve in the initial stage of hydration is caused by the wetness and dissolution of the binder particles, and the reaction of some particles on the surface of the binder particles, which can also be expressed as Ca ² dissociated from the binder. ⁺ Reaction with SiO ₄ in the alkali activator and formation of CSH colloid is also the main hydration product. Further, if high silica concentration of sodium, the dissociation of higher Ca ²⁺ SiO ₄ ^2-, Ca ²⁺ can lead to a serious shortage, thereby promoting part of the SiO ₄ ^2- polymerization reaction, it may Causes false condensation.

3. Alkali equivalent and alkali modulus ratio: the activation effect of alkali activator is closely related to the concentration. Generally speaking, when sodium citrate is used as the alkali activator, there are two variables to be considered, which are alkali modulus ratio and Contains alkali equivalent. The former alkali modulus ratio is one of the characteristics of sodium citrate, that is, the weight ratio of cerium oxide to sodium oxide, and sodium hydroxide can be adjusted according to experimental requirements. The latter alkali-containing equivalent is the weight percentage relative to the cementitious material, and the chemical formula molecular weight of the chemical agent is converted into the amount of the chemical added.

Step (B) is to test the fly ash and water quenching furnace powder of the F-class thermal power plant. In the present embodiment, the water quenching furnace stone powder is obtained by using water quenching blast furnace hearth powder produced by Zhonglian Resource Treatment Co., Ltd., and is processed and ground into powder, and the properties are in accordance with CNS 12549, and the fineness is 4000 cm ² /g, wherein The X-ray diffraction analysis (XRD) is used to understand the composition of each phase of the grit powder. The figure shows that the grit powder is an amorphous compound composition, and the X-ray fluorescence analysis (XRF) is used to investigate the content of each element in the grit powder sample. Among them, the content of elements such as CaO and SiO _{2 is the} highest, and various compounds obtained by XRD analysis are combined, and the chemical composition is calculated by gravimetric analysis, and then the percentage of oxidation state of each element of the hearth powder is calculated. In addition, the F-class thermal power plant fly ash is taken to Xingda thermal power plant, and X-ray diffraction analysis (XRD) is used to understand the composition of each phase of the fly ash of the power plant, showing that the main crystalline compound of the fly ash of the power plant is SiO ₂ , secondary The crystalline compounds are Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, K ₂ O, Na ₂ O, etc., and X-ray fluorescence analysis (XRF) is used to investigate the content of each element in the fly ash sample of the power plant. The content of C, O, Si, Al, Fe, Ca, K, Mg, Na and other elements is the highest. The chemical composition of various compounds obtained by XRD analysis is calculated by gravimetric analysis. The percentage of the content is as shown in Table 2.

Table 2. Chemical properties of water quenching furnace powder and power plant fly ash

Step (C) is to mix the qualified F-class thermal power plant fly ash with the water quenching furnace stone powder. The F-class thermal power plant fly ash and water quenching furnace stone powder need to be ground to a fineness requirement of at least 4000 (cm ² /g) or more. Among them, the percentage of fly ash in F-class thermal power plants is 20%~80%, and the percentage of water quenching furnace powder is 20%~80%. The proportion of fly ash in water quenching furnace powder/F-class thermal power plant is 20/80 (S20F80), 40/60 (S40F60), 60/40 (S60F40), 80/20 (S80F20).

Step (D) is a step of adding the material of the step (C) to sodium carbonate and sodium hydroxide for mixing with an inorganic polymer cement, wherein the liquid-to-gel ratio is 0.4 to 0.6, and the alkali equivalent is 6% to 10%. The ratio is 1.0 to 2.0, and the inorganic polymer slurry is produced. The preferred embodiment uses the No. 3 sodium citrate solution produced by Rongxiang Industrial Co., Ltd., which is a transparent colorless, odorless and viscous liquid, also known as water glass chemical agent, and is an industrial grade product in the domestic market. In use, it can be divided into a powder type and a solution type. The reason why the powder type is not used is that the powder type can provide better workability, and the reaction effect is not as good as that of the solution type, and is used in the preferred embodiment. Sodium is mainly sodium citrate solution No. 3. The sodium citrate solution is added in the preferred embodiment in order to provide sufficient Si ⁴⁺ and to enhance the properties of the inorganic polymer colloid to increase the strength of the inorganic polymer. Therefore, the preferred embodiment is a sodium citrate solution. Used to stimulate and enhance the active use of fly ash in power plants. In addition, the preferred embodiment adopts sodium hydroxide produced by Tongwei Enterprise Co., Ltd., commonly known as caustic soda, which is an industrial grade drug with a molecular weight of about 40 and a purity of over 98%. Its composition is shown in Table 3-4. It is shown that the purpose of its use is not only to stimulate and enhance the activity of the water quenching furnace powder, but also to adjust the concentration of the alkali activator with sodium citrate.

In the present embodiment, an inorganic polymer slurry having a base equivalent of 6%, 8%, 10%, a liquid-to-binder ratio of 0.4, 0.5, 0.6 and an alkali modulus ratio of 1.0, 15, and 2.0 is prepared. Table 3 below.

1. Alkali equivalent (AE): The alkali equivalent is the weight percentage of the cement material used for the alkali amount, and the chemical formula molecular weight of the chemical agent is converted.

2. Alkali modulus ratio (Ms): The alkali modulus ratio is the dose of alkali metal citrate, which is simply the weight ratio of cerium oxide to sodium oxide. Hydrogen can be used according to the test. Sodium oxide is adjusted.

3. Liquid-to-gel ratio Water/Fly Ash and Slag (W/B): In the design of this experiment, the liquid-to-gel ratio is 0.4, 0.5 and 0.6. In the alkali-activated power plant fly ash test part, the liquid-to-gel ratio is alkali. The ratio of the activator solution to the weight of the power plant fly ash water quenching furnace powder mixture, and in the Portland cement group test body, the liquid to gel ratio is the so-called water-to-binder ratio.

