CN115073108A - Method for regenerating high-strength negative carbon building material by using Ca-based solid waste and application thereof - Google Patents
Method for regenerating high-strength negative carbon building material by using Ca-based solid waste and application thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 44
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- 229910052791 calcium Inorganic materials 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
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- 229910001861 calcium hydroxide Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 9
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- 239000000126 substance Substances 0.000 description 8
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- 238000001035 drying Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 1
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Images
Classifications
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- 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
- C04B18/167—Recycled materials, i.e. waste materials reused in the production of the same 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of building materials, in particular to a method for regenerating a high-strength negative carbon building material by using Ca-based solid waste and application thereof. The method for regenerating the high-strength negative carbon building material by using the Ca-based solid waste comprises the following steps: the mineralized calcium component in the reaction raw materials is controlled to control the degree of the mineralization reaction in the system, the temperature of the system is regulated and controlled by utilizing the heat released by the mineralization reaction, the conditions required by the hydrothermal reaction are reached, and the mineralization reaction and the hydrothermal reaction can be carried out in the system, so that the high-strength building material finished product is prepared. The invention effectively realizes the high-efficiency resource utilization of industrial solid wastes, and the total carbon emission of the prepared building material product is reduced by more than 50 percent compared with the traditional portland cement product, thereby having important promotion effect on the low-carbon development of the building material industry in China.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a method for regenerating a high-strength negative carbon building material by using Ca-based solid waste and application thereof.
Background
In recent years, industrial solid waste is used as a raw material and is made into a building material by some recycling processing means, which is an effective way for resource utilization. The method can meet the development requirements of green environmental protection on one hand, and can meet the resource target of solid waste on the other hand, and is a feasible route for saving resources, protecting environment, eliminating waste and realizing 'win-win'.
At present, the main technical means of recycling building materials is mineralization, for example, chinese patent document CN109126412B provides a method for enhancing mineralization of carbon dioxide by saline wastewater, the method is characterized in that the solid waste is humidified and then dried, and then flue gas treated by wastewater is mineralized, so that carbon dioxide is effectively captured, and the utilization of bulk solid waste is realized; however, this prior art requires temperatures of 450 ℃ and 650 ℃ during the mineralization reaction. Chinese patent document CN104987034B provides a method for preparing building bricks by directly carbonizing slag, and the solid waste is mineralized after ball milling, and the temperature of 30-180 ℃ is required in the process of mineralization reaction, so that the carbon emission of the whole process is improved by the part of heat. At present, the mineralization means in the prior art all need to provide certain heat for a system, and the problem of large energy consumption exists.
Disclosure of Invention
The invention provides a method for regenerating a high-strength negative carbon building material by using Ca-based solid waste, solves the technical problems of large emission of the existing solid waste, large demand of building materials, high energy consumption for treating solid waste, difficulty in realizing resource reutilization and the like, and adopts the Ca-based solid waste to supply CO to an industrial tail gas source by a technical means without an external heating source 2 Fixing to prepare the high-strength building material.
In the actual exploration process, the fact that the reaction of carbon dioxide and mineralized calcium in solid waste is an exothermic reaction is found, the part of heat is utilized, the temperature required by the mineralization reaction can be met, the energy consumption can be reduced, and few researches are conducted at present to utilize the part of heat.
The invention provides a method for regenerating a high-strength negative carbon building material by Ca (calcium) -based solid waste, which controls the mineralization of calcium in reaction raw materials to control the degree of mineralization in a system, utilizes the heat released by the mineralization to regulate and control the temperature of the system to achieve the conditions required by hydrothermal reaction, and enables the mineralization and hydrothermal reaction in the system to be carried out, thereby preparing a high-strength building material finished product.
In some preferred embodiments, the method for regenerating the high-strength negative carbon building material from the Ca-based solid waste does not use an external heating source in the whole process, and does not need to additionally introduce water vapor.
