CN115010441B - Baking-free brick slurry formula and preparation method of baking-free brick - Google Patents

Baking-free brick slurry formula and preparation method of baking-free brick Download PDF

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CN115010441B
CN115010441B CN202210806524.4A CN202210806524A CN115010441B CN 115010441 B CN115010441 B CN 115010441B CN 202210806524 A CN202210806524 A CN 202210806524A CN 115010441 B CN115010441 B CN 115010441B
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slag
baking
cement
fly ash
free brick
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CN115010441A (en
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李磊
马双忱
刘金强
乔琳
孟旸
卢锐
王竞一
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Hebei Zhuozhou Jingyuan Thermal Electricity Co ltd
North China Electric Power University
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Hebei Zhuozhou Jingyuan Thermal Electricity Co ltd
North China Electric Power University
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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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • 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
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/10—Burned or pyrolised refuse
    • 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
    • C04B22/002—Water
    • C04B22/0046—Waste slurries or solutions used as gauging water
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • 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
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention relates to a baking-free brick slurry formula, which is mainly characterized in that in the pulping process, nanofiltration concentrated water of a desulfurization wastewater zero discharge system of a power plant is utilized to replace process water for pulping and slurry mixing; the baking-free brick slurry formula comprises the following components in percentage by mass: 20-35% of cement, 8-15% of fly ash, 30-35% of slag, 20-30% of process water and 0.05-0.4% of sodium lignin sulfonate by total mass of cement and fly ash; the slag is slag at the bottom of a power plant boiler; cement and fly ash are used as cementing materials, and the mass ratio of the cementing materials to the slag is 1:0.8-1:1. The invention utilizes the nanofiltration concentrated water of the desulfurization wastewater zero discharge system of the power plant, overcomes the defects of the nanofiltration concentrated water by adjusting the proportion of cement, fly ash, slag and sodium lignin sulfonate, exerts the advantages of the nanofiltration concentrated water, ensures that the strength of the prepared baking-free brick product reaches the standard, and meets the building requirement. The invention is also beneficial to protecting natural resources and environment, changing waste into valuable, saving occupied area, reducing pollution, protecting environment and having good economic and social benefits.

Description

Baking-free brick slurry formula and preparation method of baking-free brick
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a baking-free brick slurry formula and a preparation method of a baking-free brick.
Background
The baking-free brick is manufactured by taking industrial wastes (slag, fly ash, cement, river sand and the like) as main raw materials, does not consume clay, does not need sintering, and can reach relevant standards of building material industry after molding and curing. In addition, the baking-free brick is manufactured by using the solid wastes such as the slag and the fly ash of the power plant as raw materials, so that the solid waste treatment pressure of the power plant can be reduced. The baking-free brick has the characteristics of waste utilization, soil saving and energy saving, which are not available in any other wall bricks. In the preparation process, a scientific formula is adopted, a coagulant and a trace amount of chemical additives are added according to a certain proportion, and the mixture is subjected to strengthening treatment by special equipment by controlling granularity, humidity and mixing degree, so that the mixture reaches the optimal plastic state, and is subjected to high-pressure compression molding. The baking-free brick is a new product which can replace clay bricks and has great development prospect. The admixture can improve the performance of the slurry, and has the main effects of (1) improving the workability of the mixture, reducing the labor intensity of the physical power and being beneficial to the mechanized operation. (2) The curing time can be reduced or the steam curing time of the prefabricated part factory can be shortened. (3) The strength of the slurry solidified body is improved, the durability, the compactness, the freezing resistance and the impermeability are improved, and the drying shrinkage (the drying shrinkage rate is a physical quantity representing the volume or length reduction degree caused by drying and water loss after raw materials such as ceramics, refractory materials, bricks and tiles are made into green bodies) and the creep performance (the larger the cement dosage in concrete, the larger the creep ratio and the larger the creep ratio) are improved. The water reducing agent is the most important and widely applied additive in all additive products, can obviously improve the mechanical property of the cured body, and can also greatly improve the impermeability and durability of the cured body.
