WO2023213103A1 - 一种混凝土再生粉体碳化砖及其制备方法 - Google Patents

一种混凝土再生粉体碳化砖及其制备方法 Download PDF

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Publication number
WO2023213103A1
WO2023213103A1 PCT/CN2023/074768 CN2023074768W WO2023213103A1 WO 2023213103 A1 WO2023213103 A1 WO 2023213103A1 CN 2023074768 W CN2023074768 W CN 2023074768W WO 2023213103 A1 WO2023213103 A1 WO 2023213103A1
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Prior art keywords
calcium
group
solid waste
parts
storage tank
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English (en)
French (fr)
Inventor
张洪智
李志杰
邵滢璇
凌一峰
刘志强
陈晨
葛智
孙仁娟
管延华
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Shandong University
Shandong High Speed Group Co Ltd
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Shandong University
Shandong High Speed Group Co Ltd
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Priority to US18/358,356 priority Critical patent/US12600058B2/en
Publication of WO2023213103A1 publication Critical patent/WO2023213103A1/zh
Anticipated expiration legal-status Critical
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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
    • C04B30/00—Compositions for artificial stone, not containing binders
    • 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
    • C04B28/18—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 mixtures of the silica-lime type
    • C04B28/186—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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
    • C04B28/188—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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/14—Producing shaped prefabricated articles from the material by simple casting, the material being neither forcibly fed nor positively compacted
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B17/00—Details of, or accessories for, apparatus for shaping the material; Auxiliary measures taken in connection with such shaping
    • B28B17/0063—Control arrangements
    • B28B17/0081—Process control
    • C—CHEMISTRY; METALLURGY
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    • C04B11/00—Calcium sulfate cements
    • C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
    • C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C04B18/0445—Synthetic gypsum, e.g. phosphogypsum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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
    • C04B18/0481—Other specific industrial waste materials not provided for elsewhere in C04B18/00
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    • 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
    • C04B18/12—Waste materials; Refuse from quarries, mining or the like
    • 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
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C04B18/142—Steelmaking slags, converter slags
    • 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
    • C04B18/16—Waste materials; Refuse from building or ceramic industry
    • 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 or shrinkage compensating agents
    • 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 or shrinkage compensating agents
    • C04B22/0006—Waste inorganic materials
    • 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 or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/10—Acids or salts thereof containing carbon in the anion, e.g. carbonates
    • C04B22/106—Bicarbonates
    • 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
    • C04B28/08—Slag cements
    • C04B28/082—Steelmaking slags; Converter slags
    • 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
    • C04B28/14—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 calcium sulfate cements
    • C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate 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
    • C04B7/00—Hydraulic cements
    • C04B7/14—Cements containing slag
    • C04B7/147—Metallurgical slag
    • 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
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00198—Characterisation or quantities of the compositions or their ingredients expressed as mathematical formulae or equations
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • 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