In some preferred embodiments, the method for regenerating the high-strength negative carbon building material from the Ca-based solid waste comprises the following steps:
s1, treating Ca-based solid waste to prepare a building material prefabricated product;
s2, transferring the prefabricated building material product into a reaction kettle, and introducing CO 2 And carrying out composite mineralization reaction on the gas to obtain a high-strength negative carbon building material finished product.
In some preferred embodiments, the raw material of the Ca-based solid waste includes a carbonized material and an auxiliary material.
The carbonized material comprises one or more of but not limited to carbide slag, fly ash and white mud.
Further, the mass fraction of the calcium-based component (calcium oxide and/or calcium hydroxide) in the carbonized material is not less than 80%.
The auxiliary materials include but are not limited to one or more of fly ash, bottom ash, red mud, construction waste, waste cement, tailings and ore raw materials.
More preferably, the raw material of the Ca-based solid waste comprises a carbonized material and an auxiliary material, and the weight ratio of the carbonized material to the auxiliary material is (10-40): (40-80).
The inventor finds that in the process of exploration, the prefabricated product is obtained by stirring, powder mixing, digestion and pressing of Ca-based solid waste, and the prefabricated product is used for treating CO 2 The waste resources can be effectively recycled by mineralizing and fixing, and the problems of large waste discharge and difficult treatment are solvedAnd can meet the use requirements of the building material market. Further in the exploration process, the raw material of the solid waste and the CO content are regulated and controlled 2 The parameters of tail gas and reaction kettle device show that the calcium hydroxide content in the solid waste is controlled within a certain range, the mineralization reaction can be promoted to quickly release heat energy, the temperature of a reaction system is spontaneously increased, the temperature of the hydrothermal reaction is reached while the mineralization reaction is carried out, and the solid waste is fully utilized to carry out CO reaction 2 The strength of the product is improved by hydrothermal reaction while the effective fixation is performed. It has further been found that when the content of the calcium-based component (calcium hydroxide and/or calcium oxide) of the Ca-based solid waste satisfies a certain relationship, CO in the reaction system 2 The heat energy released by mineralized calcium can reach the optimal temperature of the hydrothermal reaction, so that the mineralization reaction and the hydrothermal reaction are balanced, on one hand, the carbon fixation rate of the building material product is increased, and on the other hand, the mechanical strength of the building material product can be kept at a higher level.
In some preferred embodiments, the step S1 is specifically that the Ca-based solid waste is first mixed with water to obtain a mixture (i.e., a reaction raw material), the mixture is digested and pulverized, and then formed to obtain a building material preform.
More preferably, the solid-to-liquid ratio of the raw material of the Ca-based solid waste to water is 1: (0.05-0.3).
In some preferred embodiments, the molding method is: transferring the material into a mold, and applying certain pressure to prepare a building material prefabricated product; further preferably, the molding pressure is 5 to 110 MPa.
In some preferred embodiments, the step S2 is embodied by transferring the building material preform to a reaction vessel and introducing a CO-containing gas into the vessel 2 And (3) carrying out composite mineralization reaction on the gas (the composite mineralization reaction is not a simple mineralization reaction, and the mineralization reaction and the hydrothermal reaction are carried out in the system), and reacting for 1-8h to obtain the high-strength building material finished product.
Further preferably, the pressure of the composite mineralization reaction in the step S2 is 0.05-1 MPa.
Further preferably, the building material preform is transferred to the reaction vessel with a fill rate of 10-60%; more preferably, the filling rate is 15 to 50%.