At present, although there are many formulas and production processes of baking-free bricks at home and abroad, the schemes only focus on optimization and improvement of solid raw materials, proportions, material granularity and the like, or mainly optimization of additive types, additive amounts and the like, and the schemes focus on improvement of process water of the baking-free bricks.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the invention provides a baking-free brick slurry formula and a baking-free brick preparation method, which are mainly characterized in that nanofiltration concentrated water of a power plant desulfurization wastewater zero discharge system is utilized to replace brick making process water, thereby realizing the resource utilization of nanofiltration concentrated water, avoiding the high cost of further treatment and purification of nanofiltration concentrated water, reducing and recycling solid wastes such as slag (producing high-value products) and carrying out harmless treatment, and bringing considerable economic benefits to enterprises. The method is characterized in that concentrated water is nano-filtered by utilizing a desulfurization wastewater zero-emission system of a power plant, and the selection and the proportion of each component of the baking-free brick are reasonably adjusted, so that the baking-free brick product with high compressive strength, low water absorption and excellent seepage resistance can be prepared, and the application performance is improved.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides a baking-free brick slurry formula, which is mainly prepared by using nanofiltration concentrated water of a desulfurization wastewater zero emission system of a power plant to replace process water in the pulping process and mixing; the baking-free brick slurry formula comprises the following components in percentage by mass: 20-35% of cement, 8-15% of fly ash, 30-35% of slag, 20-30% of process water and 0.05-0.4% of sodium lignin sulfonate by total mass of cement and fly ash; wherein the slag is slag at the bottom of a power plant boiler;
wherein the cement and the fly ash are cementing materials, and the mass ratio of the cementing materials to the slag is the cement-slag ratio; the ratio of the glue to the slag is 1:0.8-1:1; in the process water, the nanofiltration concentrated water of the power plant desulfurization wastewater zero discharge system accounts for more than 50 percent.
According to the preferred embodiment of the invention, the nanofiltration concentrated water of the desulfurization wastewater zero discharge system of the power plant accounts for 100 percent.
Preferably, the sodium lignin sulfonate accounts for 0.2-0.4% of the total mass of the cement and the fly ash.
Preferably, the sodium lignin sulfonate accounts for 0.2-0.25% or 0.35-0.40% of the total mass of the cement and the fly ash.
According to a preferred embodiment of the invention, the sodium lignin sulfonate comprises 0.2% or 0.4% and more preferably 0.2% of the total mass of cement and fly ash.
The nano-filtration concentrated water of the desulfurization wastewater zero-emission system of the power plant is subjected to water quality analysis, and the nano-filtration concentrated water comprises the following components: COD (mg/L), 1.5-1.7X10 3 The method comprises the steps of carrying out a first treatment on the surface of the Total organic carbon (mg/L), 110-128; soluble total solids/filterable residue (mg/L), 4.5-5.5X10 4 The method comprises the steps of carrying out a first treatment on the surface of the Calcium (mg/L), 75-80; magnesium (mg/L), 3.0-4.5; sodium (mg/L), 1.10-1.30X10 4 The method comprises the steps of carrying out a first treatment on the surface of the Potassium (mg/L), 260-300; ammonium salt/ammonia nitrogen (mg/L), 40-45; barium (mg/L),<0.02; strontium (mg/L),<0.20; ferric iron (mg/L),<0.05; manganese (mg/L),<0.02; sulfate (mg/L), 9.2-10×10 3 The method comprises the steps of carrying out a first treatment on the surface of the Chloride (mg/L), 7.9-8.4X10 3 The method comprises the steps of carrying out a first treatment on the surface of the Fluoride (mg/L),<0.5; nitrate (mg/L), 150-160; bromide (mg/L), 20-23; bicarbonate (mg/L),<0.001; carbonate (mg/L),<0.001; phosphate (mg/L),<0.05; boron (mg/L), 20-23; silica (mg/L), 8.5-11; ph=7-8.5.
In a second aspect, the invention provides a method for preparing baking-free bricks, comprising the following steps:
s1, preparing raw materials according to the baking-free brick slurry formula;
s2, mixing cement, fly ash, slag, sodium lignin sulfonate and the like, and putting the mixture into wheel mill stirring equipment for dry mixing;
s3, after adding process water, continuously stirring for 5-10min by adopting a wheel mill stirring device to prepare uniform plasticizing slurry;
s4, adopting static pressure equipment to press and mold to obtain green bricks;
s5, natural curing or normal-temperature steam curing in a storage yard.
