CN117361915A - Method for preparing hydrothermal curing body based on relative content of active calcium and active silicon - Google Patents
Method for preparing hydrothermal curing body based on relative content of active calcium and active silicon Download PDFInfo
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- 239000011575 calcium Substances 0.000 title claims abstract description 71
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 68
- 239000010703 silicon Substances 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 39
- 238000001723 curing Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 60
- 230000029087 digestion Effects 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- 239000002893 slag Substances 0.000 claims description 28
- 239000002689 soil Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000120 microwave digestion Methods 0.000 claims description 12
- 238000009616 inductively coupled plasma Methods 0.000 claims description 11
- 238000004993 emission spectroscopy Methods 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000009257 reactivity Effects 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000004567 concrete Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002910 solid waste Substances 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 239000012615 aggregate Substances 0.000 claims description 2
- 238000009412 basement excavation Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 150000001669 calcium Chemical class 0.000 claims 1
- 150000003376 silicon Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 238000013461 design Methods 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 5
- 238000013007 heat curing Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 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 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 230000002706 hydrostatic effect Effects 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
-
- 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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing a hydrothermal curing body based on the relative content of active calcium and active silicon. The method comprises the steps of drying, grinding and sieving raw materials to obtain raw material particles with smaller particle sizes, quantitatively measuring the content of active silicon and active calcium in each raw material by simulating hydrothermal reaction conditions, preparing the mixing proportion of each raw material by taking the molar ratio of the active calcium to the active silicon as a control parameter, and fully mixing the raw materials; and after the working procedures of molding, aging, water-heat curing and the like are carried out, the building material with high strength is finally obtained. The invention establishes a design method for the mix proportion of the raw materials of the water-heat curing product by taking the molar ratio of active calcium and active silicon as key control indexes, solves the problems of long period, high cost, material consumption and the like when the optimal mix proportion of the materials is determined by a traditional trial-and-error method and a regional experience method, has strong operability, is beneficial to popularization, and has remarkable social benefit and economic benefit.
Description
Technical Field
The invention belongs to the technical field of building materials, and relates to a method for preparing a hydrothermal curing body based on a raw material mixing ratio, in particular to a method for preparing a hydrothermal curing body based on the relative content of active calcium and active silicon.
Background
Industrial waste, construction waste, engineering waste generally contains a large amount of calcareous or siliceous compounds, and has a certain reactivity under alkaline hydrothermal conditions. According to the diagenetic mechanism of the underground hydrothermal system, the hydrothermal curing technology can shorten the diagenetic period of thousands of years of natural piled rocks to a few hours under laboratory conditions. There are many reports of harmless treatment and recycling of waste by using the technology, for example, patent "a preparation method of recycled slag brick", "a preparation method of light high-strength humidity-regulating material", "a method of solidifying waste incineration fly ash into high-strength material", "a diatom ceiling with humidity regulating function and a preparation method thereof", "a method of preparing high-strength humidity-regulating material by using lactic acid residue", "a method of wet firing sea sand into high-strength building material". Compared with the traditional sintering method for preparing the building material, the method has the characteristics of low energy consumption and high efficiency.
However, the current research is only to design raw materials by trial and error or regional experience, and the difference between different research results is large. For example, the invention patent of a preparation method of regenerated slag brick suggests that the ratio of the amount of calcium element to the amount of silicon element substance in the raw material is 0.5-0.9 according to experience. The invention patent 'a preparation method of a light high-strength humidity-regulating material' suggests that the ratio of the amount of calcium element to the amount of silicon element substances in raw materials is 0.1-0.7. Within such a broad range, it is difficult to determine the optimum raw material mix ratio of the hydrothermal curable product both efficiently and accurately. In addition, because of the remarkable spatial variability of the chemical composition and physical and chemical characteristics of each raw material, even if the optimal formula of a certain product raw material is determined through a large number of trial and error tests, the optimal formula is difficult to popularize and apply on a large scale, and the defect of the unified design control index of the mixing ratio of the raw material of the hydrothermal curing product is undoubtedly the root cause of the phenomenon.