In some preferred embodiments, the method for regenerating high-strength negative carbon building materials from Ca-based solid wastes satisfies the following formula:
a＞[H+3.593*10 5 *v/T 0 -3.593*m*10 8 /(T 0 *ρ)+4.446*v*10 6 (P-37.315/T 0 )-4.446*m*10 9 (P-37.315/T 0 )/ρ+1.321*10 6 *m-4.356*P+2.344*10 8 /(373.15-T 0 )-2.344*10 11 *m/(373.15*ρ*v-T 0 *ρ*v)]/[1.538*10 9 *m*k/(373.15-T 0 )-4.1*10 5 *m-9.86*10 5 *m*k]；
wherein: m is the mass of the building material prefabricated product, the unit is t, H is the heat capacity of the reaction kettle, and the unit is J/K; v is the volume of the reaction kettle and is in m 3 (ii) a ρ is the True Density (True Density) of the building material preform (the actual mass of the material in an absolutely dense state per unit volume of solid matter, i.e. the Density after removal of internal voids or interparticle voids), in kg/m 3 ；T 0 Is the initial reaction temperature in K; p is reaction pressure in MPa; a is the mass fraction of calcium-based components in the reaction raw materials (the total mass fraction of calcium hydroxide in the embodiment of the application), and the unit is; k is an empirical reaction constant in units of 1.
The above-mentioned
(ii) a Wherein Mi is mass M of each component of the kettle body of the reaction device 1 、M 2 、M 3 …M n Ci is the specific heat capacity C corresponding to each component of the reaction kettle body 1 、C 2 、C 3 …C n 。
The reaction device is made of a kettle body and a heat-insulating material, wherein the kettle body can be made of one or more of carbon manganese steel, stainless steel, zirconium, nickel-based (Hash, Monel) alloy, other composite materials and the like; the heat insulating material may be one or more of rare earth heat insulating material, rock wool, inorganic silicate slurry, novel inorganic heat insulating material, polystyrene board, polyurethane foam material, glass wool, aluminum silicate wool, etc.
In some preferred embodiments, the method for regenerating high-strength negative carbon building materials from Ca-based solid wastes further satisfies the following formula:
a＜[H+3.593*10 5 *v/T 0 -3.593*m*10 8 /(T 0 *ρ)+4.446*v*10 6 (P-47.315/T 0 )-4.446*m*10 9 (P-47.315/T 0 )/ρ+1.321*10 6 *m-3.435*P+2.344*10 8 /(473.15-T 0 )-2.344*10 11 *m/(473.15*ρ*v-T 0 *ρ*v)]/[1.538*10 9 *m*k/(473.15-T 0 )-4.1*10 5 *m-9.86*10 5 *m*k](ii) a The value range of k is 0.8-1.
Further preferably, k has a value in the range of 0.84 to 1.
In some preferred embodiments, in the step S2, the CO is contained 2 The gas is derived from industrial tail gas, CO 2 The volume fraction in the industrial tail gas is 5-98%; further preferably, CO 2 The volume fraction in the industrial tail gas is 8-95%.
In some preferred embodiments, the industrial tail gas comprises a mixture of one or more of chemical plant flue gas, cement plant flue gas, coal fired power plant flue gas, lime kiln flue gas, steel plant flue gas, and post carbon capture desorption gas.
The invention provides an application of a method for regenerating a high-strength negative carbon building material by using Ca-based solid waste in the field of building materials.
Has the beneficial effects that:
the method for regenerating the high-strength negative carbon building material by using the Ca-based solid waste has the following advantages:
(1) the invention fully utilizes the calcium hydroxide in the Ca-based solid waste to fix the CO 2 The building material product with good carbon-fixing performance and excellent physical performance is prepared by a large amount of reaction heat generated in the process, so that the solid waste disposal cost is greatly reduced, the tail gas recycling of various high-carbon emission industries is facilitated, and the problem of large volume of waste gas is solvedThe treatment problem of the batch solid waste is favorable for the resource development of the industry;
(2) in the method for regenerating the high-strength negative carbon building material by using the Ca-based solid waste, the active calcium component in the solid waste is effectively utilized to control the reaction heat release, the carbon fixation performance of the mineralized product is improved, and the temperature in the system reaches the temperature required by the hydration reaction, so that the hydration reaction is carried out in the later stage of the mineralization reaction of the product, the mechanical strength of the product is further improved, and the waste CO in industrial production is absorbed 2 Meanwhile, the loss of excessive active ingredients is avoided, the cost of the building material is further reduced, solid wastes are fully utilized and converted into high-strength building material products with excellent performance;
(3) the invention takes pure bulk solid waste as raw material and uses CO 2 The source gas is directly introduced into the reaction kettle for mineralization and maintenance, and high-quality building material finished products can be prepared under the control of specific technological parameters, so that the large-batch use requirements of the building material industry can be greatly met, and the method has extremely high popularization and application values;
(4) the invention effectively realizes the high-efficiency resource utilization of industrial solid wastes, and the total carbon emission of the prepared building material product is reduced by more than 50 percent compared with the traditional portland cement product, thereby having important promotion effect on the low-carbon development of the building material industry in China.