Definitions

  • the invention relates to a concrete recycled powder carbonized brick and a preparation method thereof, and belongs to the technical field of concrete materials.
  • the calcium hydroxide in the brick undergoes a carbonization reaction in an environment rich in carbon dioxide to form calcium carbonate, thereby gaining strength.
  • the production of carbonized bricks can effectively realize the recycling of industrial waste residue and waste gas, and the product has high strength, does not require calcination, and is green and environmentally friendly.
  • existing carbonized brick preparation methods usually use carbonization curing technology.
  • the diffusion rate of carbon dioxide gas to the concrete matrix is slow, and the carbon dioxide sequestration rate is not high, resulting in problems such as insufficient recycling of waste resources and long production time.
  • the present invention provides a concrete regenerated powder carbonized brick and a preparation method thereof.
  • Industrial solid waste is used to provide a calcium source. Based on the principle of liquid phase carbonation technology, industrial waste gas containing carbon dioxide is dissolved in water to produce The carbonate ions react with the calcium ions dissolved in the industrial solid waste to form a calcium bicarbonate solution, which is then passed into a mold containing regenerated powder to generate carbonized bricks.
  • the carbon dioxide sequestration rate is high, and the carbonized bricks produced are economical. Good, high production efficiency, no need for calcination or pressing, green and environmentally friendly.
  • a method for preparing concrete recycled powder carbonized bricks including the following steps:
  • group A is industrial solid waste material
  • the temperature of the molding mold is controlled to be 45 to 55°C, preferably 50°C.
  • the calcium bicarbonate solution is thermally decomposed, and the generated carbon dioxide reacts with the calcium ions leached from the C-S-H gel in the regenerated powder to generate calcium carbonate, which reacts with the calcium bicarbonate solution.
  • the calcium carbonate produced by decomposition together precipitates, crystallizes and cements the recycled powder in the mold to produce strength;
  • the final compressive strength of the carbonized brick is about 15MPa, that is, when the pressure is 1/10 to 1/5 of the compressive strength of the carbonized brick, the calcite has cemented the regenerated powder and built a network structure, generating strength , the amount of calcium bicarbonate solution introduced is sufficient, and the solution can be stopped at this time;
  • the principle of the present invention is:
  • the principle of carbonation reaction involves a series of physical adsorption and diffusion processes. Based on the gas-liquid-solid phase reaction theory, the process can be roughly divided into four stages: First, under normal temperature and pressure, the calcium-based activity in industrial solid waste The substance dissolves and hydrolyzes in the water medium, releasing hydroxide ions, which increases the pH value of the slurry.
  • the slurry shows strong alkalinity and has a strong ability to capture and sequester carbon dioxide; carbon dioxide dissolves in water to form carbonic acid, which reacts with the slurry Hydroxide ions and calcium ions react rapidly, causing the pH value of the slurry to begin to drop and calcium carbonate precipitation is generated; then the rate of hydrolysis of solid waste materials to produce hydroxide ions is basically the same as the rate of bicarbonate ionization to produce hydrogen ions, and the pH value of the slurry Remain relatively stable; as the mineralization reaction continues, the rate of hydrolysis to produce hydroxide ions is gradually lower than the rate of hydrogen ions produced by carbon dioxide introduction, and when the pH value of the slurry gradually drops to remain unchanged, the carbonation reaction is basically completed.
  • the calcium bicarbonate solution decomposes at a temperature of about 50°C in the mold, producing carbon dioxide and calcium carbonate precipitation.
  • the CSH gel structure in the regenerated powder is unstable, causing the calcium element to leach out, and reacts with the carbon dioxide produced by the decomposition of calcium bicarbonate to form calcium carbonate precipitation.
  • the precipitated calcium carbonate forms crystals (calcite) under warm and humid conditions. After the crystals are mixed with the regenerated powder, they grow and develop in the gaps to form Fill the pores, cement the regenerated powder and build each other to form a network structure, and finally form the strength.
  • the regenerated powder determines the particle gradation based on the principle of close packing, which can effectively improve the density of the slurry.
  • the group A includes any one or more combinations of calcium-containing industrial solid waste materials such as carbide slag, fly ash, steel slag, desulfurization gypsum, granulated blast furnace slag, tailings, coal gangue, etc.
  • calcium-containing industrial solid waste materials such as carbide slag, fly ash, steel slag, desulfurization gypsum, granulated blast furnace slag, tailings, coal gangue, etc.
  • y Ca is the sum of the calcium content of all solid waste materials in group A; x is the mass of the solid waste material with the highest calcium content in group A; N represents the solid waste material with the highest calcium content in group A.
  • M is the total mass of all solid waste materials in group A;
  • 0.516 (M-x) is the sum of the calcium content of other solid waste materials in group A, 0.516 is the calcium content of other solid waste materials in group A Empirical coefficient derived from the sum of element proportions.
  • the empirical coefficients 0.045 and 0.516 are based on multiple sets of calcium content data of solid waste materials and are obtained by fitting in the software. Since they are obtained by analyzing a large amount of data, they are representative.
  • the quality of other solid waste materials can be determined by the following formula:
  • y Si and y Mg are respectively the silicon content and the magnesium content in all solid waste materials in group A; Z is the proportion of silicon in the selected solid waste materials; E is the magnesium content in the selected solid waste materials. Proportions of elements; (M-x) respectively represent the content of silicon and magnesium in other solid waste materials. By adding the two parts, you can get the sum of the silicon and magnesium elements contained in all solid waste materials in group A.
  • the empirical coefficients 1.95 and 10.14 are based on multiple sets of silicon and magnesium element content data of solid waste materials and are obtained by fitting in the software. Since they are obtained by analyzing a large amount of data, they are representative.
  • the main components of the regenerated powder are silica, calcium hydroxide, calcium aluminosilicate, ettringite, etc.;
  • C-S-H gel accounts for approximately 70% of the total volume
  • calcium hydroxide accounts for approximately 20% of the total volume
  • the liquid storage pool is connected with a pH monitor and a temperature controller.
  • the temperature controller keeps the temperature of the liquid storage pool stable, and the pH monitor monitors changes in the pH value of the liquid storage pool to regulate the introduction time of carbon dioxide.
  • a liquid inlet main pipe and a liquid outlet main pipe are connected between the liquid storage tank and the forming mold, the water pump is arranged on the liquid inlet main pipe, and a pipeline pressure monitor is provided near the liquid inlet main pipe close to the forming mold;
  • the forming mold includes a plurality of grids that are as large as the size of the carbonized bricks to be prepared.
  • the size can be 240mm ⁇ 115mm ⁇ 53mm, 240mm ⁇ 115mm ⁇ 180mm, 180mm ⁇ 180mm ⁇ 90mm, etc.
  • the particle gradation of the recycled powder satisfies The most tightly packed state, after filling into the grid, it will be in a uniform and dense state, the powder will not float easily, and there is no need to make the recycled powder into wet material and put it into the molding mold;
  • Heating tubes are arranged around each grid, and each grid is provided with a liquid inlet branch pipe and a liquid outlet branch pipe. Multiple liquid inlet branch pipes are connected to the liquid inlet main pipe, and multiple liquid outlet branch pipes are connected to the liquid outlet main pipe.
  • the water pump circulates the calcium bicarbonate solution into the molding mold. After entering the molding mold, the calcium bicarbonate solution flows through each pipe branch and enters each grid.
  • the compressive strength and water absorption rate of the carbonized bricks are tested according to GB/T 2452-2012 "Test Methods for Wall Bricks", and the carbon capture rate is calculated based on the thermogravimetric test results of the carbonized bricks, as follows:
  • w(CO2) is the mass fraction of carbon dioxide in the carbonized brick
  • M Ca and M CO2 represent the molar mass of calcium and carbon dioxide respectively
  • Q Ca is the carbon dioxide before carbonation (that is, before being put into the storage tank, which has not participated in any reaction) Solid waste materials) Mass fraction of calcium in industrial solid waste materials.
  • U(D) is the volume fraction of particles with a particle size smaller than D, %; D is the particle size, ⁇ m; D1 is the particle size of the largest particle in the system, ⁇ m; n is the distribution index, taken as 1/3.
  • the particle size distribution of the regenerated powder in the most closely packed state is shown in Table 2.
  • the particle distribution is in the most closely packed state:
  • the chemical composition of the regenerated powder is The composition mainly includes calcium oxide and silica, and silica is the most important crystal phase component in the regenerated powder.
  • Regenerated powder made from waste concrete already contains hydration products such as calcium hydroxide, calcium aluminosilicate and ettringite, which mainly exist in the form of gels. The degree of hydration of different waste concretes varies greatly, leading to hydration Product content varies greatly.
  • the group A includes carbide slag, fly ash and steel slag, wherein in terms of parts by mass, the carbide slag is 30 parts, fly ash is 35 parts, and steel slag is 20 parts;
  • the group A includes carbide slag, fly ash and steel slag, wherein in terms of parts by mass, the carbide slag is 33 parts, fly ash is 30 parts, and steel slag is 20 parts;
  • the group A includes carbide slag, fly ash and desulfurization gypsum, wherein in terms of parts by mass, the carbide slag is 30 parts, the fly ash is 30 parts, and the desulfurization gypsum is 25 parts;
  • carbide slag examples include 79.68 ⁇ 84.90wt% CaO, 1.56 ⁇ 3.28wt% SiO2, 2.20 ⁇ 2.29wt% Al2O3, 0.19 ⁇ 0.73wt% MgO, and 8.80 ⁇ 16.37wt% others.
  • fly ash examples include 3.42 ⁇ 8.45wt% CaO, 45.71 ⁇ 48.10wt% SiO2, 23.20 ⁇ 31.34wt% Al2O3, 2.47 ⁇ 3.17wt% Na2O, 0.57 ⁇ 3.97wt% MgO, and 4.97 ⁇ 24.63wt% others.
  • the steel slag composition includes 40.61 ⁇ 43.15wt% CaO, 12.12 ⁇ 15.28wt% SiO2, 4.72 ⁇ 5.31wt% Al2O3, 6.95 ⁇ 7.02wt% Fe2O3, 10.35 ⁇ 11.62wt% FeO, 10.34 ⁇ 12.39wt% MgO, 1.21 ⁇ 2.52wt% MnO, 2.71 ⁇ 13.7wt% others.
  • a concrete recycled powder carbonized brick is prepared by the above method.
  • the invention uses industrial solid wastes such as carbide slag, fly ash, steel slag, desulfurization gypsum, granulated blast furnace slag, tailings, coal gangue, etc. to provide calcium sources.