The relative amounts of calcareous and siliceous materials in the raw materials directly affect the classification of the hydrothermal reaction product. At present, tobolmullite (5CaO.6SiOo is widely known 2 ·5H 2 O) is a major cause of the increase in strength of the hydrothermally cured product. The theoretical Ca/Si molar ratio of tobermorite is 0.83. However, because of the existence of the raw materials without the hydrothermal reactionCalcareous and siliceous compounds, which lead to a large difference in the molar ratio Ca/Si in the optimum raw material formulation of the hydrothermally curable products, generally from 0.83. The Ca/Si molar ratio cannot be directly used as a control index for the design of the mixing ratio of raw materials. Moreover, there is still a lack of a more general method for preparing high strength hydrothermally cured bodies based on raw material mix ratios in the prior art.
Disclosure of Invention
In order to solve the problems in the background art, the invention aims to provide a method for preparing a hydrothermal curing body based on the relative content of active calcium and active silicon, and aims to solve the problems of long period, high cost, material consumption and the like when the optimal mixing ratio of materials is determined by a traditional trial-and-error method and a regional experience method.
The technical scheme adopted by the invention comprises the following steps:
s1, obtaining a plurality of raw materials, respectively drying, grinding and sieving the raw materials, and respectively sieving the raw materials to obtain raw material particles with the particle size smaller than 0.15mm;
s2, quantitatively measuring the content of active calcium and the content of active silicon in each raw material particle;
the active calcium content and the active silicon content are respectively the calcium content and the silicon content with hydrothermal reaction activity in the raw material particles.
S3, pouring all raw material particles into a container according to a certain proportion, and uniformly mixing to obtain a uniform mixture;
and S4, adding tap water into the mixture obtained in the step S3, blending the water content of the mixture to be near the optimal water content, preparing the mixture into a molded block sample by a pressing mode, aging the molded block sample for 4-7 days at the temperature of 20-30 ℃, performing a hydrothermal curing reaction on the block sample at the temperature of 100-250 ℃ for 0-24 hours, and finally preparing the high-strength hydrothermal curing body finished product. In the step S4, the mixture can be prepared into samples with different shapes by using a die, and the final finished product is obtained through a hydrothermal curing reaction.
In the step S1, the raw materials comprise one or more of engineering dregs, industrial solid waste, construction waste and raw material regulator.
In the step S2, the content of active calcium is specifically the content of calcium element which can participate in hydrothermal reaction under the conditions of alkaline environment, 100-250 ℃ and 0.1-4 MPa; the active silicon content is specifically the silicon element content which can participate in the hydrothermal reaction under the alkaline environment, the temperature condition of 100-250 ℃ and the pressure of 0.1-4 MPa.
The step S2 specifically comprises the following steps: the several raw material particles obtained in step S1 were mixed with an alkaline solution in a liquid-solid ratio of 10:1, mixing to obtain a raw material mixed solution, then carrying out treatment procedures such as digestion, acid washing, dilution, filtration and the like on the raw material mixed solution, and finally measuring the calcium content and the silicon content with hydrothermal reactivity in the filtered raw material mixed solution by utilizing an inductively coupled plasma emission spectrometry (ICP-OES).
In the step S3, the molar ratio between the active calcium and the active silicon in the mixture obtained by mixing the raw material particles is 0.83. The mixture comprises one or a combination of more of engineering dregs, industrial solid waste, construction waste and raw material regulator.
In the step S3, the pH value of the leachate of the mixture is not lower than 11.
The leaching solution of the mixture is specifically prepared from the mixture and water in a liquid-solid ratio of 1:2.5 mixing to obtain a solution.
The engineering slag soil comprises one or more of foundation pit excavation soil, shield slag soil and dehydrated mud cake; the industrial solid waste comprises one or a plurality of compositions of fly ash, slag, fly ash, steel slag, coal gangue, red mud and carbide slag; the construction waste comprises one or more of concrete, brick aggregate, ceramic and glass; the raw material regulator comprises one or a combination of more of lime, calcium hydroxide, quartz sand and sodium hydroxide.
In the step S2, the alkaline solution is sodium hydroxide solution, and the concentration of the alkaline solution is not lower than 100g/L.
In the step S2, the specific steps of digestion, acid washing and dilution treatment are as follows:
firstly, sealing the raw material mixed solution in a high-temperature high-pressure reaction kettle or a microwave digestion instrument for digestion treatment to obtain digestion solution; then adding dilute hydrochloric acid solution into the digestion solution, heating the digestion solution to boiling, keeping the temperature for 15-20 minutes, cooling to room temperature, and finally adding enough deionized water to dilute the solution, so that the concentration of the salt solution is in the range of the inductively coupled plasma emission spectrometer.