Drawings
FIG. 1 is a graph of the glass transition temperature of carbide slag;
FIG. 2 is a comparison of the thermogravimetric analysis curves of TG/DTG of examples 2, 6 and 7.
Detailed Description
Examples 1 to 8
The method for regenerating the high-strength negative carbon building material by using the Ca-based solid waste comprises the following steps:
s1, preparing a building material prefabricated product by using Ca-based solid waste;
s2, transferring the prefabricated building material product into a reaction kettle, and introducing CO 2 And carrying out composite mineralization reaction on the gas to obtain a high-strength negative carbon building material finished product.
And S1, specifically, mixing the Ca-based solid waste with water uniformly to obtain a mixture, transferring the mixture into a digestion system for digestion for 40min, then feeding into a mechanical forming system, pressing into blocks, wherein the forming pressure is 10MPa, and the specification of the building material prefabricated product is 200mm x 95mm x 53 mm.
The S2 step is specifically that 90.6t of building material prefabricated product is transferred into a reaction kettle (the filling rate is 30 percent) and CO is introduced 2 Carrying out composite mineralization reaction on the gas, wherein the initial temperature of the composite mineralization reaction is room temperature (25 ℃), the reaction time is 360min, the reaction pressure in the kettle is 0.6MPa, and CO is 2 The volume concentration is 76.5 percent, and the high-strength building material finished product is obtained after the composite mineralization reaction is finished.
The raw materials of the Ca-based solid waste comprise a carbonized material and an auxiliary material; the amounts of the carbonized material, the auxiliary materials and water added and the content of calcium hydroxide of the raw material of the Ca-based solid waste in each example are shown in table 1 (weight percent).
The carbonization material is specifically carbide slag of a certain coal chemical plant, the water content is 31.73%, and the chemical components and the weight percentage of the carbonization material are shown in a table 2 after XRF analysis; the auxiliary material adopts two materials, wherein one auxiliary material is coal ash of a certain coal chemical industry plant, the water content of the coal ash is 2%, and the chemical components and the weight percentage of the coal ash are shown in a table 3 by XRF analysis; the second auxiliary material is a reclaimed material of a certain building material factory, the water content of the reclaimed material is 1 percent, and the chemical components and the weight percent of the reclaimed material are shown in Table 4 by XRF analysis.
In the step S2, the carbon monoxide is contained 2 The gas comes from tail gas produced by a coal chemical plant for compounding fertilizer and the composition of the tail gas is shown in a table 5.
CaO and Ca (OH) listed in the following tables 2 There is a conversion relationship, taking the carbide slag containing 15.10% (example 1) in the green body as an example, the moisture content of the carbide slag is 31.73%, the absolutely dry carbide slag content is 10.31%, fig. 1 is a glass transition temperature diagram of the carbide slag, wherein the corresponding mass reduction at 400-The actual phase composition in the material, wherein CaO in the auxiliary material is inert calcium carbonate and does not participate in the reaction, so that only the active calcium component in the carbide slag is calculated), namely a is 9.0% in example 1; similarly, in examples 2 to 8, a is 11.0%, 13.5%, 17.0%, 18.0%, 20.1%, 25.0%, and 27.0%, respectively.