(III) beneficial effects
The beneficial technical effects of the invention include:
(1) The baking-free brick is manufactured by adopting the nano-filtered concentrated water of the zero emission system of the desulfurization wastewater of the cement, the fly ash, the slag and the power plant as the main raw materials, and compared with the baked brick, the baking-free brick is energy-saving and environment-friendly; compared with other baking-free bricks, a great amount of cement is saved. On one hand, a large amount of industrial solid waste (fly ash and slag) is consumed, the cost is reduced, and on the other hand, the nano-filtration concentrated water of the desulfurization wastewater zero-emission system is adopted to replace the common process water of the baking-free bricks, so that the nano-filtration concentrated water is not required to be further treated, the water treatment cost is saved, the nano-filtration wastewater is changed into valuable, and the method has important environmental protection significance.
(2) The invention uses the nano-filtered concentrated water of the desulfurization wastewater zero-emission system of the power plant to replace the common process water (usually tap water or underground water), and aims at solving the problems that ettringite, wollastonite and the like are easy to generate due to higher sulfate content in the nano-filtered concentrated water, and the method of reducing the water-cement ratio to enhance the compactness of a solidified body, adding more mineral admixtures such as fly ash, slag and the like, controlling the cement-slag ratio and the like is adopted to inhibit the post-expansion caused by ettringite when preparing the baking-free brick slurry. For Na contained in nanofiltration concentrated water + When the baking-free brick slurry is prepared, the problem of higher content can be solved by adding the air entraining agent (sodium lignin sulfonate has micro-gas permeability) or adding fly ash, slag and the like in a proper proportion, so that the reaction expansion of alkali aggregate can be reduced to a certain extent. So that the baking-free brick has high 28d compressive strength and low water absorption.
(3) The invention uses the nanofiltration concentrated water of the power plant desulfurization wastewater zero discharge system to fully utilize chloride ions, calcium and OH carried by the nanofiltration concentrated water - Silica, sulfate (sulfate can generate ettringite, and a proper amount of ettringite can be formed to compensate the contractility of cement paste), and the like, participate in Friedel salt reaction, fixation reaction of the ettringite on chloride ions, volcanic ash reaction and other strength curing reactions, and fully utilize the advantages brought by self ions in nanofiltration concentrated water of a desulfurization wastewater zero-emission system of a power plant.
Because the nanofiltration concentrated water has certain hardness, the water reducing agent selected by the invention is sodium lignin sulfonate, has good diffusion performance, can be dissolved in water with any hardness, has good chemical stability, is easy to dissolve in water, is not influenced by pH value change, has colloid characteristic, and increases the viscosity of the solution along with the increase of the concentration.
(4) The baking-free brick 28d prepared by the method has the highest compressive strength reaching 21mpa, the 28d water absorption rate reaching 18%, and the finished brick reaches the brick standard of the building material industry and can be used as a building material.
In summary, the preparation method of the baking-free brick of the invention utilizes the nanofiltration concentrated water of the desulfurization wastewater zero discharge system of the power plant, overcomes the defects of the nanofiltration concentrated water and plays the advantages of the nanofiltration concentrated water by adjusting the proportion of cement, fly ash, slag and sodium lignin sulfonate, so that the strength of the prepared baking-free brick product reaches the standard, and meets the requirements of building materials. The raw materials of the preparation method from solid powder and gel materials to process water are all from wastes except cement, the raw materials are convenient to select and environment-friendly, natural resources and environment are protected, waste is changed into valuables, occupied space is saved, pollution is reduced, the environment is protected, the manufacturing cost of building bricks is reduced, and the preparation method has good economic and social benefits.
Drawings
Fig. 1 is a flowchart of a method for preparing baking-free bricks according to the present invention.
FIG. 2 shows the compressive strength of 14d and 28d of baking-free bricks prepared with different cement to slag ratios.
Fig. 3 shows the water absorption of 14d and 28d of baking-free bricks prepared with different cement to slag ratios.
Fig. 4 shows the compressive strength of baking-free bricks 13d and 28d at different sodium lignin sulfonate addition levels.