  • industrial solid wastes such as carbide slag, fly ash, steel slag, desulfurization gypsum, granulated blast furnace slag, tailings, coal gangue, etc.
  • the industrial waste gas containing carbon dioxide is dissolved in water
  • the generated carbonate ions react with the calcium ions dissolved in the industrial solid waste to form a calcium bicarbonate solution with high solubility, which effectively increases the carbon dioxide storage capacity and conversion rate;
  • the calcium bicarbonate solution is passed into the molding machine containing regenerated powder After the mold is formed, calcium bicarbonate is decomposed by heat.
  • the reaction contact area is large and the speed is fast.
  • the generated carbon dioxide precipitates with calcium carbonate.
  • the carbon dioxide reacts with the calcium ions precipitated from the waste concrete regenerated powder in the mold to also generate calcium carbonate precipitates.
  • instruments used in the present invention such as temperature controllers, pH monitors, pipeline pressure monitors, etc., can all be commercially available models and will not affect the implementation of the present invention.
  • the present invention uses recycled powder obtained by crushing and grinding waste concrete and industrial solid waste such as fly ash and calcium carbide slag, and the cost of raw materials is low.
  • the fine particle size of the recycled powder is beneficial to the micro-aggregate filling effect; the specific surface area and particle fineness of the recycled powder are generally larger than those of commonly used cement, which is beneficial to stimulating its activity, and the process equipment is simple, which is beneficial to industrial production.
  • the present invention selects the gradation of regenerated powder particles in the most closely packed state. Calcium carbonate precipitates and crystallizes to form closely packed calcite particles, making the carbonized brick product dense, with high compressive strength and stable strength.
  • the existing carbonized brick preparation process mostly involves demoulding the molded specimen and placing it in a carbonization chamber for carbonization and curing for at least 3 hours or even several days before the brick body is produced.
  • the production time is long.
  • the process of carbon dioxide gas diffusing into the concrete matrix is relatively slow, and the carbon sequestration rate is low, resulting in insufficient resource recycling and low production efficiency.
  • the present invention uses solid waste materials dissolved in water to provide calcium sources, fixes and converts carbon dioxide gas into liquid state, has high solubility, and can effectively increase the carbon dioxide fixation rate. Calcium carbonate crystallizes and polymerizes, cements regenerated powder, omits carbonization and maintenance links, and demolds after molding. It can be put into use immediately, effectively shortening production time.
  • the present invention can permanently capture and store the greenhouse gas carbon dioxide produced in the industrial production process, and does not require calcination during the preparation process and does not emit any polluting gases, which is beneficial to mitigating the greenhouse effect and achieving "carbon emission reduction” and resource recycling. ,protect environment.
  • Figure 1 is a schematic diagram of the principle of the present invention
  • Figure 2 is a schematic diagram of the preparation process of concrete recycled powder carbonized bricks
  • 1-liquid storage tank 2-industrial solid waste material, 3-stirring rod, 4-forming mold, 5-water pump, 6-carbonized brick, 7-pH monitor, 8-temperature controller, 9-input Liquid main pipe, 10-liquid outlet main pipe, 11-pipe pressure monitor, 12-heating pipe, 13-regenerated powder.
  • a method for preparing concrete recycled powder carbonized bricks includes the following steps:
  • group A is industrial solid waste material 2;
  • the molding mold 4 is connected to the liquid storage tank 1 through a pipeline.
  • a water pump 5 is provided on the pipeline, and the water pump 5 moves the liquid in the liquid storage tank.
  • Calcium bicarbonate solution is circulated and pumped into the mold.
  • the flow rate of the solution is 1.0m/s ⁇ 3.0m/s. The appropriate flow rate can ensure that the calcium bicarbonate solution passes into the mold.
  • the solution is fully heated to decompose and undergo subsequent precipitation and crystallization reactions.
  • the solution flow rate is too fast, which may cause part of the calcium bicarbonate solution to flow out of the mold without decomposition or precipitation, reducing the conversion efficiency; the flow rate is too slow, which may cause the production time to be too long and reduce the cost of carbonized bricks. preparation efficiency;
  • the temperature of the molding mold is controlled to 50°C.
  • the calcium bicarbonate solution is decomposed by heat.
  • the generated carbon dioxide reacts with the calcium ions leached from the C-S-H gel in the regenerated powder to generate calcium carbonate, which is combined with the calcium carbonate produced by the decomposition of the calcium bicarbonate solution.
  • Precipitating, crystallizing and cementing the recycled powder in the mold creates strength;
  • the principle of the present invention is:
  • the principle of carbonation reaction involves a series of physical adsorption and diffusion processes. Based on the gas-liquid-solid phase reaction theory, the process can be roughly divided into four stages: First, under normal temperature and pressure, the calcium-based activity in industrial solid waste The substance dissolves and hydrolyzes in the water medium, releasing hydroxide ions, which increases the pH value of the slurry.
  • the slurry shows strong alkalinity and has a strong ability to capture and sequester carbon dioxide; carbon dioxide dissolves in water to form carbonic acid, which reacts with the slurry Hydroxide ions and calcium ions react rapidly, causing the pH value of the slurry to begin to drop and calcium carbonate precipitation is generated; then the rate of hydrolysis of solid waste materials to produce hydroxide ions is basically the same as the rate of bicarbonate ionization to produce hydrogen ions, and the pH value of the slurry Remain relatively stable; as the mineralization reaction continues, the rate of hydrolysis to produce hydroxide ions is gradually lower than the rate of hydrogen ions produced by carbon dioxide introduction, and when the pH value of the slurry gradually drops to remain unchanged, the carbonation reaction is basically completed.
  • the calcium bicarbonate solution decomposes at a temperature of about 50°C in the mold, producing carbon dioxide and calcium carbonate precipitation.
  • the C-S-H gel structure in the regenerated powder is unstable, causing the calcium element to leach out, and reacts with the carbon dioxide produced by the decomposition of calcium bicarbonate to form calcium carbonate precipitation.
  • the precipitated calcium carbonate forms crystals (calcite) under warm and humid conditions. After the crystals are mixed with the regenerated powder, they grow and develop in the gaps to fill the pores, cement the regenerated powders and build each other to form a network structure, and finally form the strength.
  • the regenerated powder determines the particle gradation based on the principle of close packing, which can effectively improve the slurry. Body density, as shown in Figure 1.
  • Group A includes carbide slag, fly ash, steel slag, desulfurization gypsum, granulated blast furnace slag, tailings, and coal gangue Any one or combination of calcium-containing industrial solid waste materials.
  • C-S-H gel accounts for approximately 70% of the total volume
  • calcium hydroxide accounts for approximately 20% of the total volume
  • a method for preparing concrete regenerated powder carbonized bricks as described in Embodiment 1, except that the liquid storage tank 1 is connected to a pH monitor 7 and a temperature controller 8, and the temperature of the liquid storage tank is adjusted through the temperature controller 8. Keep it stable, and monitor the changes in pH value of the liquid storage tank through the pH monitor 7 to regulate the carbon dioxide introduction time.
  • a liquid inlet main pipe 9 and a liquid outlet main pipe 10 are connected between the liquid storage tank 1 and the forming mold 4.
  • the water pump 5 is arranged on the liquid inlet main pipe.
  • the liquid inlet main pipe 9 is provided with a pipeline pressure monitor 11 near the forming mold;
  • the forming mold 4 includes a plurality of grids with the same size as the carbonized bricks to be prepared.
  • the size can be 240mm ⁇ 115mm ⁇ 53mm, 240mm ⁇ 115mm ⁇ 180mm, 180mm ⁇ 180mm ⁇ 90mm, etc.
  • the particle gradation of the recycled powder satisfies the optimal Closely packed state, after filling into the grid, it will be in a uniform and dense state, the powder will not float easily, and there is no need to make the recycled powder into wet material and put it into the molding mold;
  • Heating tubes 12 are arranged around each grid, and each grid is provided with a liquid inlet branch pipe and a liquid outlet branch pipe. Multiple liquid inlet branch pipes are connected to the liquid inlet main pipe 9 , and multiple liquid outlet branch pipes are connected to the liquid outlet main pipe 10 .
  • the water pump 5 circulates the calcium bicarbonate solution into the mold. After entering the mold, the calcium bicarbonate solution flows through each pipe branch and enters each grid.
  • Group A includes carbide slag, fly ash and steel slag, wherein in parts by mass, the carbide slag is 30 parts, Fly ash is 35 parts and steel slag is 20 parts;
  • carbide slag examples include 79.68 ⁇ 84.90wt% CaO, 1.56 ⁇ 3.28wt% SiO2, 2.20 ⁇ 2.29wt% Al2O3, 0.19 ⁇ 0.73wt% MgO, and 8.80 ⁇ 16.37wt% others.
  • fly ash examples include 3.42 ⁇ 8.45wt% CaO, 45.71 ⁇ 48.10wt% SiO2, 23.20 ⁇ 31.34wt% Al2O3, 2.47 ⁇ 3.17wt% Na2O, 0.57 ⁇ 3.97wt% MgO, and 4.97 ⁇ 24.63wt% others.
  • the steel slag composition includes 40.61 ⁇ 43.15wt% CaO, 12.12 ⁇ 15.28wt% SiO2, 4.72 ⁇ 5.31wt% Al2O3, 6.95 ⁇ 7.02wt% Fe2O3, 10.35 ⁇ 11.62wt% FeO, 10.34 ⁇ 12.39wt% MgO, 1.21 ⁇ 2.52wt% MnO, 2.71 ⁇ 13.7wt% others.
  • Group A includes carbide slag, fly ash and steel slag, wherein in parts by mass, the carbide slag is 33 parts, Fly ash is 30 parts and steel slag is 20 parts;
  • Group A includes carbide slag, fly ash and desulfurization gypsum, in which the carbide slag is 30 parts by mass. , fly ash is 30 parts, desulfurization gypsum is 25 parts;
  • w(CO2) is the mass fraction of carbon dioxide in the carbonized brick
  • MCa and MCO2 represent the molar mass of calcium and carbon dioxide respectively
  • QCa is the solid waste material that has not participated in any reaction before carbonation (that is, before being put into the liquid storage tank) ) Mass fraction of calcium in industrial solid waste materials.
  • U(D) is the volume fraction of particles with a particle size smaller than D, %; D is the particle size, ⁇ m; D1 is the particle size of the largest particle in the system, ⁇ m; n is the distribution index, taken as 1/3.
  • the particle size distribution of the regenerated powder in the most closely packed state is shown in Table 2.
  • the particle distribution is in the most closely packed state:
  • Group C that is, the particle gradation of the regenerated powder should meet the most closely packed state.
  • the calcium oxide and silicon dioxide contents are 17.51 ⁇ 29.20wt% and 27.80 ⁇ 43.26wt%.
  • a concrete recycled powder carbonized brick is prepared by the method described in Example 7.