In the step S2, the temperature in the high-temperature high-pressure reaction kettle and the microwave digestion instrument is 100-250 ℃, and the digestion treatment time is 0-2 h; the concentration of the dilute hydrochloric acid solution added in the pickling treatment process is 0.5 mol/L-0.7 mol/L.
The formation and growth of tobermorite crystals is the primary cause of the increase in the strength of the hydrothermal cured body. The relative contents of active calcium and silicon in the raw materials are reasonably prepared, so that the formation of tobermorite can be directionally induced under the conditions of hydrothermal and strong alkalinity, and the hydrothermal curing body with certain strength is prepared.
Compared with the prior art, the method quantitatively measures the content of the calcium and the silicon with the hydrothermal reactivity in the raw materials by simulating the hydrothermal reaction conditions, and provides corresponding control indexes, so that the optimal mixing ratio of the raw materials can be more efficiently determined. The process flow is simple and clear, and is easy to popularize.
The engineering dregs and the construction waste generally contain silicon element with higher content, the industrial solid waste generally contains calcium element with higher content, and the compound has certain reactivity under alkaline hydrothermal conditions.
The raw material regulator in the method is mainly used for preparing the content of active calcium and active silicon of the mixture and the pH value of the mixture leaching solution, so that the situation that the related indexes of the mixture cannot be prepared to the expected values is avoided.
The chemical reactivity of the raw materials is related to temperature, pressure and pH value, so that the calcium and silicon with hydrothermal reactivity refer to the calcium and silicon elements capable of participating in hydrothermal reaction under the conditions of high temperature (100-250 ℃), high pressure (0.1-4 MPa) and alkalinity.
For raw materials containing calcium carbonate material, the actual active calcium content should be corrected on the basis of the measured value by subtracting the amount of calcium element contributed by the calcium carbonate.
Calcium carbonate is very stable in alkaline environments and does not chemically react with siliceous raw materials even under hydrothermal conditions. But it is readily soluble in an acidic environment. To avoid overestimating the active calcium content of the feed, it is necessary to determine the calcium carbonate content of the feed in advance by pre-experiments.
The invention establishes a method for designing the mix proportion of the raw materials of the water-heat curing product by taking the molar ratio of active calcium to active silicon as a key control parameter, solves the problems of long period, high cost, material consumption and the like when the optimal mix proportion of the materials is determined by a traditional trial-and-error method and a regional experience method, has strong operability, is beneficial to popularization, and has remarkable social benefit and economic benefit.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, the contents of active calcium and active silicon in raw materials are quantitatively measured by simulating hydrothermal reaction conditions, a raw material mixing ratio design system taking the molar ratio of the active calcium and the active silicon as a key control index is established, the problem that the optimal raw material mixing ratio of a hydrothermal curing product is difficult to efficiently and accurately determine by the existing trial-and-error method and regional experience method is solved, and the cost of manpower and material resources is remarkably reduced.
2. The invention is a breakthrough of the design method of the mixing proportion of the raw materials of the water-heat curing product, and has important significance in the fields of novel building materials and resource utilization of waste materials.
Drawings
FIG. 1 is a flow chart of the design of the proportions of the raw materials of the hydrothermal curing body;
FIG. 2 is a flow chart of a method for measuring the content of active calcium and active silicon in a raw material;
FIG. 3 is an electron micrograph of a hydrothermally cured product of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1
The method of the invention comprises the following steps, as shown in fig. 1 and 2:
step S1, drying engineering slag soil in a baking oven at 100 ℃ to constant weight, crushing the engineering slag soil by using a rubber hammer, sieving, and controlling the particle size of the sieved engineering slag soil particles to be smaller than 0.15mm;
step S2, quantitatively measuring the content of active calcium and the content of active silicon in each raw material particle:
mixing and shaking 1 part of the sieved engineering residue soil particles and 10 parts of 100g/L sodium hydroxide solution in a digestion tank according to mass fraction to obtain a raw material mixed solution, sealing the digestion tank storing the raw material mixed solution, placing the sealed digestion tank in a microwave digestion instrument for digestion treatment, setting the temperature in the microwave digestion instrument to be 200 ℃, and obtaining a digestion solution after digestion for 1 hour; and after digestion is finished, transferring the obtained digestion solution into 100 parts of 0.6mol/L dilute hydrochloric acid solution, heating the digestion solution to boiling, cooling to room temperature after keeping for 15 minutes, diluting to 12500 parts by deionized water, filtering out solid particles in the diluted solution by using a 0.45 mu m filter head, and finally testing the calcium content and the silicon content in the processed raw material mixed solution by using an inductively coupled plasma emission spectrometry.