Fig. 5 shows the water absorption of baking-free bricks 28d at various sodium lignin sulfonate addition levels.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
In the following specific embodiments, the full analysis results of nanofiltration concentrate water quality of the desulfurization wastewater zero discharge system of the power plant are shown in table 1.
TABLE 1 nanofiltration concentrated water quality component
Figure BDA0003737933640000051
Figure BDA0003737933640000061
From the water quality analysis result, the content of chloride ions in the nanofiltration concentrated water is higher than the concrete mixing water standard, but the corrosion influence of the chloride ions on the steel bars is not required to be considered because the research purpose is to manufacture baking-free brick products, so that the doping of the chloride ions can not be seriously influenced.
The high sulfate content in the nanofiltration concentrated water can lead to the generation of ettringite and wollastonite, so that the baking-free bricks are expanded, cracked and the like. However, the formation of an appropriate amount of ettringite compensates for the shrinkage of the cement slurry. Therefore, when the ingredients of the invention are used for preparing baking-free bricks, the precautions adopted mainly are as follows: (1) enhancing the compactness of the solidified body by reducing the water-cement ratio; (2) mineral admixtures such as fly ash and slag are mixed, and the ratio of the glue to the slag is controlled to inhibit the post-expansion caused by ettringite.
From the analysis result of nanofiltration concentrated water quality, na + The content is relatively high, the damage caused by alkali aggregate reaction is considered in the process of producing the baking-free brick, and the reaction expansion of the alkali aggregate can be reduced to a certain extent by doping an air entraining agent (sodium lignin sulfonate has micro-gas permeability) or mineral admixture fly ash, slag and the like.
Nanofiltration systems are increasingly being used for the salt separation treatment of desulfurization wastewater. The nanofiltration membrane can effectively intercept divalent and multivalent anions in the wastewater, has good selective permeation effect on monovalent anions, and is particularly suitable for salt separation treatment of desulfurization wastewater. The nanofiltration concentrated water after nanofiltration treatment mainly contains divalent ions such as calcium magnesium hardness ions and sulfate radical and the like, and the calcium ions and the sulfate radical have an enhancement effect on the performance of the baking-free bricks. Moderate chloride ions in the high-salinity water react with C3A phase in the cement to generate Friedel's salt, and the compressive strength of the solidified body is also improved.
It should be noted that the nanofiltration concentrated water quality of the desulfurization wastewater zero emission system of the power plant has a certain fluctuation, and in general, the nanofiltration concentrated water quality of the desulfurization wastewater zero emission system of the power plant has the following characteristics: COD (mg/L), 1.5-1.7X10 3 The method comprises the steps of carrying out a first treatment on the surface of the Total organic carbon (mg/L), 110-128; soluble total solids/filterable residue (mg/L), 4.5-5.5X10 4 The method comprises the steps of carrying out a first treatment on the surface of the Calcium (mg/L), 75-80; magnesium (mg/L), 3.0-4.5; sodium (mg/L), 1.10-1.30X10 4 The method comprises the steps of carrying out a first treatment on the surface of the Potassium (mg/L), 260-300; ammonium salt/ammonia nitrogen (mg/L), 40-45; barium (mg/L),<0.02; strontium (mg/L),<0.20; ferric iron (mg/L),<0.05; manganese (mg/L),<0.02; sulfate (mg/L), 9.2-10×10 3 The method comprises the steps of carrying out a first treatment on the surface of the Chloride (mg/L), 7.9-8.4X10 3 The method comprises the steps of carrying out a first treatment on the surface of the Fluoride (mg/L),<0.5; nitrate (mg/L), 150-160; bromide (mg/L), 20-23; bicarbonate (mg/L),<0.001; carbonate (mg/L),<0.001; phosphate (mg/L),<0.05; boron (mg/L), 20-23; silica (mg/L), 8.5-11; ph=7-8.5.
As shown in fig. 1, the process for preparing the baking-free brick of the present invention comprises:
step 1, preparing materials
In the embodiment, the nano-filtration concentrated water of the desulfurization wastewater zero-emission system of the power plant comprises 20-35% of cement, 8-15% of fly ash, 30-35% of slag and 20-30% of nano-filtration concentrated water. In addition, 0.05 to 0.4 percent of sodium lignin sulfonate is added based on the total mass of the cement and the fly ash.