Step (E) is carried out for 3 to 28 days of maintenance work, and various tests are performed. Among them, the test items include a condensation time test, a compressive strength test, a water absorption test, a length change test, and the crystal state is observed by a scanning electron microscope.

First, the condensation time test

Concrete begins to produce hydration after adding water. The hydration process produces CSH colloid and obtains strength, which makes the internal structure more dense. The fly ash inorganic polymer in the power plant converts between liquid and solid during condensation, and is excited by alkali. The agent stimulates the activity of the fly ash in the power plant and generates a polymerization reaction. However, the setting time is also one of the important indicators for evaluating the workability.

(1) Effect of alkali equivalent: The test of hydraulic cement setting time was measured by a Fischer-Tropsch needle. The initial setting time of the cement was 1.5 to 3 hours, and the final setting time was 3 to 6 hours. Taking an alkali modulus ratio of 1.0 and a liquid-to-gel ratio of 0.4 as an example, when the alkali equivalent is 6%, 8%, and 10%, the final setting time falls within the range of 6 minutes to 245 minutes, and the mixing ratio of S20F80, S40F60, S60F40, etc. Only when the alkali equivalent AE is 8% meets the requirements as shown in Figure 1(a). Taking an alkali modulus ratio of 1.5 and a liquid-to-gel ratio of 0.6 as an example, when the alkali equivalent is 6%, 8%, and 10%, the final setting time falls within the range of 63 minutes to 332 minutes, and only the S20F80 and S40F60 mixed ratios are in the alkali. The equivalent AE is 10% to meet the requirements as shown in Figure 2(c).

Taking an alkali modulus ratio of 2.0 and a liquid-to-gel ratio of 0.5 and 0.6 as an example, when the base equivalent is 6%, 8%, and 10%, the final setting time falls within the range of 42 minutes to 200 minutes, and only the S20F80 mixed ratio is equivalent to the base equivalent. The AE is 10% to meet the requirements as shown in Figure 3(b)(c). The results show that the increase of alkali equivalent promotes the tendency of the setting time to shorten. The main reason is that the concentration of the high alkali solution is increased due to the increase of the alkali equivalent, which causes the OH-ion to break the structure of the cement and increase the dissolution of Si4+, Al3+ and Ca2+. The phenomenon that the fly ash inorganic polymer of the power plant accelerates the polymerization reaction and produces a hard solid colloid, thereby causing the condensation time to be shortened. If no additives with a retarding effect are added, reducing the alkali equivalent can also improve the problem of too fast setting time.

(2) Effect of alkali modulus ratio: When the liquid-to-binder ratio is 0.5 and the alkali equivalent AE is 6%, 8%, and 10%, the final setting time increases as the alkali modulus ratio increases from 1.0 to 2.0. Between 10~61 minutes, 33~150 minutes, and 42~200 minutes, as shown in Figure 1(b), Figure 2(b), and Figure 3(b). The mixing ratio of S20F80, S40F60, S60F40, etc. only meets the requirement when the alkali equivalent AE is 8%, as shown in Fig. 1(a). Only S20F80 mixed mix ratio in alkali modulus ratio 2.0, liquid glue The ratio is 0.5, and the alkali equivalent AE is 10% to meet the requirements as shown in Fig. 3(b).

When the liquid-to-binder ratio is 0.6 and the alkali equivalent AE is 6%, 8%, and 10%, the final setting time is between 10 and 20 minutes, 63~ as the alkali modulus ratio increases from 1.0 to 2.0. Between 332 minutes and 60 to 185 minutes, as shown in Fig. 1 (c), Fig. 2 (c), and Fig. 3 (c). Only S20F80, S40F60 mixed mix ratio in the alkali modulus ratio of 1.5, liquid to rubber ratio of 0.6, alkali equivalent AE of 10% meet the requirements, as shown in Figure 2 (c).

It can be seen that the setting time will decrease with the increase of the alkali modulus ratio, mainly because the Si4+ content in the slurry of the plant fly ash inorganic polymer increases when the alkali modulus ratio increases, and the Si/Al atom Moh The ratio changes, thus causing the polymerization to accelerate.

(3) the influence of liquid to rubber ratio

When the fixed alkali equivalent 6% and the alkali modulus ratio are 1.0, 1.5 and 2.0, the liquid gel ratio is raised from 0.4 to 0.6, and the final setting time is between 12 and 20 minutes and between 23 and 235 minutes. 41 to 112 minutes are shown in Figure 1 (a) (b) (c), Figure 2 (a) (b) (c), Figure 3 (a) (b) (c). Among them, the mixing ratio of S20F80, S40F60, etc. is only 6% of alkali equivalent AE, the ratio of alkali modulus is 1.5, and the ratio of liquid to rubber is 0.6, as shown in Fig. 2(a)(b)(c).

When the fixed base equivalent weight is 8% and the alkali modulus ratio is 1.0, 1.5 and 2.0, the liquid gel ratio is raised from 0.4 to 0.6, and the final setting time is between 10 and 245 minutes and between 35 and 210 minutes. Between 38 and 115 minutes is shown in Figure 1 (a) (b) (c), Figure 2 (a) (b) (c), Figure 3 (a) (b) (c). Among them, S20F80, S40F60 and other mixed ratios only meet the requirements when the alkali equivalent AE is 8%, the alkali modulus ratio is 1.0, the liquid-to-binder ratio is 0.4, and the alkali equivalent AE is 8%, and the alkali modulus ratio is 1.5. Figure 1 (a) (b) (c), Figure 2 (a) (b) (c).

When the fixed base equivalent is 10% and the alkali modulus ratio is 1.0, 1.5 and 2.0, the liquid gel ratio is raised from 0.4 to 0.6, and the final setting time is between 6 and 19 minutes and between 33 and 332 minutes. Between 53 and 200 minutes is shown in Figure 1 (a) (b) (c), Figure 2 (a) (b) (c), Figure 3 (a) (b) (c). Among them, S20F80, S40F60 and other mixed ratios only meet the requirements when the alkali equivalent AE is 10%, the alkali modulus ratio is 1.5, the liquid-to-binder ratio is 0.6, and the alkali equivalent AE is 10%, and the alkali modulus ratio is 2.0. , as shown in Figure 2 (a) (b) (c), Figure 3 (a) (b) (c).