TABLE 1
| Carbonized material | Auxiliary material one | Auxiliary material 2 | Water (W) | Calcium hydroxide content | |
| Example 1 | 15.10% | 36.35% | 36.35% | 12.20% | 9.0% |
| Example 2 | 18.45% | 35.20% | 35.20% | 11.15% | 11.0% |
| Example 3 | 22.65% | 33.77% | 33.77% | 9.81% | 13.5% |
| Example 4 | 28.52% | 31.77% | 31.77% | 7.94% | 17.0% |
| Example 5 | 30.21% | 31.19% | 31.19% | 7.41% | 18.0% |
| Example 6 | 33.69% | 30% | 30% | 6.31% | 20.0% |
| Example 7 | 41.95% | 26.61% | 26.61% | 3.16% | 25.0% |
| Example 8 | 45.30% | 26.04% | 26.04% | 2.62% | 27.0% |
TABLE 2
| Elemental composition | CaO | CO 2 | SiO 2 | Al 2 O 3 | SO 3 | Fe 2 O 3 | MgO | Na 2 O | LOSS |
| Content (%) | 90.6 | 3.3 | 2.9 | 1.2 | 0.6 | 0.3 | 0.1 | 0.1 | 0.9 |
TABLE 3
| Elemental composition | SiO 2 | Al 2 O 3 | CO 2 | CaO | Fe 2 O 3 | Na 2 O | SO 3 | MgO | LOSS |
| Content (%) | 43.3 | 31.5 | 12.5 | 2.7 | 4.4 | 0.8 | 0.7 | 0.4 | 3.7 |
TABLE 4
| Elemental composition | SiO 2 | Al 2 O 3 | CO 2 | CaO | Fe 2 O 3 | K 2 O | MgO | Na 2 O | LOSS |
| Content (%) | 44.7 | 10.5 | 22.2 | 9.62 | 5.04 | 2.43 | 1.47 | 0.871 | 3.169 |
TABLE 5
| Gas composition | CO 2 | N 2 | SOx | NOx | VOCs |
| Coal chemical industry tail gas | 76.5% | 18.9% | 2.3% | 2% | 0.3% |
The relevant information of the reaction kettle, the building material prefabricated product and the like in the step S2 is as follows:
the volume v of the reaction kettle is 178m 3 The thickness of the steel is 10 mm, and the density of the steel is 7950 kg/m 3 The thickness of the heat preservation rock wool is 100 mm, and the density of the rock wool is 120kg/m 3 (ii) a H = 23345514J/K; the building material prefabricated product has a true density of 1690kg/m 3 (ii) a The reaction pressure P is 0.6 MPa; the initial reaction temperature was 298.15K, the building material preform mass was 90.6t, and the empirical reaction constant K was 1.
Substituting the above parameters into a formula can obtain: 9.75% < a < 25.55%.
Performance test method
1. Compressive strength
The compressive strength of the high-strength building material finished products in examples 1 to 8 is tested by referring to GBT4111-2013 concrete block and brick test method. The strength of the test block is measured after the test block is naturally air-dried for 24 hours, and the specific operation is as follows: the YE-30 type hydraulic pressure tester is used for the compression test. And 5 parallel samples are arranged on each high-strength building material finished product, and the average value of the compressive strength of the parallel samples is calculated. If the measured compressive strength value of the sample differs from the average value by not more than 15%, using the average value as the compressive strength; if the difference between a certain measured value and the average value is more than 15%, the value is cut off, and the average value is calculated by using the rest values; if more than 2 measured values differ from the average by more than 15%, the experiment is repeated. The test results are shown in Table 6.
The compressive strength can be calculated by the following formula: σ D = P/F =4P/π D 2 =P/0.875d 2
Wherein σ D-compressive strength, kgf/cm 2 (ii) a P-crush load, kgf; d-average diameter of the pellet sample, cm.
2. Carbon fixation rate
The carbon fixation rate test method specifically comprises the following steps:
1) 1/8 in volume of the finished brick prepared in the embodiment 1-10 is taken and crushed into powder to be tested for the integral carbon fixation rate;
2) crushing a powdery sample for the test of the overall carbon sequestration rate by using a crusher, drying 50g of the crushed sample in a 105 ℃ drying oven for 12 hours without vacuumizing, keeping the drying oven sealed, and placing NaOH particles in a large beaker in the drying oven; after drying, taking out 5g of sample, grinding the sample in a mortar until no granular sensation exists (only about 1-2 minutes), and filling the sample in a small self-sealing bag; the small valve bag is placed in the big bag, and the silica gel desiccant is placed in the big bag.