By adopting the raw material proportion of the invention, a large amount of slag can be consumed, a large amount of natural sand materials are saved, the investment of cement is reduced, and the cost is reduced; on the other hand, the nanofiltration concentrated water of the desulfurization wastewater zero discharge system of the power plant can be directly utilized, the nanofiltration concentrated water does not need to be further purified, and a large amount of wastewater treatment cost is saved.
Step 2: and (3) putting the prepared cement, fly ash, slag, sodium lignin sulfonate and the like into wheel mill stirring equipment for dry mixing.
Step 3: adding nanofiltration concentrated water of a desulfurization wastewater zero-emission system of a power plant into wheel mill stirring equipment, and continuously carrying out wet mixing for 5-10min to prepare uniform plasticized slurry;
step 4: adopting static pressure equipment to press and mold to obtain green bricks; the press forming is performed in a mold.
Step 5: natural curing or normal temperature steam curing in a storage yard. Preferably, the curing is to put the green bricks into deionized water for natural curing for 28d; of course, the curing method is not limited thereto.
The main reactions of the main substances participating in the curing process are as follows, which are sources of curing strength of baking-free bricks:
formation of calcium silicate hydrate and calcium hydroxide:
3CaO·SiO 2 +nH 2 O＝xCaO·SiO 2 ·yH 2 O+(3-x)Ca(OH) 2
2CaO·SiO 2 +nH 2 O＝xCaO·SiO 2 ·yH 2 O+(2-x)Ca(OH) 2
formation of ettringite:
C 3 A·CaSO 4 ·12H 2 O+2CaSO 4 +20H 2 O＝C 3 A·3CaSO 4 ·32H 2 O
friedel salt formation:
3CaO·Al 2 O 3 +Cl - +H 2 O→3CaO·Al 2 O 3 ·CaCl 2 ·10H 2 O
immobilization of chloride ions by the gefite:
4CaO·Al 2 O 3 ·Fe 2 O 3 +Cl - +H 2 O→3CaO·Fe 2 O 3 ·CaCl 2 ·10H 2 O
pozzolanic reaction:
(SiO 2 )x+2H 2 O+OH - →(SiO 2 ) x-1 +Si(OH) 5 1-
Ca 2+ +Si(OH) 5 1- +OH - →(CaO)(SiO 2 )(H 2 O) 3
Ca(OH) 2 +SiO 2 +Al 2 O 3 +H 2 O→(CaO) x (SiO 2 ) y (Al 2 O 3 ) z (H 2 O) w
the baking-free brick does not need to be sent into a kiln for baking in the whole preparation process, so that a large amount of baking energy consumption and kiln equipment cost can be saved; the method uses solid wastes such as fly ash, slag and the like as main reasons, uses the zero-emission nanofiltration concentrated water of the desulfurization waste water of the power plant as main process water, does not need sintering, and can realize natural curing and normal-temperature evaporation curing, and the compressive strength and the impermeability of the finished brick reach the brick standards of the building material industry.
The added water reducing agent sodium lignin sulfonate can not only remarkably improve the mechanical property of concrete, but also greatly improve the impermeability of concrete and improve the durability of concrete materials. The sodium lignin sulfonate has the characteristics of abundant sources, low price, innocuity, diversified molecular structures, easy chemical modification and the like, has certain air entraining property, and can neutralize Na in nanofiltration water + The content ratio is higher, which brings adverse effects.
The polar hydrophilic group of sodium lignin sulfonate is directionally adsorbed on the surfaces of particles such as cement, fly ash and slag, associates with water molecules in a hydrogen bond mode, and combines with the hydrogen bond association among water molecules to form a stable water film on the surfaces of the particles of the cement, the fly ash and the slag, so that direct contact among the particles is prevented, the sliding capacity among the particles is improved, the lubricating effect is achieved, and the fluidity of slurry is further improved. In the baking-free brick slurry, after cement hydration, due to the Van der Waals force action among ions and the coagulation generated by different charges of cement hydrated minerals and cement main minerals in the hydration process, negative ions-SO-, -COO-in the water reducer can be in positive charge Ca of cement particles 2+ The ions are adsorbed on the cement particles under the action of the ore, and the ion distribution of the diffusion double-electron layer is formed on the surface. The baking-free brick is manufactured by sodium lignin sulfonate, so that on one hand, the mixing workability of the mixture slurry can be improved; on the other hand, the strength of the slag brick is enhanced, and experiments prove that the addition amount of sodium lignin sulfonate has obvious influence on the strength of the baking-free brick.