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Abstract

一种混凝土再生粉体碳化砖及其制备方法，属于混凝土材料领域，包括：将组集A加入贮液池；将组集B通入贮液池中与固废溶液反应生成碳酸氢钙溶液；将再生粉体填入成型模具中，碳酸氢钙溶液受热分解，生成的二氧化碳与再生粉体中C-S-H凝胶浸出的钙离子反应，生成碳酸钙，并与碳酸氢钙溶液分解产生的碳酸钙一起在模具中沉淀、结晶和胶结，再生粉体产生强度。以工业固体废弃物提供钙源，使含二氧化碳的工业废气溶于水产生的碳酸根离子与工业固体废弃物中溶出的钙离子反应制成碳酸氢钙溶液，并通入含再生粉体的成型模具生成碳化砖，二氧化碳封存率较高，制得的碳化砖具有经济性好，生产效率高，无需煅烧、压制，绿色环保的特点。

Description

一种混凝土再生粉体碳化砖及其制备方法 技术领域
本发明涉及一种混凝土再生粉体碳化砖及其制备方法，属于混凝土材料技术领域。
背景技术
伴随我国城镇化建设进程的加快，不可避免地对原有建筑物进行拆除、改造和重建，随着建筑施工项目数量越来越多，产生的废弃混凝土数量也在不断增加，其垃圾资源化的方式主要为粉碎再利用。目前，废弃混凝土经过科学的技术处理而产生的再生粗、细骨料制备的再生混凝土及砂浆等材料，在力学性能上可以达到普通混凝土的要求并应用到建筑、道路、桥梁工程中。然而，针对废弃混凝土经逐级破碎、粉磨后产生的一定细度的再生粉体的回收研究并不充分，直接丢弃会造成资源浪费，另外，由于其粒径较小(一般定义为<0.16mm)且容易漂浮于空气中，会造成大气污染，危及人类健康。因此，提高废弃混凝土再生粉体的利用效率，对降低二次环境污染和资源浪费有重要意义。
目前，全球范围内空气中的二氧化碳浓度日益升高，造成严重气候变化。为实现“碳中和”目标，有效缓解全球变暖，在大力开展新能源研发、应用的同时，还需要安全、有效、经济的实现二氧化碳捕捉、封存。在传统的烧结砖生产工艺中，人工干燥及焙烧环节所排放大气污染物总量较高，随着时间的推移，国家关于砖瓦工业大气污染物的排放标准日益严格，大气污染防治工作已成为制约砖瓦行业可持续、高质量发展的主要因素。“碳化砖”是一种非烧结砖，砖坯中的氢氧化钙在富含二氧化碳的环境中，发生碳化反应生成碳酸钙，从而获得强度。碳化砖的生产可有效实现对工业废渣和废气的循环利用，且产品强度高、无需煅烧、绿色环保。然而，现有的碳化砖制备方法通常采用碳化养护技术，二氧化碳气体扩散至混凝土基体的速率较慢，且二氧化碳封存率不高，造成了废弃资源再生利用率不足、生产时间较长等问题。
发明内容
针对现有技术的不足，本发明提供一种混凝土再生粉体碳化砖及其制备方法，以工业固体废弃物提供钙源，基于液相碳酸化技术原理，使含二氧化碳的工业废气溶于水产生的碳酸根离子与工业固体废弃物中溶出的钙离子反应制成碳酸氢钙溶液，并通入含再生粉体的成型模具生成碳化砖，二氧化碳封存率较高，制得的碳化砖具有经济性好，生产效率高，无需煅烧、压制，绿色环保的特点。
本发明的技术方案如下：
一种混凝土再生粉体碳化砖的制备方法，包括以下步骤：
(1)称取一定质量组集A，并加入带有去离子水的贮液池中作为钙离子源，其中，组集A为工业固废材料；
(2)将组集B中一种或多种气体通入贮液池中，控制气体流速0.30～0.60L/min，优选为0.30L/min，开启搅拌装置，设置有搅拌棒，搅拌速率为700～1000r/min，优选为700r/min，与固废溶液反应生成碳酸氢钙溶液，贮液池温度保持在4～8℃，优选为4℃，在该温度下，钙离子溶解度高且利于方解石形成，当贮液池内pH值降低至6.0～6.3并保持不变时，贮液池中固废材料水解基本完成，封存二氧化碳已到达饱和状态，可暂时停止气体通入，更换贮液池中新的组集A，其中，组集B即碳酸氢根源，为空气或含有二氧化碳的工业废气等；
(3)称取组集C，即再生粉体，填入成型模具中，成型模具与贮液池通过管道连接，管道上设置有水泵，该水泵将贮液池中的碳酸氢钙溶液循环泵入成型模具中，溶液流速为1.0m/s～3.0m/s，适宜的流速可以保证通入成型模具的碳酸氢钙溶液充分受热分 解，并进行后续沉淀结晶反应，溶液流速过快可能造成部分碳酸氢钙溶液未发生分解或沉淀便流出成型模具，降低转化效率；流速过慢可能导致生产时间过长，降低碳化砖制备效率；
控制成型模具温度为45～55℃，优选为50℃，碳酸氢钙溶液受热分解，生成的二氧化碳与再生粉体中C-S-H凝胶浸出的钙离子发生反应，生成碳酸钙，并与碳酸氢钙溶液分解产生的碳酸钙一起在模具中沉淀、结晶和胶结再生粉体产生强度；
(4)当溶液流入成型模具处的压强达到1.5～3MPa时，优选为1.5MPa，表示成型模具中再生粉体已胶结成型并产生强度，此时关闭水泵，停止输送碳酸氢钙溶液；
由实例可判断该碳化砖最终抗压强度约15MPa左右，即拟定当压强为碳化砖抗压强度的1/10到1/5时，方解石已胶结再生粉体并搭建起网状结构，产生强度，通入的碳酸氢钙溶液量已足够，此时可以停止通入溶液；
(5)由于再生粉体与方解石颗粒均紧密堆积，方解石颗粒间存在牢固的机械咬合作用，可使成型模具中组集C材料迅速胶结，无需压制成型。停止碳酸氢钠溶液通入后,等待约30min后即可脱模，无需进行养护，在自然条件下晾干即可投入使用。
上述采用废弃混凝土再生粉体制备碳化砖的方法中，由组集A固废材料矿化封存二氧化碳至碳化砖成型投入使用，历时约3～5小时，可有效节约生产时间。
本发明的原理为：
碳酸化反应原理涉及一系列物理吸附和扩散过程，基于气-液-固相反应理论，该过程可大致分为四个阶段：首先在常温常压状态下，工业固体废弃物中的钙基活性物质溶解，在水介质中发生水解，释放出氢氧根离子，使浆液pH值上升，浆液表现出强碱性从而有很强的捕捉、封存二氧化碳能力；二氧化碳溶于水生成碳酸，与浆液中氢氧根离子和钙离子迅速反应，导致浆液pH值开始下降并生成碳酸钙沉淀；之后固废材料水解产生氢氧根离子的速率基本与碳酸氢根电离出氢离子的速率持平，浆液pH值保持相对稳定；随着矿化反应不断进行，水解产生氢氧根离子的速率逐渐低于二氧化碳通入产生氢离子的速率，浆液pH值逐渐下降至保持不变时，碳酸化反应基本完成。
随着二氧化碳过量通入，浆液呈弱酸性，碳酸钙沉淀逐渐消失，转化为碳酸氢钙，即下式反应：
CaO+H2O＝Ca(OH)2
Ca(OH)2＝Ca2++2OH-