It is known from the experimental results that the setting time will prolong with the increase of the liquid-to-gel ratio, mainly due to the fixed alkali equivalent and the alkali modulus ratio, and the alkali equivalent concentration is increased by the alkali metal sodium citrate solution. The water is diluted, resulting in a decrease in the alkali equivalent and the alkali modulus ratio, so that the setting time of the slurry is increased.

Second, the compressive strength

Compressive strength is one of the most important indicators of general concrete and alkali cement, mainly to understand the internal compactness and porosity of the sample.

(1) Effect of alkali equivalent: To investigate the effect of alkali equivalent on the compressive strength of the fly ash inorganic polymer sample of power plant, aim at the range of 6%, 8% and 10% alkali equivalent, and control the alkali modulus ratio to 1.0. Under the conditions of 0.4, 0.5 and 0.6, the compressive strength range of the 3-day curing time when the alkali equivalent is changed from 6% to 10% is 209.17~619.21kgf/cm ² and 217.48~637.29kgf/cm ^{2 respectively.} 161.24~458.43kgf/cm ² , in the 7-day curing age, it is 275.32~710.73kgf/cm ² , 251.15~675.48kgf/cm ² , 157.96~537.16kgf/cm ² , in its 28-day curing age The time is 319.08~1001.13kgf/cm ² , 345.89~963.16kgf/cm ² , 202.97~689.15kgf/cm ² , as shown in Fig. 4(a)(b)(c). It can be seen from the above strength trend that the compressive strength increases with the increase of the curing time, and gradually decreases with the increase of the alkali equivalent. Among them, the mixed ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6% of the alkali equivalent. 8% and 10%, liquid-to-plastic ratio of 0.4, and alkali modulus ratio of 1.0 have the highest compressive strength and have reached the requirements of ordinary cement (Type I) compressive strength.

When the alkali modulus ratio is 1.5 and the liquid-to-binder ratio is 0.4, 0.5 and 0.6, the compressive strength range of the 3-day curing time when the alkali equivalent is changed from 6% to 10% is 295.33~851.36kgf/cm ² , respectively. 295.73~878.37kgf/cm ² and 247.01~754.29kgf/cm ² , which are 348.83~839.28kgf/cm ² , 423.08~859.96kgf/cm ² and 339.97~769.69kgf/cm ² respectively during the 7-day curing period. At the 28-day curing age, they were 364.88~965.23kgf/cm ² , 73.77~1014.92kgf/cm ² and 175.16~699.15kgf/cm ^{2 respectively} , as shown in Fig. 5(a)(b)(c). Among them, S20F80, S40F60, S60F40, S80F20 and other mixed ratios are 6%, 8% and 10% in alkali equivalent, liquid-to-gel ratio is 0.4, and alkali modulus ratio is 1.5. The compressive strength is the highest, which has reached the ordinary cement (Type I) resistance. Pressure strength requirements.

When the alkali modulus ratio is 2.0 and the liquid-to-binder ratio is 0.4, 0.5 and 0.6, the compressive strength range of the 3-day curing time when the alkali equivalent is changed from 6% to 10% is 359.23~797.41kgf/cm ² , respectively. 308.61~834.53kgf/cm ² , 276.43~761.97kgf/cm ² , respectively, at the 7-day curing age, 345.39~981.67kgf/cm ² , 336.43~1013.61kgf/cm ² , 165.67~850.41kgf/cm ² , At the 28-day curing age, they are 259.15~963.36kgf/cm ² , 408.31~1050.24kgf/cm ² , and 443.56~988.36kgf/cm ^{2 respectively,} as shown in Fig. 6(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%, 8% and 10%, the ratio of liquid to rubber is 0.4, and the ratio of alkali modulus to 2.0 is the highest. It can be seen from the above strength trend that the compressive strength increases with the increase of the curing time, and gradually decreases with the increase of the alkali equivalent. Among them, the mixed ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%. Increased to 10%, liquid-to-gel ratio of 0.4, alkali modulus ratio of 2.0, 3 days, 7 days and 28 days, the highest compressive strength, has reached the requirements of ordinary cement (Type I) compressive strength. The main reason is that the alkali equivalent is increased, the alkali activator concentration is increased, and the activation effect is better, and the hydroxide ions are also contained. Therefore, the glassy surface of the fly ash surface can be quickly destroyed, and more aluminum and strontium elements are precipitated. The CSH colloid of the product also increases, and the compressive strength of the inorganic polymer is increased.

(2) Effect of alkali modulus ratio: Under the condition of controlling alkali equivalent 6% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, changing the compressive strength range of the 3-day curing time when the alkali modulus is 1.0, 1.5 and 2.0 They are 193.11~619.21kgf/cm ² , 288.60~851.36kgf/cm ² and 314.12~761.97kgf/cm ² respectively, which are 279.87~710.73kgf/cm ² and 348.83~859.96kgf/cm respectively during the 7-day curing age. ² , 336.43~859.83kgf/cm ² , in the 28-day curing age, they are 522.28~1001.13kgf/cm ² , 341.44~965.23kgf/cm ² , 518.32~963.36kgf/cm ^{2 respectively} , as shown in Figure 4 (a ) (b) (c), Figure 5 (a) (b) (c), Figure 6 (a) (b) (c). It can be seen from the above-mentioned strength trend that the compressive strength increases with the increase of the curing time, and increases with the increase of the alkali modulus, among which the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, liquid-to-binder ratio 0.4, the alkali modulus ratio is the highest in compressive strength of 2.0, and has reached the requirements of ordinary cement (Type I) compressive strength.