In concrete, the addition of the sodium lignin sulfonate water reducer is 0.20-0.30% of the mass of cement, the common mixing amount is 0.25%, and the dosage of the water reducer in the concrete is directly related to the dosage of cement. In the present invention, however, the sodium lignin sulfonate water reducing agent is used in an amount of about 0.05% to about 0.4% and about 0.2% by weight based on the total mass of the cement and the fly ash.
It should be noted that, the baking-free brick is manufactured by the slurry with the proportion, but in the actual production and application process, the slurry raw material composition of the baking-free brick can also be adjusted according to the actual use of the finished product, for example, a certain amount of coarse aggregate, other cementing materials or additives and the like are added to ensure that the application performance of the baking-free brick meets the relevant industry standards.
The following are examples of baking-free bricks prepared according to the above preparation method.
Example 1
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
31 parts of Po42.5 cement, 10 parts of fly ash, 32.8 parts of slag and 26.09 parts of nanofiltration concentrate of a desulfurization wastewater zero-emission system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.26% sodium lignin sulfonate (0.1066 parts by mass, 0.106% of the total ingredients) was added based on the total mass of cement and fly ash. The fly ash and cement are used as cementing materials, and the dosage ratio of the slag to the cementing materials is the cement-slag ratio. In this example, the cement to slag ratio=1:0.8.
Step 2: and (3) putting the prepared cement, fly ash, slag, sodium lignin sulfonate and the like into wheel mill stirring equipment for dry mixing.
Step 3: adding nanofiltration concentrated water of a desulfurization wastewater zero-emission system of a power plant into wheel mill stirring equipment, and continuously carrying out wet mixing for 10min to prepare uniform plasticized slurry;
step 4: and adopting static pressure equipment to press and form the green bricks in a mould.
Step 5: and placing the green bricks into deionized water for natural curing for 28d.
Example 2
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
25 parts of Po42.5 cement, 10 parts of fly ash, 35 parts of slag and 29.91 parts of nanofiltration concentrated water of a desulfurization wastewater zero emission system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.26% sodium lignin sulfonate (the amount of which is 0.091 parts by mass, accounting for 0.091% of the total ingredients) was added based on the total mass of cement and fly ash. Wherein, the glue residue ratio=1:1.
Other preparation steps were the same as in example 1.
Example 3
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
21.16 parts of Po42.5 cement, 8 parts of fly ash, 35 parts of slag and 35.76 parts of nanofiltration concentrate of a desulfurization wastewater zero-emission system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.26% sodium lignin sulfonate (0.0758 parts by mass, 0.0758% of the total ingredients) was added based on the total mass of cement and fly ash. Wherein, the glue residue ratio=1:1.2.
Other preparation steps were the same as in example 1.
Comparative example 1
In this comparative example, the baking-free brick slurry composition was: 15.33 parts of Po42.5 cement, 8 parts of fly ash, 35 parts of slag and 41.61 parts of nanofiltration concentrate of a desulfurization wastewater zero-emission system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.26% sodium lignin sulfonate (0.0607 parts by mass, 0.0607% of the total ingredients) was added based on the total mass of cement and fly ash. Wherein, the glue residue ratio=1:1.5. Other preparation steps were the same as in example 1.
The compressive strength of the finished baking-free bricks 14d and 28d of examples 1 to 3 and comparative example 1 were tested, and the experimental results are shown in FIG. 2.
As can be seen from the results of FIG. 2, the curing of the baking-free brick was carried out at a cement-slag ratio of 1:0.8, the compressive strength of the baking-free brick was maximized at 28d, which was approximately 19MPa, and the compressive strength of the baking-free brick was maximized at a cement-slag ratio of 1:1, which was approximately 15MPa. Since baking-free bricks are usually used after curing for 28 days, the preferable ratio of glue to slag is 1:0.8-1:1. Where the cement to slag ratio of 1:1.5 in comparative example 1, the compressive strength of both baking-free bricks 14d and 28d was small.