Ca2++HCO3 -＝CaCO3+H+

碳酸氢钙溶液在成型模具50℃左右温度条件下，发生分解，产生二氧化碳与碳酸钙沉淀。在pH＝5～8条件下，再生粉体中C-S-H凝胶结构不稳定导致钙元素浸出，并与碳酸氢钙分解产生的二氧化碳发生反应，生成碳酸钙沉淀。沉淀下来的碳酸钙在温湿条件下形成结晶体(方解石)。该结晶体与再生粉体混合后，在间隙中生长发育从而 填充孔隙，胶结再生粉体并互相搭建形成网状结构，最终形成强度，再生粉体基于紧密堆积原理确定颗粒级配，可有效提高浆体密实度。
优选的，所述组集A包括电石渣、粉煤灰、钢渣、脱硫石膏、粒化高炉矿渣、尾矿、煤矸石等含钙工业固废材料中的任意一种或多种组合。
根据组集A中材料钙、铝、镁等元素占比，确定各组分质量占比，计算公式如下：
式中，y Ca为组集A中所有固废材料所含钙量之和；x为组集A中含钙量最高的固废材料的质量；N表示组集A中含钙量最高的固废材料中钙元素所占比例；xN/0.045表示组集A中含钙量最高的固废材料中钙元素含量；0.045为根据组集A中含钙量最高的固废材料含钙量所推导出的经验系数；M为组集A中所有固废材料总质量；0.516(M-x)为组集A中其它固废材料含钙量之和，0.516为根据组集A中其他固废材料含钙元素比例总和推导出的经验系数。
由于固废材料来源不同，化学组成中各成分占比有时会有较大差异，成分复杂，该经验系数具有修正作用，提高公式对多种类型的固废材料的适用性。
经验系数0.045、0.516为基于多组固废材料钙元素含量数据，在软件中拟合得到，由于由大量数据分析得到，具有代表性。
根据公式确定了组集A中含钙量最高的固废材料的质量后，选定硅、镁元素的适当含量，通过下式可确定其他固废材料的质量：