Under the condition of controlling alkali equivalent 8% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, the compressive strength range of the three-day curing time when the alkali modulus is changed from 1.0, 1.5 and 2.0 is respectively 199.27~637.29kgf/cm ² , ^{314.47 ~ 878.37kgf / cm 2, 276.43} ~ 834.53kgf / cm 2, while its curing period 7 days were ^{168.61 ~ 675.48kgf / cm 2, 369.95} ~ 830.51kgf / cm 2, 378.49 ~ 981.67kgf / cm 2, At the 28-day curing age, they are 319.08~838.09kgf/cm ² , 313.03~1014.92kgf/cm ² , and 499.96~1050.24kgf/cm ^{2 respectively} , as shown in Figure 4(a)(b)(c), Figure 5 (a) (b) (c) and Figure 6 (a) (b) (c). It can be seen from the above strength trend that the compressive strength increases with the increase of the curing time, and increases with the increase of the alkali modulus. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 8% in alkali equivalent, liquid-to-binder ratio 0.4, the alkali modulus ratio is the highest in compressive strength of 2.0, and has reached the requirements of ordinary cement (Type I) compressive strength.

Under the conditions of controlling the alkali equivalent of 10% and the liquid-to-binder ratio of 0.4, 0.5 and 0.6, the compressive strength ranges of the three-day curing time when the alkali modulus is changed from 1.0, 1.5 and 2.0 are respectively 161.24~568.63kgf/cm ² , 247.01~798.87kgf/cm ² and 315.77~797.41kgf/cm ² are respectively 157.96~611.17kgf/cm ² , 339.97~815.81kgf/cm ² and 165.67~936.03kgf/cm ² during the 7-day curing age. At the 28-day curing age, they are 202.97~592.08kgf/cm ² , 73.77~570.12kgf/cm ² and 259.15~913.15kgf/cm ^{2 respectively} , as shown in Figure 4(a)(b)(c), Figure 5 (a) (b) (c) and Figure 6 (a) (b) (c). It can be seen from the above-mentioned strength trend that the compressive strength increases with the increase of the curing time, and gradually slows down with the increase of the alkali modulus. Among them, the mixture ratio of S20F80, S40F60, S60F40, S80F20 and the like is 10% of the alkali equivalent, and the liquid The rubber ratio is 0.4, and the alkali modulus ratio is 2.0. The increase in the alkali modulus ratio is beneficial to the improvement of the compressive strength because the ratio of the alkali modulus is increased, and sufficient SiO ₂ content can be provided to form more CSH colloids, and the internal structure of the slurry is more dense. Achieve the benefits of increased strength.

(3) the influence of liquid to rubber ratio

Under the conditions of controlling alkali modulus 1.0, alkali equivalent 6%, 8% and 10%, the compressive strength range of the 3-day curing time when the liquid-to-binder ratio is 0.4, 0.5 and 0.6 is 193.11~619.21kgf/cm ^{2 respectively.} 199.27~637.29kgf/cm ² and 161.24~568.63kgf/cm ² are 271.87~710.73kgf/cm ² , 168.61~675.48kgf/cm ² and 233.68~611.17kgf/cm ² respectively during the 7-day curing period. At the 28-day curing age, they are 522.28~1001.13kgf/cm ² , 319.08~838.09kgf/cm ² , 202.97~592.08kgf/cm ² , as shown in Figure 4(a)(b)(c). . It can be seen from the above strength trend that the compressive strength increases with the increase of the curing time, and increases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, and liquid-to-binder ratio. 0.4. When the alkali modulus is 1.0, the compressive strength is the highest, which has reached the requirement of ordinary cement (Type I) compressive strength.

Under the conditions of controlling alkali modulus 1.5, alkali equivalent 6%, 8% and 10%, the compressive strength range of the 3-day curing time when the liquid-to-binder ratio is 0.4, 0.5 and 0.6 is 288.60~851.36kgf/cm ^{2 respectively. , 314.47 ~ 878.37kgf / cm 2,} 247.01 ~ 798.87kgf / cm 2, while its curing period 7 days were ^{348.83 ~ 859.96kgf / cm 2, 369.95} ~ 830.51kgf / cm 2, 339.97 ~ 815.81kgf / cm 2 At the 28-day curing age, they are 341.44~965.23kgf/cm ² , 313.03~1014.92kgf/cm ² and 73.77~481.15kgf/cm ^{2 respectively} , as shown in Figure 5(a)(b)(c). . It can be seen from the above strength trend that the compressive strength increases with the increase of the curing time, and increases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, and liquid-to-binder ratio. 0.4, 0.5 and 0.6, the alkali modulus ratio is 1.5, the compressive strength is the highest, and has reached the requirements of ordinary cement (Type I) compressive strength.

Under the conditions of controlling alkali modulus 2.0, alkali equivalent 6%, 8% and 10%, the compressive strength range of the 3-day curing time when the liquid-to-binder ratio is 0.4, 0.5 and 0.6 is 314.12~761.97kgf/cm ^{2 respectively.} 276.43~834.53kgf/cm ² and 315.77~797.41kgf/cm ² , which are 336.43~850.41kgf/cm ² , 378.49~981.67kgf/cm ² and 165.67~1013.61kgf/cm ² respectively during the 7-day curing period. At the 28-day curing age, they are 491.35~963.36kgf/cm ² , 499.96~1050.24kgf/cm ² , and 259.15~913.15kgf/cm ² , as shown in Figure 6(a)(b)(c). . It can be seen from the above strength trend that the compressive strength increases with the increase of the curing time, and increases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, and the ratio of liquid to rubber is 0.4, 0.5 and 0.6, the alkali modulus ratio is 2.0, the compressive strength is the highest, and has reached the requirements of ordinary cement (Type I) compressive strength.

It is known from the test results that the increase of the liquid-to-gel ratio will lower the compressive strength. The reason is that the concentration of the alkali activator is diluted due to the increase of the liquid-to-gel ratio, and the reaction mechanism of the inorganic polymer is mainly the strong base. The solution destroys the vitreous surface of the fly ash surface of the power plant to produce a chemical hydration reaction, and the precipitation of strontium and aluminum ions in the chemical hydration reaction affects the integrity of the polymerization, so once the concentration of the alkali activator is lowered, the alkali activation furnace The benefits of stone will also decrease, resulting in a decrease in compressive strength.