3) Putting the prepared sample into a sample bin, and setting the experimental atmosphere to be N 2 The temperature range is from room temperature to 1000 ℃, and the heating rate is 10 ℃/min. The test analysis was performed by using a STA409EP comprehensive thermal analyzer manufactured by german stony-school (NETZSCH); the test results are shown in Table 6;
4) obtaining a TG/DTG thermogravimetric analysis curve after the test is finished; the thermogravimetric analysis curves of TG/DTG of examples 2, 6 and 8 are compared in FIG. 1.
Note: the application takes CO as raw material 2 The carbon absorption effect of the sample, which is the absorption of CO by solid wastes, was evaluated 2 The mass of the solid waste is in percentage of the mass of the test block, and the solid waste absorbs CO 2 The content of (b) is obtained by testing a TG/DTG thermogravimetric analysis curve of the mineralized product, the content of carbon dioxide absorbed by the mineralized product is 605-820 ℃ of mass reduction, and the mass of the test block is the mass of the mineralized product at 105 ℃.
Performance test data
TABLE 6
| Compressive strength (MPa) | Carbon fixation Rate (%) | |
| Example 1 | 6.75 | 4.59 |
| Example 2 | 7.43 | 7.80 |
| Example 3 | 9.37 | 10.34 |
| Example 4 | 11.36 | 13.20 |
| Example 5 | 13.36 | 14.72 |
| Example 6 | 15.41 | 15.28 |
| Example 7 | 17.72 | 12.30 |
| Example 8 | 19.41 | 7.32 |
As can be seen from Table 6, the compressive strength and the carbon fixation of the finished building material products prepared when the mass fraction of the calcium-based component (i.e., calcium hydroxide in the examples) in the reaction raw materials (i.e., the mixes used to prepare the building material preforms) of examples 2-7 was within the range calculated according to the formula of the present application (9.75% < a < 25.55%). The calcium hydroxide content of the building material in example 1 is 9 percent, which is lower than the range defined by the calculation result of the formula, so that the compressive strength and the carbon fixation rate of the prepared building material finished product are both obviously lower than those of other examples. In example 8, the content of calcium hydroxide reaches 27 percent, which is higher than the range defined by the calculation result of the formula, and although high compressive strength is obtained, the carbon fixation rate is poor. The materials are mixed according to the calculation result of the formula, which is beneficial to obtaining building material products with higher compressive strength and carbon fixation rate.
As shown in Table 6, the calcium content in example 1 was not at its minimum, and the compressive strength and carbon fixation rate of the finished building material were low; the carbon fixation rate of the embodiment 2-3 is rapidly improved along with the increase of the carbide slag content, and the strength of the building material finished product is rapidly improved along with the increase of the carbide slag content; on one hand, the theoretical carbon-fixing amount in the building material finished product is increased due to the increase of the content of mineralized calcium in the blank, and on the other hand, the carbon-fixing rate is increased due to the increase of the disturbance of carbon dioxide gas and the increase of the contact probability with the mineralized calcium due to the increase of the temperature of the reaction kettle, but the strength of the material is enhanced by the calcium carbonate generated by mineralization in a limited way, so that the acceleration of the compressive strength is slower, and the hydrothermal reaction in the system is less due to the lower environmental temperature, so that the strength of the test block is not obviously improved; in the examples 4 to 6, the carbon fixation rate is gradually increased along with the increase of the carbide slag content, and the strength of the product is rapidly increased, because the increase of the calcium content enables the temperature of the reaction kettle to reach a certain temperature, the hydroxide radical destroys the silicon-oxygen bond and the aluminum-oxygen bond in the silicon-aluminum solid waste, and simultaneously the generated silicate ions and the calcium ions are combined with each other to generate CSH gel/tobermorite, so that the strength of the product is rapidly increased, and the carbon fixation rate is slowly increased; in examples 7 to 8, the carbon fixation rate of the finished building material product is significantly reduced with the rapid increase of the calcium content, because the mineralized calcium content is increased, the mineralization degree at the initial stage of the reaction is relatively high, the temperature in the reaction kettle is greatly increased, a large amount of calcium hydroxide and calcium oxide which are remained after a certain temperature are subjected to hydrothermal reaction with silicon and aluminum to generate a large amount of CSH, and the mineralized calcium hydroxide and calcium oxide are rapidly reduced to reduce the carbon fixation rate and significantly improve the compressive strength.