式中，y Si,y Mg分别为组集A中所有固废材料中硅元素含量、镁元素含量；Z为所选固废材料中硅元素所占比例；E为所选用固废材料中镁元素所占比例；xN/1.95、xN/10.14分别表示组集A中含钙量最高的固废材料所含硅元素、镁元素量，其中1.95、10.14分别为经验系数；Z(M-x)、E(M-x)分别表示其他固废材料中硅元素、镁元素含量。两部分相加，即可得到组集A中所有固废材料所含硅、镁元素量之和。
同上，经验系数1.95、10.14为基于多组固废材料硅、镁元素含量数据，在软件中拟合得到，由于由大量数据分析得到，具有代表性。
优选的，所述再生粉体，其主要成分为二氧化硅、氢氧化钙、硅铝酸钙和钙矾石等；
优选的，充分水化后的再生粉体中C-S-H凝胶占约总体积70％，氢氧化钙约占总体积20％。
优选的，所述贮液池连接有pH监测仪和温度控制器，通过温度控制器使贮液池温度保持稳定，通过pH监测仪监测贮液池的pH值变化，以调控二氧化碳通入时间。
优选的，所述贮液池和成型模具之间连接有进液主管和出液主管，水泵设置于进液主管上，所述进液主管靠近成型模具处设置有管道压强监测仪；
所述成型模具内包括多个与所制备的碳化砖尺寸等大的格子，尺寸可为240mm×115mm×53mm，240mm×115mm×180mm，180mm×180mm×90mm等，再生粉体的颗粒级配满足最紧密堆积状态，填入格子后呈均匀密实状态，粉体不易漂浮，无需将再生粉体制成湿物料装入成型模具中；
每个格子周围设置有加热管，且每一格子均设置有进液支管和出液支管，多个进液支管与进液主管连接，多个出液支管与出液主管连接。水泵将碳酸氢钙溶液循环泵送进成型模具，进入成型模具后，碳酸氢钙溶液流经各管道分支，进入每一格内。
优选的，依据GB/T 2452-2012《砌墙砖试验方法》测试所制碳化砖抗压强度与吸水率，基于碳化砖热重试验结果计算碳捕捉率，如下述公式：
式中，w(CO2)为碳化砖中二氧化碳的质量分数；M Ca和M CO2分别代表钙和二氧化碳的摩尔质量；Q Ca为碳酸化前(即放入贮液池前，未参加任何反应的固废材料)工业固废材料中钙的质量分数。
再生粉体符合最紧密堆积理论，颗粒间空隙最小，所制碳化砖整体更均匀、密实。基于Andreasen紧密堆积理论来评价颗粒级配，最紧密堆积状态下的粒度分布为：
式中，U(D)为粒径小于D的颗粒体积分数，％；D为颗粒粒径，μm；D1为体系中最大颗粒的粒径，μm；n为分布指数，取1/3。
再生粉体最紧密堆积状态下的粒度分布如表2所示，再生粉体的颗粒级配满足图表2时，颗粒分布为最紧密堆积状态：
表2：Andreasen分布最紧密堆积状态下的再生粉体颗粒级配(D max＝31.6μm)
组集C即再生粉体颗粒级配应满足最紧密堆积状态，如表2所示，氧化钙、二氧化硅含量为17.51～29.20wt％、27.80～43.26wt％，所述再生粉体的化学组成中主要包括氧化钙与二氧化硅，二氧化硅是再生粉体中最主要的晶相成分。由废弃混凝土制成的再生粉体中已有氢氧化钙、硅铝酸钙和钙矾石等水化产物，主要以凝胶体形式存在，不同废弃混凝土水化程度差异较大，导致水化产物含量差异较大。
优选的，所述组集A包括电石渣、粉煤灰和钢渣，其中按质量份，所述电石渣为30份、粉煤灰为35份、钢渣20；
贮液池中水51份，贮液池中水：组集A＝0.6，组集C中再生粉体30份。
优选的，所述组集A包括电石渣、粉煤灰和钢渣，其中按质量份，所述电石渣为33份、粉煤灰为30份、钢渣20；
贮液池中水51份，贮液池中水：组集A＝0.6，组集C中再生粉体30份。
优选的，所述组集A包括电石渣、粉煤灰和脱硫石膏，其中按质量份，所述电石渣为30份、粉煤灰为30份、脱硫石膏25；
贮液池中水51份，贮液池中水：组集A＝0.6，组集C中再生粉体30份。
电石渣成分包括79.68～84.90wt％CaO、1.56～3.28wt％SiO2、2.20～2.29wt％Al2O3、0.19～0.73wt％MgO，8.80～16.37wt％其它。
粉煤灰成分包括3.42～8.45wt％CaO、45.71～48.10wt％SiO2、23.20～31.34wt％Al2O3、2.47～3.17wt％Na2O、0.57～3.97wt％MgO，4.97～24.63wt％其它。
钢渣成分包括40.61～43.15wt％CaO、12.12～15.28wt％SiO2、4.72～5.31wt％Al2O3、6.95～7.02wt％Fe2O3、10.35～11.62wt％FeO、10.34～12.39wt％MgO、1.21～2.52wt％MnO，2.71～13.7wt％其它。
一种混凝土再生粉体碳化砖，由上述方法制备得到。
本发明以电石渣、粉煤灰、钢渣、脱硫石膏、粒化高炉矿渣、尾矿、煤矸石等工业固体废弃物提供钙源，基于液相碳酸化技术原理，使含二氧化碳的工业废气溶于水 产生的碳酸根离子与工业固体废弃物中溶出的钙离子反应，制成碳酸氢钙溶液，溶解度高，有效增加了二氧化碳封存量与转化率；将碳酸氢钙溶液通入含再生粉体的成型模具后，碳酸氢钙受热分解，反应接触面积大，速率快，产生的二氧化碳与碳酸钙沉淀，二氧化碳与成型模具中废弃混凝土再生粉体析出的钙离子反应同样生成碳酸钙沉淀，碳酸钙沉淀经结晶、聚合和胶结紧密堆积状态下的再生粉体，使制品产生强度，最终制得一种经济性好、生产效率高、无需煅烧、绿色环保的碳化砖，各方面性能均能满足国家标准要求的建筑材料，对实现“碳减排”目标具有现实作用。
值得注意的是，本发明所使用的仪器，如温度控制器、pH监测仪、管道压强监测仪等，均可采用市售机型，不影响本发明的实施。
本发明未详尽之处，均可采用现有技术。
本发明的有益效果为：
(1)本发明采用由废弃混凝土破碎、粉磨而成的再生粉体与粉煤灰、电石渣等工业固体废弃物，原料成本较低。粒径细小的再生粉体有利于其微集料填充效应的发挥；再生粉体的比表面积和颗粒细度一般大于常用水泥，有利于激发其活性，且工艺设备简单，有益于工业化生产。
(2)本发明选用最紧密堆积状态下的再生粉体颗粒级配，碳酸钙沉淀结晶形成紧密堆积的方解石颗粒，使得碳化砖产品密实，抗压强度高且强度稳定。
(3)与传统碳化砖生产工艺对比：现有的碳化砖制备工艺，多是将成型试件脱模后放入碳化室进行碳化养护至少3h甚至多天后制得砖体，生产时间较长，且二氧化碳气体扩散到混凝土基体的过程较为缓慢，固碳率较低，造成资源再生利用不充分、生产效率较低。本发明采用溶于水中的固废材料提供钙源，将二氧化碳气体固定转化为液态，溶解度高，可以有效提升二氧化碳固定率，碳酸钙结晶聚合、胶结再生粉体，省略碳化养护环节，成型脱模后即可立即投入使用，有效缩短生产时间。
(4)本发明可以永久捕捉、封存工业生产过程中产生的温室气体二氧化碳，且制备过程中无需煅烧，不排放任何污染性气体，有益于缓解温室效应，实现“碳减排”与资源再生利用，保护环境。
附图说明
图1为本发明的原理示意图；
图2为混凝土再生粉体碳化砖的制备过程示意图；
图中，1-贮液池，2-工业固废材料，3-搅拌棒，4-成型模具，5-水泵，6-碳化砖，7-pH监测仪，8-温度控制器，9-进液主管，10-出液主管，11-管道压强监测仪，12-加热管，13-再生粉体。
具体实施方式：
为使本发明要解决的技术问题、技术方案和优点更加清楚，下面将结合附图及具体实施例进行详细描述，但不仅限于此，本发明未详尽说明的，均按本领域常规技术。
实施例1：
一种混凝土再生粉体碳化砖的制备方法，如图1-2所示，包括以下步骤：
(1)称取一定质量组集A，并加入带有去离子水的贮液池1中作为钙离子源，其中，组集A为工业固废材料2；
(2)将组集B中一种或多种气体通入贮液池1中，控制气体流速为0.30L/min，开启搅拌装置，如图2所示，设置有搅拌棒3，搅拌速率为700r/min，与固废溶液反应生成碳酸氢钙溶液，贮液池温度保持在4℃，在该温度下，钙离子溶解度高且利于方解石形成，当贮液池1内pH值降低至6.0～6.3并保持不变时，贮液池中固废材料水解基本完成，封存二氧化碳已到达饱和状态，可暂时停止气体通入，更换贮液池中新的组集A，其中，组集B即碳酸氢根源，为空气或含有二氧化碳的工业废气等；
(3)称取组集C，即再生粉体13，填入成型模具4中，成型模具4与贮液池1通过管道连接，管道上设置有水泵5，该水泵5将贮液池中的碳酸氢钙溶液循环泵入成型模具中，溶液流速为1.0m/s～3.0m/s，适宜的流速可以保证通入成型模具的碳酸氢钙溶 液充分受热分解，并进行后续沉淀结晶反应，溶液流速过快可能造成部分碳酸氢钙溶液未发生分解或沉淀便流出成型模具，降低转化效率；流速过慢可能导致生产时间过长，降低碳化砖制备效率；
控制成型模具温度为50℃，碳酸氢钙溶液受热分解，生成的二氧化碳与再生粉体中C-S-H凝胶浸出的钙离子发生反应，生成碳酸钙，并与碳酸氢钙溶液分解产生的碳酸钙一起在模具中沉淀、结晶和胶结再生粉体产生强度；
(4)当溶液流入成型模具4处的压强达到1.5MPa，表示成型模具中再生粉体已胶结成型并产生强度，生成碳化砖6，此时关闭水泵，停止输送碳酸氢钙溶液；
(5)由于再生粉体与方解石颗粒均紧密堆积，方解石颗粒间存在牢固的机械咬合作用，可使成型模具中组集C材料迅速胶结，无需压制成型。停止碳酸氢钠溶液通入后,等待约30min后即可脱模，无需进行养护，在自然条件下晾干即可投入使用。
本发明的原理为：
碳酸化反应原理涉及一系列物理吸附和扩散过程，基于气-液-固相反应理论，该过程可大致分为四个阶段：首先在常温常压状态下，工业固体废弃物中的钙基活性物质溶解，在水介质中发生水解，释放出氢氧根离子，使浆液pH值上升，浆液表现出强碱性从而有很强的捕捉、封存二氧化碳能力；二氧化碳溶于水生成碳酸，与浆液中氢氧根离子和钙离子迅速反应，导致浆液pH值开始下降并生成碳酸钙沉淀；之后固废材料水解产生氢氧根离子的速率基本与碳酸氢根电离出氢离子的速率持平，浆液pH值保持相对稳定；随着矿化反应不断进行，水解产生氢氧根离子的速率逐渐低于二氧化碳通入产生氢离子的速率，浆液pH值逐渐下降至保持不变时，碳酸化反应基本完成。
随着二氧化碳过量通入，浆液呈弱酸性，碳酸钙沉淀逐渐消失，转化为碳酸氢钙，即下式反应：
CaO+H2O＝Ca(OH)2
Ca(OH)2＝Ca2++2OH-