Third, water absorption rate

(1) Effect of alkali equivalent: To investigate the effect of alkali equivalent on the water absorption of the fly ash inorganic polymer sample of the power plant, for the range of 6%, 8% and 10% alkali equivalent, and control the alkali modulus ratio of 1.0 and liquid Under the condition of 0.4, 0.5 and 0.6, the water absorption rate of the 3-day curing time when changing the alkali equivalent of 6% to 10% is 0.05%~0.41%, 0.05%~0.05%, 0.05%~0.13%, respectively. The 7-day curing age was 0.36%~2.02%, 0.95%~3.04%, 0.05%~1.23%, respectively, which was 0.49%~3.83% and 1.37%~5.58% in the 28-day curing age. 0.37%~4.13%, as shown in Figure 7(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%, 8% and 10%, the ratio of liquid to rubber is 0.4, and the ratio of alkali to modulus is 1.0.

When the alkali modulus ratio is 1.5 and the liquid-to-binder ratio is 0.4, 0.5 and 0.6, the water absorption rate of the 3-day curing time when the alkali equivalent is changed from 6% to 10% is 0.15%~0.34%, 0.10%~0.53, respectively. %, 0.13%~0.54%, 0.38%~1.56%, 0.19%~1.18%, 0.18%~1.40% in the 7-day curing age, respectively, 0.05% in the 28-day curing age. 5.07%, 0.38%~2.80%, 0.38%~3.07%, as shown in Fig. 8(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%, 8% and 10%, the ratio of liquid to rubber is 0.4, and the ratio of alkali to modulus is 1.5.

When the alkali modulus ratio is 2.0 and the liquid-to-binder ratio is 0.4, 0.5, and 0.6, the 3-day curing time is absorbed when the alkali equivalent is changed from 6% to 10%. The water rate ranges from 0.31% to 1.16%, 0.39% to 1.06%, and 0.34% to 0.74%, respectively, which are 0.39% to 2.31%, 0.56% to 2.55%, and 0.57% to 2.62%, respectively, during the 7-day curing period. At the 28-day curing age, they were 0.29% to 4.93%, 0.51% to 5.26%, and 0.58% to 6.26%, respectively, as shown in Figure 9(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%, 8% and 10%, the liquid-to-gel ratio is 0.4, and the alkali modulus ratio is 2.0. It can be seen from the above that the water absorption rate decreases as the alkali equivalent increases, and decreases with the increase of the curing time, mainly because the high alkali equivalent can cause more Si-O-Si and Al-O-Al frameworks. The structure, the internal structure is more dense, the strength is increased and the pores are less, and the water absorption rate also tends to decrease.

(2) Effect of alkali modulus ratio: Under the condition of controlling alkali equivalent 6% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, the water absorption rate of the three-day curing time when the alkali modulus is changed from 1.0, 1.5 and 2.0 respectively is 0.05%~0.41%, 0.13%~0.34%, 0.31%~0.16%, which were 0.36%~2.02%, 0.38%~1.56%, 0.39%~2.31% in the 7-day curing age, respectively, in 28 days. At the age of maintenance, they were 0.49%~3.83%, 0.05%~5.07%, and 0.29%~4.93%, as shown in Figure 7(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is the lowest in the base equivalent of 6%, the liquid-to-binder ratio of 0.4, and the alkali modulus ratio of 1.0.

Under the condition of controlling alkali equivalent 8% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, the water absorption rate of the three-day curing time when the alkali modulus was changed from 1.0, 1.5 and 2.0 was 0.05%~0.05% and 0.10%~0.53, respectively. %, 0.39%~1.06%, 0.95%~3.04%, 0.19%~1.18%, 0.56%~2.55% in the 7-day curing age, respectively, 1.37% in the 28-day curing age. 5.58%, 0.38%~2.80%, 0.51%~5.26%, as shown in Figure 8(a)(b)(c). Among them, S20F80, S40F60, S60F40, S80F20 and other mixed ratios have the lowest water absorption rate of 8% alkali equivalent, liquid-to-liquid ratio of 0.4, and alkali modulus ratio of 1.5.

Under the conditions of controlling alkali equivalent of 10% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, the water absorption rate of the three-day curing time when the alkali modulus is changed from 1.0, 1.5 and 2.0 is 0.05%~0.13%, 0.13%~0.54, respectively. %, 0.34%~0.74%, which is 0.05%~1.23%, 0.18%~1.40%, 0.49%~2.62% in the 7-day curing age, and 0.37%~4.13% in the 28-day curing age. 0.38% to 3.07% and 0.58% to 6.26%, as shown in Figure 9(a)(b)(c). Among them, S80F20, S40F60, S60F40, S80F20 and other mixed ratios have the lowest water absorption rate of 8% in alkali equivalent, 0.4 in liquid-to-gel ratio, and 2.0 in alkali modulus.

(3) the influence of liquid to rubber ratio

Under the conditions of controlling alkali modulus 1.0, alkali equivalent 6%, 8% and 10%, the water absorption ratio of the 3-day curing time when the liquid-to-gel ratio is 0.4, 0.5 and 0.6 is 0.05%~0.41%, 0.05%~ 0.05%, 0.05%~0.13%, 0.36%~2.02%, 0.95%~3.04%, 0.05%~1.23%, respectively, at the 7-day curing age, 0.46% in the 28-day curing age. ~3.83%, 1.37%~5.58%, 0.37%~4.13%, as shown in Figure 7(a)(b)(c). It can be seen from the above strength trend that the water absorption rate decreases with the increase of the curing time, and decreases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, and the ratio of liquid to rubber is 0.4. When the alkali modulus is 1.0, the water absorption rate is the lowest.

Under the conditions of controlling the alkali modulus 1.5, alkali equivalent 6%, 8% and 10%, the water absorption ratio of the 3-day curing time when the liquid-to-gel ratio is 0.4, 0.5 and 0.6 is 0.13%~0.34%, 0.10%~ 0.53%, 0.13%~0.54%, 0.38%~1.56%, 0.19%~1.18%, 0.26%~1.40% in the 7-day curing age, respectively, 0.05% in the 28-day curing age. ~5.07%, 0.38%~2.80%, 0.38%~3.07%, as shown in Figure 8(a)(b)(c). It can be seen from the above strength trend that the water absorption rate increases and decreases, and decreases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent and 0.4 in liquid-to-adhesive ratio. 0.5 and 0.6, the alkali modulus ratio is the lowest at 1.5 water absorption.