In examples 1-2, the strength of baking-free bricks maintained for 28 days can reach the MU15 and MU20 standards.
The finished baking-free bricks 14d and 28d of examples 1 to 3 and comparative example 1 were tested for water absorption and the results are shown in FIG. 3. The smaller the water absorption, the better the impermeability of the baking-free slag brick. As shown, the water absorption of the baking-free bricks 28d is lowest when the cement-slag ratio is 1:0.8; when the glue and slag ratio of the baking-free brick is 1:1.2, the water absorption rate of 14d is the lowest, but when the glue and slag ratio is 1:1.2, the water absorption rate of the baking-free brick 28d is higher. Therefore, the ratio of the gum to the slag is preferably 1:0.8-1:1. Considering the comprehensive compressive strength, the cement-slag ratio is more preferably 1:0.8. the above examples illustrate that the brick products made according to the formulation of the present invention meet the JC/T525-2007 Standard for slag brick.
Example 4
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
31 parts of Po42.5 cement, 10 parts of fly ash, 32.8 parts of slag and 26.04 parts of nanofiltration concentrate of a desulfurization wastewater zero discharge system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.4% sodium lignin sulfonate (0.164 parts by mass, 0.164% of the total ingredients) was added based on the total mass of cement and fly ash. The fly ash and cement are used as cementing materials, and the dosage ratio of the slag to the cementing materials is the cement-slag ratio. In this example, the cement to slag ratio=1:0.8.
Other preparation steps were the same as in example 1.
Example 5
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
31 parts of Po42.5 cement, 10 parts of fly ash, 32.8 parts of slag and 26.08 parts of nanofiltration concentrate of a desulfurization wastewater zero discharge system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.3% sodium lignin sulfonate (0.123 parts by mass, 0.123% of the total ingredients) was added based on the total mass of cement and fly ash. The fly ash and cement are used as cementing materials, and the dosage ratio of the slag to the cementing materials is the cement-slag ratio. In this example, the cement to slag ratio=1:0.8.
Other preparation steps were the same as in example 1.
Example 6
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
31 parts of Po42.5 cement, 10 parts of fly ash, 32.8 parts of slag and 26.12 parts of nanofiltration concentrate of a desulfurization wastewater zero discharge system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.2% sodium lignin sulfonate (0.082 parts by mass, 0.082% of the total ingredients) was added based on the total mass of cement and fly ash. The fly ash and cement are used as cementing materials, and the dosage ratio of the slag to the cementing materials is the cement-slag ratio. In this example, the cement to slag ratio=1:0.8.
Other preparation steps were the same as in example 1.
Example 7
The embodiment provides a preparation method of a slag baking-free brick, which comprises the following steps:
step 1, preparing materials
31 parts of Po42.5 cement, 10 parts of fly ash, 32.8 parts of slag and 26.18 parts of nanofiltration concentrate of a desulfurization wastewater zero-emission system of a power plant. The quality of the nanofiltration concentrate is shown in table 1. In addition, 0.05% sodium lignin sulfonate (0.0205 mass parts, 0.0205% of total ingredients) was added based on the total mass of cement and fly ash. The fly ash and cement are used as cementing materials, and the dosage ratio of the slag to the cementing materials is the cement-slag ratio. In this example, the cement to slag ratio=1:0.8.
Other preparation steps were the same as in example 1.