In addition, the calcium carbonate content in the raw materials is measured by utilizing a precise concrete carbonization measuring instrument, the calcium content obtained by subtracting the contribution of calcium carbonate from the calcium content measured by an inductively coupled plasma emission spectrometry is the final active calcium content, and the silicon content measured by inductive coupling is the active silicon content.
S3, adding calcium hydroxide into the crushed and sieved engineering slag soil particles to obtain a mixture, wherein the molar ratio of active calcium to active silicon in the mixture is 0.83;
and S4, preparing the water content of the mixture to the optimal water content, placing the mixture into a block mold, preparing a compacted block by a hydrostatic press method, controlling the compactness of the compacted block to be 90%, aging the block for 5 days, placing the block into a high-temperature high-pressure reaction kettle for hydrothermal curing reaction, wherein the temperature in the kettle is 200 ℃, the vapor pressure is 1.55MPa, the reaction time is 12 hours, obtaining a hydrothermal sample, and drying the hydrothermal sample to constant weight at 60 ℃ to obtain the final finished block.
Example 2
Step S1, drying engineering slag soil in a baking oven at 100 ℃ to constant weight, crushing the engineering slag soil by using a rubber hammer, sieving, and controlling the particle size of the sieved engineering slag soil particles to be smaller than 0.15mm;
step S2, quantitatively measuring the content of active calcium and the content of active silicon in each raw material particle:
mixing and shaking 1 part of the sieved engineering residue soil particles and 10 parts of 100g/L sodium hydroxide solution in a digestion tank according to mass fraction to obtain a raw material mixed solution, sealing the digestion tank storing the raw material mixed solution, placing the sealed digestion tank in a microwave digestion instrument for digestion treatment, setting the temperature in the microwave digestion instrument to be 200 ℃, and obtaining a digestion solution after digestion for 1 hour; and after digestion is finished, transferring the obtained digestion solution into 100 parts of 0.6mol/L dilute hydrochloric acid solution, heating the digestion solution to boiling, cooling to room temperature after keeping for 15 minutes, diluting to 12500 parts by deionized water, filtering out solid particles in the diluted solution by using a 0.45 mu m filter head, and finally testing the calcium content and the silicon content in the processed raw material mixed solution by using an inductively coupled plasma emission spectrometry.
And then, measuring the calcium carbonate content in the raw material by using a precise concrete carbonization measuring instrument, wherein the calcium content obtained by subtracting the calcium content contributed by the calcium carbonate from the calcium content measured by an inductively coupled plasma emission spectrometry is the final active calcium content, and the silicon content measured by inductive coupling is the active silicon content.
S3, adding calcium hydroxide into the crushed and sieved engineering slag soil particles to obtain a mixture, wherein the molar ratio of active calcium to active silicon in the mixture is 0.83;
and S4, preparing the water content of the mixture to the optimal water content, placing the mixture into a block mold, preparing a compacted block by a hydrostatic press method, controlling the compactness of the compacted block to be 90%, aging the block for 5 days, placing the block into a high-temperature high-pressure reaction kettle for hydrothermal curing reaction, wherein the temperature in the kettle is 200 ℃, the vapor pressure is 1.55MPa, the reaction time is 18 hours, obtaining a hydrothermal sample, and drying the hydrothermal sample to constant weight at 60 ℃ to obtain the final finished block.