Under the conditions of controlling alkali modulus 2.0, alkali equivalent 6%, 8% and 10%, the water absorption ratio of the 3-day curing time when the liquid-to-gel ratio was 0.4, 0.5 and 0.6 was 0.31%~1.16%, 0.39%~ 1.06%, 0.34%~0.74%, 0.39%~2.31%, 0.56%~2.55%, 0.49%~2.62% in the 7-day curing age, respectively, 0.29% in the 28-day curing age. ~4.93%, 0.51%~5.26%, 0.63%~6.26%, as shown in the figure 9(a)(b)(c). It can be seen from the above strength trend that the water absorption rate decreases with the increase of the curing time, and decreases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, and the ratio of liquid to rubber is 0.4. , 0.5 and 0.6, the alkali modulus ratio is the lowest at 2.0 water absorption. It is known from the test results that the increase of the liquid-to-gel ratio will increase the water absorption rate. The reason is that the concentration of the alkali activator is diluted due to the increase of the liquid-to-gel ratio, and the strong alkali solution is mainly used in the reaction mechanism of the inorganic polymer. Destroying the vitreous surface of the fly ash surface of the power plant to produce a chemical hydration reaction, and the precipitation of strontium and aluminum ions in the chemical hydration reaction will affect the integrity of the polymerization. Therefore, once the concentration of the alkali stimulant is lowered, the alkali activated power plant flies. The benefits of ash are reduced, resulting in an increase in water absorption.

Fourth, the shrinkage change

This study mainly uses the dry shrinkage test to understand the volume stability of the fly ash inorganic polymer in the power plant. Therefore, the digital length measuring instrument is used to measure the change in the length of the test body shrinkage caused by the dehydration of the inorganic polymer, so it is dry. The smaller the shrinkage, the better. The following discussion will be made on the influence of the alkali equivalent of the polymer fly ash, the alkali modulus, and the liquid-to-binder ratio on the volume stability.

(1) Effect of alkali equivalent: In order to investigate the effect of alkali equivalent on the dry shrinkage of fly ash inorganic polymer test materials, the range of 6%, 8% and 10% alkali equivalents is controlled, and the alkali modulus ratio is controlled to be 1.0. Under the condition of liquid-gel ratio of 0.4, 0.5 and 0.6, the 3-day curing time shrinkage range of 6% to 10% of alkali equivalent is -0.85 ^mm ~0.10 ^mm , -0.052 ^mm ~0.125 ^mm , -0.092 ^mm ~ 0.117 ^mm, while its curing period 7 days were ^{-0.041 mm ~ 0.286 mm, -0.087 mm} ~ 0.191 mm, -0.020 mm ~ 0.018 mm, while its curing period is 28 days, respectively, is -0.009 ^mm ~ 0.782 ^mm , -0.196 ^mm ~ 0.112 ^mm , -0.058 ^mm ~0.021 ^mm , as shown in Figure 10(a)(b)(c), Figure 11(a)(b)(c), Figure 12(a)(b) (c) is shown. It can be seen from the above that the dry shrinkage increases with the increase of the alkali equivalent, and also increases with the increase of the curing age. Since the high alkali equivalent can effectively stimulate the activity of the fly ash inorganic polymer in the power plant, the internal polymerization due to the polymerization and The hydration reaction produces more CSH colloids to fill the pores in the material, making it more dense; among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6%, 8% and 10% in alkali equivalent, liquid-to-binder ratio 0.4, the alkali modulus is the lowest compared to 1.0.

When the alkali modulus ratio is 1.5 and the liquid-to-binder ratio is 0.4, 0.5, and 0.6, the 3-day curing time dry shrinkage range of 6% to 8% of the alkali equivalent is -0.223 ^mm ~ 0.02 ^mm , -0.216, respectively. ^Mm ~0.03 ^mm and -0.335 ^mm ~0.015 ^mm , which are -0.064 ^mm ~0.022 ^mm , -0.173 ^mm ~0.043 ^mm , -0.183 ^mm ~0.011 ^{mm at the} 7-day curing age, at 28-day curing age The time is -0.088 ^mm ~0.019 ^mm , -0.098 ^mm ~0.006 ^mm , -0.144 ^mm ~0.02 ^mm , as shown in Figure 10 (a) (b) (c), Figure 11 (a) (b) (c), Figure 12 (a) (b) (c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%, 8% and 10% of alkali equivalent, the ratio of liquid to rubber is 0.4, and the ratio of alkali modulus to 1.5 is the lowest.

When the alkali modulus ratio is 2.0 and the liquid-to-binder ratio is 0.4, 0.5, and 0.6, the 3-day curing time dry shrinkage range when the alkali equivalent is changed from 6% to 8% is -0.481 ^mm to 0.044 ^mm , -0.261, respectively. ^Mm ~0.014 ^mm and -0.151 ^mm ~-0.602 ^mm , which are -0.048 ^mm ~0.045 ^mm , -0.057 ^mm ~-0.23 ^mm , -0.055 ^mm ~-0.203 ^{mm at the} 7-day curing age, 28 days The curing age is -0.046 ^mm ~0.074 ^mm , -0.185 ^mm ~-0.020 ^mm , -0.078 ^mm ~0.110 ^mm , as shown in Figure 10(a)(b)(c), Figure 11(a)(b) (c), as shown in Figure 12(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is 6%, 8% and 10% of alkali equivalent, the ratio of liquid to rubber is 0.4, and the ratio of alkali modulus to 2.0 is the lowest.