Ca2++HCO3 -＝CaCO3+H+

碳酸氢钙溶液在成型模具50℃左右温度条件下，发生分解，产生二氧化碳与碳酸钙沉淀。在pH＝5～8条件下，再生粉体中C-S-H凝胶结构不稳定导致钙元素浸出，并与碳酸氢钙分解产生的二氧化碳发生反应，生成碳酸钙沉淀。沉淀下来的碳酸钙在温湿条件下形成结晶体(方解石)。该结晶体与再生粉体混合后，在间隙中生长发育从而填充孔隙，胶结再生粉体并互相搭建形成网状结构，最终形成强度，再生粉体基于紧密堆积原理确定颗粒级配，可有效提高浆体密实度，如图1所示。
实施例2：
一种混凝土再生粉体碳化砖的制备方法，如实施例1所述，所不同的是，组集A包括电石渣、粉煤灰、钢渣、脱硫石膏、粒化高炉矿渣、尾矿、煤矸石等含钙工业固废材料中的任意一种或多种组合。
实施例3：
一种混凝土再生粉体碳化砖的制备方法，如实施例1所述，所不同的是，再生粉体，其主要成分为二氧化硅、氢氧化钙、硅铝酸钙和钙矾石等；
充分水化后的再生粉体中C-S-H凝胶占约总体积70％，氢氧化钙约占总体积20％。
实施例4：
一种混凝土再生粉体碳化砖的制备方法，如实施例1所述，所不同的是，贮液池1连接有pH监测仪7和温度控制器8，通过温度控制器8使贮液池温度保持稳定，通过pH监测仪7监测贮液池的pH值变化，以调控二氧化碳通入时间。
贮液池1和成型模具4之间连接有进液主管9和出液主管10，水泵5设置于进液主管上，进液主管9靠近成型模具处设置有管道压强监测仪11；
成型模具4内包括多个与所制备的碳化砖尺寸等大的格子，尺寸可为240mm×115mm×53mm，240mm×115mm×180mm，180mm×180mm×90mm等，再生粉体的颗粒级配满足最紧密堆积状态，填入格子后呈均匀密实状态，粉体不易漂浮，无需将再生粉体制成湿物料装入成型模具中；
每个格子周围设置有加热管12，且每一格子均设置有进液支管和出液支管，多个进液支管与进液主管9连接，多个出液支管与出液主管10连接。水泵5将碳酸氢钙溶液循环泵送进成型模具，进入成型模具后，碳酸氢钙溶液流经各管道分支，进入每一格内。
实施例5：
一种混凝土再生粉体碳化砖的制备方法，如实施例1所述，所不同的是，组集A包括电石渣、粉煤灰和钢渣，其中按质量份，所述电石渣为30份、粉煤灰为35份、钢渣20；
贮液池中水51份，贮液池中水：组集A＝0.6，组集C中再生粉体30份。
电石渣成分包括79.68～84.90wt％CaO、1.56～3.28wt％SiO2、2.20～2.29wt％Al2O3、0.19～0.73wt％MgO，8.80～16.37wt％其它。
粉煤灰成分包括3.42～8.45wt％CaO、45.71～48.10wt％SiO2、23.20～31.34wt％Al2O3、2.47～3.17wt％Na2O、0.57～3.97wt％MgO，4.97～24.63wt％其它。
钢渣成分包括40.61～43.15wt％CaO、12.12～15.28wt％SiO2、4.72～5.31wt％Al2O3、6.95～7.02wt％Fe2O3、10.35～11.62wt％FeO、10.34～12.39wt％MgO、1.21～2.52wt％MnO，2.71～13.7wt％其它。
实施例6：
一种混凝土再生粉体碳化砖的制备方法，如实施例5所述，所不同的是，组集A包括电石渣、粉煤灰和钢渣，其中按质量份，所述电石渣为33份、粉煤灰为30份、钢渣20；
贮液池中水51份，贮液池中水：组集A＝0.6，组集C中再生粉体30份。
实施例7：
一种混凝土再生粉体碳化砖的制备方法，如实施例5所述，所不同的是，组集A包括电石渣、粉煤灰和脱硫石膏，其中按质量份，所述电石渣为30份、粉煤灰为30份、脱硫石膏25；
贮液池中水51份，贮液池中水：组集A＝0.6，组集C中再生粉体30份。
实施例8：
一种混凝土再生粉体碳化砖的制备方法，如实施例7所述，所不同的是，依据GB/T2452-2012《砌墙砖试验方法》测试所制碳化砖抗压强度与吸水率，基于碳化砖热重试验结果计算碳捕捉率，如下述公式，结果如表1所示：
式中，w(CO2)为碳化砖中二氧化碳的质量分数；MCa和MCO2分别代表钙和二氧化碳的摩尔质量；QCa为碳酸化前(即放入贮液池前，未参加任何反应的固废材料)工业固废材料中钙的质量分数。
表1：碳化砖抗压强度、碳捕捉率
再生粉体符合最紧密堆积理论，颗粒间空隙最小，所制碳化砖整体更均匀、密实。基于Andreasen紧密堆积理论来评价颗粒级配，最紧密堆积状态下的粒度分布为：
式中，U(D)为粒径小于D的颗粒体积分数，％；D为颗粒粒径，μm；D1为体系中最大颗粒的粒径，μm；n为分布指数，取1/3。
再生粉体最紧密堆积状态下的粒度分布如表2所示，再生粉体的颗粒级配满足图表2时，颗粒分布为最紧密堆积状态：
表2：Andreasen分布最紧密堆积状态下的再生粉体颗粒级配(Dmax＝31.6μm)
组集C即再生粉体颗粒级配应满足最紧密堆积状态，如表2所示，氧化钙、二氧化硅含量为17.51～29.20wt％、27.80～43.26wt％。
实施例8：
一种混凝土再生粉体碳化砖，如实施例7所述的方法制备得到。
以上所述是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明所述原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (8)