The finished baking-free bricks 13d and 28d of examples 4 to 7 were tested for compressive strength and the experimental results are shown in FIG. 4. As shown in the figure, when the glue-slag ratio is 1:0.8 and the addition amount of sodium lignin sulfonate is 0.2% of the mass of the cementing material (the sum of the fly ash and the cement is the cementing material), the compressive strength of the baking-free brick curing 13d and 28d reaches the peak value, wherein the compressive strength at 28d is 21Mpa and the compressive strength at 13d is close to 19Mpa. Wherein, when the addition amount of sodium lignin sulfonate is 0.4 percent of the mass of the cementing material, the compressive strength of the baking-free brick 28d is close to 19Mpa, and the compressive strength of the baking-free brick 13d is close to 17Mpa. When the addition amount of sodium lignin sulfonate is 0.05% of the mass of the cementing material, the compressive strength of the baking-free bricks 13d and 28d is lower. Therefore, the addition amount of sodium lignin sulfonate is preferably 0.1% or more, and preferably 0.2 to 0.4%; however, when the addition amount of sodium lignin sulfonate is 0.3%, the baking-free brick compression strength is caused to reach the valley bottom instead, so that the addition amount of sodium lignin sulfonate can be determined to be 0.2-0.25% or 0.35-0.4% of the mass of the cementing material, and is most preferably 0.2% of the mass of the cementing material. As can be seen from fig. 4, the compressive strength of the baking-free bricks 13d and 28d is consistent with the effect of the addition amount of sodium lignin sulfonate.
The finished baking-free bricks 28d of examples 4-7 were tested for water absorption and the experimental results are shown in FIG. 5. As shown in the figure, when the glue-slag ratio is 1:0.8 and the addition amount of sodium lignin sulfonate is 0.2% of the mass of the cementing material (the sum of the fly ash and the cement is the cementing material), the water absorption rate of the baking-free brick curing 28d is the lowest and is 18%; and when the addition amount of the sodium lignin sulfonate is 0.4% of the mass of the cementing material, the water absorption rate of baking-free brick curing 28d is also lower, about 18.5%. Therefore, the addition amount of sodium lignin sulfonate is determined to be 0.2-0.4% by mass of the cement, more preferably 0.2%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (2)

1. A baking-free brick slurry formula is characterized in that in the pulping process, nanofiltration concentrated water of a desulfurization wastewater zero discharge system of a power plant is utilized to replace process water for pulping and slurry mixing;
the baking-free brick slurry formula comprises the following components in percentage by mass: 20-35% of cement, 8-15% of fly ash, 30-35% of slag, 20-30% of process water and sodium lignin sulfonate accounting for 0.2-0.26% of the total mass of the cement and the fly ash; wherein the slag is slag at the bottom of a power plant boiler;
cement and fly ash are cementing materials, and the mass ratio of the cementing materials to slag is the cement-slag ratio; the ratio of the glue to the slag is 1:0.8-1:1; the nanofiltration concentrated water of the desulfurization wastewater zero discharge system of the power plant in the process water accounts for 100 percent;
the nanofiltration concentrated water of the desulfurization wastewater zero discharge system of the power plant is subjected to water quality analysis, and the components are as follows: COD is 1.5-1.7X10 3 mg/L; 110-128 mg/L total organic carbon; soluble total solids/filterable residue 4.5-5.5X10 4 mg/L; 75-80 mg/L of calcium; 3.0-4.5 mg/L of magnesium; sodium 1.10-1.30X10 4 mg/L; 260-300 mg/L of potassium; ammonium salt/ammonia nitrogen 40-45 mg/L; barium (Ba)<0.02 mg/L, strontium<0.20 mg/L; ferric iron<0.05 mg/L; manganese (Mn)<0.02 mg/L, sulfate 9.2-10×10 3 mg/L, chloride 7.9-8.4X10 3 mg/L; fluoride compounds<0.5 mg/L; nitrate 150-160 mg/L; bromide 20-23 mg/L; bicarbonate salt<0.001 mg/L; carbonate salt<0.001 mg/L; phosphate salts<0.05 mg/L; 20-23 mg/L of boron; 8.5-11 mg/L of silicon dioxide; ph=7-8.5.
2. The preparation method of the baking-free brick is characterized by comprising the following steps:
s1, preparing raw materials according to the baking-free brick slurry formula of claim 1;
s2, mixing cement, fly ash, slag and sodium lignin sulfonate, and putting the mixture into wheel mill stirring equipment for dry stirring;
s3, after adding process water, continuously stirring for 5-10min by adopting a wheel mill stirring device to prepare uniform plasticizing slurry;
s4, adopting static pressure equipment to press and mold to obtain green bricks;
s5, natural curing or normal-temperature steam curing in a storage yard.
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