(2) Effect of alkali modulus ratio: Under the condition of controlling alkali equivalent 6% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, the range of dry shrinkage of the three-day curing time when the alkali modulus is changed from 1.0, 1.5 and 2.0 respectively It is -0.85 ^mm ~0.050 ^mm , -0.217 ^mm ~0.020 ^mm , -0.481 ^mm ~0.044 ^mm , which is -0.041 ^mm ~0.286 ^mm , -0.064 ^mm ~0.022 ^mm , -0.048 ^{mm in the} 7-day curing age. 0.045 ^mm , which is -0.009 ^mm ~ 0.782 ^mm , -0.088 ^mm ~ 0.02 ^mm , -0.046 ^mm ~ 0.074 ^{mm at} 28 days of maintenance, as shown in Figure 10(a)(b)(c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is the lowest in alkali equivalent 6%, liquid-to-gel ratio 0.4, and alkali modulus ratio 1.0.

Under the conditions of controlling alkali equivalent 8% and liquid-to-gel ratio of 0.4, 0.5 and 0.6, the dry shrinkage of the three-day curing time when the alkali modulus was changed from 1.0, 1.5 and 2.0 was -0.052 ^mm ~ 0.069 ^mm , -0.216, respectively. ^Mm ~0.03 ^mm and -0.261 ^mm ~0.014 ^mm , which are -0.087 ^mm ~0.191 ^mm , -0.173 ^mm ~0.043 ^mm , -0.057 ^mm ~0.218 ^{mm at the} 7-day curing age, at 28-day curing age The time is -0.196 ^mm ~ 0.112 ^mm , -0.098 ^mm ~ 0.006 ^mm , -0.02 ^mm ~ -0.185 ^mm , as shown in Figure 11 (a) (b) (c). Among them, S20F80, S40F60, S60F40, S80F20 and other mixed mix ratios are 8% in alkali equivalent, 0.4 in liquid to rubber ratio, and 1.5 in alkali modulus ratio.

Under the conditions of controlling the alkali equivalent of 10% and the liquid-to-binder ratio of 0.4, 0.5 and 0.6, the dry shrinkage of the 3-day curing time of the alkali modulus from 1.0, 1.5 and 2.0 was -0.092 ^mm ~ 0.065 ^mm , -0.335, respectively. ^{mm ~ 0.015 mm, -0.151 mm ~} -0.602 mm, while its curing period 7 days were ^{-0.020 mm ~ 0.018 mm, -0.183 mm} ~ -0.011 mm, -0.055 mm ~ -0.203 mm, its 28 days The curing age is -0.035 ^mm ~0.021 ^mm , -0.144 ^mm ~-0.020 ^mm , -0.008 ^mm ~0.110 ^mm , as shown in Figure 12(a)(b)(c). Among them, the mixing ratio of S80F20, S40F60, S60F40, S80F20, etc. is the lowest in alkali equivalent 8%, liquid-to-gel ratio 0.4, and alkali modulus ratio 2.0.

(3) the influence of liquid to rubber ratio

Under the conditions of controlling the alkali modulus of 1.0 and the alkali equivalent of 6%, 8% and 10%, the dry shrinkage of the 3-day curing time when the liquid-to-binder ratio is 0.4, 0.5 and 0.6 is -0.85 ^mm ~ 0.10 ^mm , respectively - 0.052 ^mm ~0.125 ^mm , -0.092 ^mm ~0.117 ^mm , at -1041 ^mm ~0.286 ^mm , -0.087 ^mm ~0.191 ^mm , -0.020 ^mm ~0.018 ^{mm at} 7 days of maintenance, respectively, at 28 days of maintenance age The period is -0.009 ^mm ~0.782 ^mm , -0.196 ^mm ~0.112 ^mm , -0.058 ^mm ~0.021 ^mm , as shown in Figure 10(a)(b)(c), Figure 11(a)(b)(c) Figure 12 (a) (b) (c). It can be seen from the above strength trend that the water absorption rate decreases with the increase of the curing time, and decreases with the decrease of the liquid-to-gel ratio. Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20, etc. is 6% in alkali equivalent, and the ratio of liquid to rubber is 0.4. When the alkali modulus is 1.0, the dry shrinkage is the lowest.

Under the conditions of controlling the alkali modulus 1.5 and the alkali equivalent 6%, 8% and 10%, the dry shrinkage range of the 3-day curing time when the liquid-to-binder ratio is 0.4, 0.5 and 0.6 is -0.223 ^mm ~ 0.02 ^mm , respectively. 0.216 ^mm ~0.03 ^mm and -0.335 ^mm ~0.015 ^mm , which are -0.064 ^mm ~0.022 ^mm , -0.173 ^mm ~0.043 ^mm , -0.183 ^mm ~0.011 ^mm at the 7-day curing age, at 28 days of maintenance age The period is -0.088 ^mm ~0.019 ^mm , -0.098 ^mm ~0.006 ^mm , -0.144 ^mm ~0.02 ^mm , as shown in Fig. 10(a)(b)(c), Fig. 11(a)(b)(c) Figure 12 (a) (b) (c). Among them, the mixing ratio of S20F80, S40F60, S60F40, S80F20 and the like is the lowest in the alkali equivalent 6%, the liquid-to-gel ratio 0.4, 0.5 and 0.6, and the alkali modulus ratio is 1.5.

Under the conditions of controlling alkali modulus 2.0, alkali equivalent 6%, 8% and 10%, the dry shrinkage of the 3-day curing time when the liquid-to-binder ratio was 0.4, 0.5 and 0.6 was -0.481 ^mm ~ 0.044 ^mm , respectively - 0.261 ^mm ~0.014 ^mm and -0.151 ^mm ~-0.602 ^mm , which are -0.048 ^mm ~0.045 ^mm , -0.057 ^mm ~-0.23 ^mm , -0.055 ^mm ~-0.203 ^{mm at} 7 days of maintenance age, respectively. when the day curing period were ^{-0.046 mm ~ 0.074 mm, -0.185 mm} ~ -0.020 mm, -0.008 mm ~ 0.110 mm, FIG. 10 (a) (b) ( c), FIG. 11 (a) (b ) (c), Figure 12 (a) (b) (c). The results show that when the liquid-to-gel ratio is increased from 0.4 to 0.6, the dry shrinkage tends to increase. Since the low liquid-to-binder ratio can reduce the retained water inside the sample, the dry shrinkage is reduced, but with the increase of the liquid-to-gel ratio. The concentration of the alkali activator is diluted by the retained water, thereby affecting the activity of the fly ash inorganic polymer in the power plant, resulting in more residual water retention. When the test body is dried and hardened, the retained water is lost, and the dry shrinkage is increased. high.