  1. 一种混凝土再生粉体碳化砖的制备方法，其特征在于，包括以下步骤：
    (1)称取一定质量组集A，并加入带有去离子水的贮液池中作为钙离子源，其中，组集A为工业固废材料；
    (2)将组集B气体通入贮液池中，控制气体流速0.30～0.60L/min，开启搅拌装置，与固废溶液反应生成碳酸氢钙溶液，贮液池温度保持在4～8℃，在该温度下，钙离子溶解度高且利于方解石形成，当贮液池内pH值降低至6.0～6.3并保持不变时，贮液池中固废材料水解完成，封存二氧化碳已到达饱和状态，暂时停止气体通入，更换贮液池中新的组集A，其中，组集B为空气或含有二氧化碳的工业废气；
    (3)称取组集C 30份，即再生粉体，填入成型模具中，成型模具与贮液池通过管道连接，管道上设置有水泵，该水泵将贮液池中的碳酸氢钙溶液循环泵入成型模具中，溶液流速为1.0m/s～3.0m/s，控制成型模具温度为45～55℃，碳酸氢钙溶液受热分解，生成的二氧化碳与再生粉体中C-S-H凝胶浸出的钙离子发生反应，生成碳酸钙，并与碳酸氢钙溶液分解产生的碳酸钙一起在模具中沉淀、结晶和胶结再生粉体产生强度；
    (4)当溶液流入成型模具处的压强达到1.5～3MPa时，表示成型模具中再生粉体已胶结成型并产生强度，此时关闭水泵，停止输送碳酸氢钙溶液；
    (5)等待30min后即可脱模，在自然条件下晾干即可投入使用；
    根据组集A中材料钙、铝、镁等元素占比，确定各组分质量占比，计算公式如下：
    式中，y Ca为组集A中所有固废材料所含钙量之和；x为组集A中含钙量最高的固废材料的质量；N表示组集A中含钙量最高的固废材料中钙元素所占比例；xN/0.045表示组集A中含钙量最高的固废材料中钙元素含量；0.045为根据组集A中含钙量最高的固废材料含钙量所推导出的经验系数；M为组集A中所有固废材料总质量；0.516(M-x)为组集A中其它固废材料含钙量之和，0.516为根据组集A中其他固废材料含钙元素比例总和推导出的经验系数；
    根据公式确定了组集A中含钙量最高的固废材料的质量后，选定硅、镁元素的适当含量，通过下式可确定其他固废材料的质量：

    式中，y Si,y Mg分别为组集A中所有固废材料中硅元素含量、镁元素含量；Z为所选固废材料中硅元素所占比例；E为所选用固废材料中镁元素所占比例；xN/1.95、xN/10.14分别表示组集A中含钙量最高的固废材料所含硅元素、镁元素量，其中1.95、10.14分别为经验系数；Z(M-x)、E(M-x)分别表示其他固废材料中硅元素、镁元素含量，两部分相加，即可得到组集A中所有固废材料所含硅、镁元素量之和；
    所述组集A包括电石渣、粉煤灰、钢渣、脱硫石膏、粒化高炉矿渣、尾矿、煤矸石中的任意一种或多种组合；
    所述再生粉体包括二氧化硅、氢氧化钙、硅铝酸钙和钙矾石；
    再生粉体最紧密堆积状态下的粒度分布为：
    式中，U(D)为粒径小于D的颗粒体积分数，％；D为颗粒粒径，μm；D 1为体系中最大颗粒的粒径，μm；n为分布指数，取1/3。
  2. 根据权利要求1所述的混凝土再生粉体碳化砖的制备方法，其特征在于，充分水化后的再生粉体中C-S-H凝胶占总体积70％，氢氧化钙占总体积20％。
  3. 根据权利要求1所述的混凝土再生粉体碳化砖的制备方法，其特征在于，所述贮液池连接有pH监测仪和温度控制器，通过温度控制器使贮液池温度保持稳定，通过pH监测仪监测贮液池的pH值变化，以调控二氧化碳通入时间。
  4. 根据权利要求1所述的混凝土再生粉体碳化砖的制备方法，其特征在于，所述贮液池和成型模具之间连接有进液主管和出液主管，水泵设置于进液主管上，所述进液主管靠近成型模具处设置有管道压强监测仪；
    所述成型模具内包括多个与所制备的碳化砖尺寸等大的格子，再生粉体的颗粒级配满足最紧密堆积状态，填入格子后呈均匀密实状态；
    每个格子周围设置有加热管，且每一格子均设置有进液支管和出液支管，多个进液支管与进液主管连接，多个出液支管与出液主管连接。
  5. 根据权利要求1所述的混凝土再生粉体碳化砖的制备方法，其特征在于，所述组集A包括电石渣、粉煤灰和钢渣，其中按质量份，所述电石渣为30份、粉煤灰为35份、钢渣20；
    贮液池中水51份，组集C中再生粉体30份。
  6. 根据权利要求1所述的混凝土再生粉体碳化砖的制备方法，其特征在于，所述组集A包括电石渣、粉煤灰和钢渣，其中按质量份，所述电石渣为33份、粉煤灰为30份、钢渣20；
  7. 根据权利要求1所述的混凝土再生粉体碳化砖的制备方法，其特征在于，所述组集A包括电石渣、粉煤灰和脱硫石膏，其中按质量份，所述电石渣为30份、粉煤灰为30份、脱硫石膏25；
  8. 一种混凝土再生粉体碳化砖，其特征在于，由权利要求4所述方法制备得到。
PCT/CN2023/074768 2022-05-06 2023-02-07 一种混凝土再生粉体碳化砖及其制备方法 Ceased WO2023213103A1 (zh)

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