Claims (10)
1. A method for regenerating high-strength negative carbon building materials by Ca-based solid wastes is characterized in that the mineralization reaction degree in a system is controlled by controlling mineralized calcium components in reaction raw materials, the temperature of the system is regulated and controlled by utilizing the heat released by the mineralization reaction, the conditions required by a hydrothermal reaction are reached, and the mineralization reaction and the hydrothermal reaction can be carried out in the system, so that a high-strength building material finished product is prepared.
2. The method for regenerating the high-strength negative carbon building material from the Ca-based solid waste as claimed in claim 1, wherein no external heat source is used in the whole process of the method for regenerating the high-strength negative carbon building material from the Ca-based solid waste, and no additional water vapor is introduced.
3. The method for regenerating the high-strength negative carbon building material from the Ca-based solid waste as claimed in claim 1 or 2, wherein the method for regenerating the high-strength negative carbon building material from the Ca-based solid waste comprises the following steps:
s1, preparing a building material prefabricated product by using Ca-based solid waste;
s2, transferring the prefabricated building material product into a reaction kettle, and introducing CO 2 And carrying out composite mineralization reaction on the gas to obtain a high-strength negative carbon building material finished product.
4. The method for regenerating high-strength negative carbon building material with Ca-based solid waste as claimed in claim 1, wherein the raw material of the Ca-based solid waste comprises carbonized material and auxiliary material; the carbonized material comprises one or more of carbide slag, white mud and fly ash; the auxiliary material comprises one or more of fly ash, bottom ash, red mud, construction waste, waste cement, tailings and ore raw materials.
5. The method for regenerating high-strength negative carbon building material from Ca-based solid waste according to claim 4, characterized in that the mass fraction of the calcium-based component in the carbonized material is not less than 80%.
6. The method for regenerating the high-strength negative carbon building material from the Ca-based solid waste as claimed in claim 3, wherein the step S1 is specifically that the Ca-based solid waste is uniformly mixed with water to obtain a mixture, the mixture is subjected to digestion and powder mixing, and then molding is performed to obtain the building material prefabricated product.
7. The method for regenerating high-strength negative carbon building material from Ca-based solid waste according to claim 1, wherein the method for regenerating high-strength negative carbon building material from Ca-based solid waste satisfies the following formula:
wherein: m is the mass of the prefabricated building material product, H is the heat capacity of the reactor, v is the volume of the reactor, rho is the true density of the prefabricated building material product, and T 0 P is the reaction initial temperature, P is the reaction pressure, a is the mass fraction of the calcium-based component in the reaction raw material, and k is the empirical reaction constant.
8. The method for recycling high-strength negative carbon building material from Ca-based solid waste according to claim 7, wherein the method for recycling high-strength negative carbon building material from Ca-based solid waste further satisfies the following formula:
the value range of k is 0.8-1.
9. The method for regenerating high-strength negative carbon building material from Ca-based solid waste as claimed in claim 3, wherein in step S2, the CO is contained 2 The gas is derived from industrial tail gas, CO 2 The volume fraction in the industrial tail gas is 5-98%.
10. The application of the method for regenerating the high-strength negative carbon building material from the Ca-based solid waste according to any one of claims 1 to 9 in the field of building materials.
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