Fifth, the structure observation of scanning electron microscope

The fly ash of the power plant was made into an inorganic polymer and placed in a 5cm×5cm×5cm square. The sample was taken for 7 days and sampled. The scanning electron microscope (SEM) was used to observe the crystal phase change of the fly ash inorganic polymer in the power plant, as shown in Figures 13 to 24. It can be seen that the CSH colloid adheres to the structure of the product formed by the melt polymerization when the same liquid-to-gel ratio is 0.4, the same alkali modulus ratio is 2.0, and the alkali equivalent AE is 6%, 8%, and 10%. When the alkali equivalent is increased from 6% to 10%, the CSH colloid decreases with the increase of the water quenching furnace powder in the S20F80, S40F60, S60F40, and S80F20, and cracks appear in it. 13 to 16, as shown in FIGS. 17 to 20, and as shown in FIGS. 21 to 24. When the alkali activator has a low alkalinity, both the C-S-H colloid and the Si-O-Si framework structure coexist, and the C-S-H colloid can fill the pores generated by the Si-O-Si framework structure. thus It can be seen that when the alkalinity is low, the strength source is mainly C-S-H colloid; however, when the alkalinity is high, the Si-O-Si framework is dominant.

The preferred embodiment is to study the production technology of the inorganic fly ash produced by the power plant fly ash. The base equivalent (AE), the alkali modulus ratio (Ms) and the liquid-to-binder ratio (L/) are prepared based on the fly ash of the power plant. B), the power plant fly ash is made into inorganic polymer green cement. S20F80, S40F60, S60F40, S80F20, etc. are mixed, and the alkali equivalent (AE), alkali modulus ratio (Ms), liquid-to-binder ratio (L/S) are prepared, and the test body is prepared and cured for 3 days. At 7 days and 28 days, the effects of coagulation time, compressive strength, water absorption rate and dry shrinkage were discussed. The results of the test were analyzed to summarize the following conclusions:

1. For the range of 6%, 8% and 10% alkali equivalent, the alkali modulus ratio is 1.5 and 2.0, and the liquid-to-binder ratio is 0.5 and 0.6, and the mixed fly ash inorganic polymerization of S20F80, S40F60, etc. The final setting time meets the requirements of cement specifications.

2. For the range of 6%, 8% and 10% alkali equivalent, the alkali modulus ratio is 2.0, and the liquid-to-binder ratio is 0.4, the mixture of S20F80, S40F60, S60F40, S80F20, etc. The compressive strength has reached the requirements of ordinary cement (Type I) compressive strength.

3. For the range of 6%, 8% and 10% alkali equivalent, the ratio of alkali modulus is 1.0, 1.5, 2.0, and the ratio of liquid to rubber is 0.4, and the water absorption ratio of S20F80, S40F60, S60F40, S80F20, etc. lowest. The water absorption rate decreases as the alkali equivalent increases, and decreases as the curing time increases.

4. For the range of 6%, 8% and 10% alkali equivalent, and control the alkali modulus ratio of 1.0, 1.5, 2.0, and the liquid-to-binder ratio is 0.4, mix with S20F80, S40F60, S60F40, S80F20, etc. The ratio is the lowest.

5. For the range of 6%, 8% and 10% alkali equivalent, the alkali modulus ratio is 1.0, the liquid-to-binder ratio is 0.6, and the mixed fly ash inorganic polymer is mixed with S20F80, S40F60, S60F40, S80F20, etc. The condensation time is the shortest.

Claims (10)

The invention relates to a method for manufacturing an inorganic polymerized cement, comprising the steps of: (A) obtaining a fly ash and water quenching furnace powder of a F-class thermal power plant; (B) detecting the fly ash and water quenching furnace powder of the F-class thermal power plant; (C) The qualified F-class thermal power plant fly ash and water quenching furnace powder are blended, wherein the percentage of fly ash in F-class thermal power plant is 20%~80%, and the percentage of water quenching furnace powder is 20%~80%; D) adding the material of step (C) to sodium carbonate and sodium hydroxide for mixing of inorganic polymer cement, wherein the liquid-to-gel ratio is 0.4 to 0.6, the alkali equivalent is 6% to 10%, and the alkali modulus ratio is 1.0~2.0, made into inorganic polymer slurry; and (E) 3~28 days of maintenance work, and carry out various tests. The method for producing an inorganic polymeric cement according to the first aspect of the invention, wherein in the step (D), sodium citrate and sodium hydroxide are used for adjusting the alkali-containing equivalent ratio to the alkali modulus ratio, and the hydrazine is used. Sodium is a sodium citrate solution. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (B), the physical properties of the fly ash of the F-class thermal power plant are tested, and XRD and XRF analysis are performed. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (D), an inorganic polymer slurry having a base equivalent of 6%, 8%, and 10% is prepared. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (D), an inorganic polymer slurry having an alkali modulus ratio of 1.0, 1.5, and 2.0 is prepared. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (D), the inorganic polymer slurry having a liquid to rubber ratio of 0.4, 0.5, and 0.6 is used. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (E), the curing operation is performed for 3 days, 7 days, and 28 days. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (C), the proportion of the fly ash of the water quenching furnace powder/F-class thermal power plant is 20/80, 40/60, 60/ respectively. 40, 80/20. The method for producing an inorganic polymeric cement according to the first aspect of the invention, wherein in the step (E), a compression test, a coagulation time test, and a dry shrink test are performed. The method for producing an inorganic polymeric cement according to claim 1, wherein in the step (C), the fly ash and the water quenching furnace powder of the F-class thermal power plant are ground to a fineness requirement of at least 4000 (cm ² / g) above.