Example 3
Step S1, drying engineering slag soil in a baking oven at 100 ℃ to constant weight, crushing the engineering slag soil by using a rubber hammer, sieving, and controlling the particle size of the sieved engineering slag soil particles to be smaller than 0.15mm;
step S2, quantitatively measuring the content of active calcium and the content of active silicon in each raw material particle:
mixing 1 part of engineering residue soil particles after sieving and 10 parts of 100g/L sodium hydroxide solution in a digestion tank according to mass fraction, shaking uniformly to obtain raw material mixed solution, sealing the digestion tank storing the raw material mixed solution, placing the sealed digestion tank in a microwave digestion instrument for digestion treatment, setting the temperature in the microwave digestion instrument to 220 ℃, and obtaining digestion solution after digestion for 0.5 h; and after digestion is finished, transferring the obtained digestion solution into 100 parts of 0.6mol/L dilute hydrochloric acid solution, heating the digestion solution to boiling, cooling to room temperature after keeping for 15 minutes, diluting to 12500 parts by deionized water, filtering out solid particles in the diluted solution by using a 0.45 mu m filter head, and finally testing the calcium content and the silicon content in the processed raw material mixed solution by using an inductively coupled plasma emission spectrometry.
And then, measuring the calcium carbonate content in the raw material by using a precise concrete carbonization measuring instrument, wherein the calcium content obtained by subtracting the calcium content contributed by the calcium carbonate from the calcium content measured by an inductively coupled plasma emission spectrometry is the final active calcium content, and the silicon content measured by inductive coupling is the active silicon content.
S3, adding calcium hydroxide into the crushed and sieved engineering slag soil particles to obtain a mixture, wherein the molar ratio of active calcium to active silicon in the mixture is 0.83;
and S4, preparing the water content of the mixture to the optimal water content, placing the mixture into a block mold, preparing a compacted block by a hydrostatic press, controlling the compactness of the compacted block to be 90%, aging the block for 5 days, placing the block into a high-temperature high-pressure reaction kettle for hydrothermal curing reaction, wherein the temperature in the kettle is 220 ℃, the vapor pressure is 2.32MPa, the reaction time is 12 hours, obtaining a hydrothermal sample, drying the hydrothermal sample to constant weight at 60 ℃, and obtaining a finished block, wherein an electron microscopic image of the block is shown as 3.
Example 4
Step S1, drying engineering slag soil in a baking oven at 100 ℃ to constant weight, crushing the engineering slag soil by using a rubber hammer, sieving, and controlling the particle size of the sieved engineering slag soil particles to be smaller than 0.15mm;
step S2, quantitatively measuring the content of active calcium and the content of active silicon in each raw material particle:
mixing 1 part of engineering residue soil particles after sieving and 10 parts of 100g/L sodium hydroxide solution in a digestion tank according to mass fraction, shaking uniformly to obtain raw material mixed solution, sealing the digestion tank storing the raw material mixed solution, placing the sealed digestion tank in a microwave digestion instrument for digestion treatment, setting the temperature in the microwave digestion instrument to 220 ℃, and obtaining digestion solution after digestion for 0.5 h; and after digestion is finished, transferring the obtained digestion solution into 100 parts of 0.6mol/L dilute hydrochloric acid solution, heating the digestion solution to boiling, keeping the temperature for 15 minutes, cooling to room temperature, diluting the solution to 12500 parts by deionized water, filtering solid particles in the diluted solution by using a 0.45 mu m filter head, and finally testing the calcium content and the silicon content with hydrothermal reactivity in the raw material mixed solution after treatment by using an inductively coupled plasma emission spectrometry.
And then, measuring the calcium carbonate content in the raw material by using a precise concrete carbonization measuring instrument, wherein the calcium content obtained by subtracting the calcium content contributed by the calcium carbonate from the calcium content measured by an inductively coupled plasma emission spectrometry is the final active calcium content, and the silicon content measured by inductive coupling is the active silicon content.
S3, adding calcium hydroxide into the crushed and sieved engineering slag soil particles to obtain a mixture, wherein the molar ratio of active calcium to active silicon in the mixture is 0.83;
and S4, preparing the water content of the mixture to the optimal water content, placing the mixture into a block mold, preparing a compacted block by a hydrostatic press method, controlling the compactness of the compacted block to be 95%, aging the block for 5 days, placing the block into a high-temperature high-pressure reaction kettle for hydrothermal curing reaction, wherein the temperature in the kettle is 220 ℃, the vapor pressure is 2.32MPa, the reaction time is 12 hours, obtaining a hydrothermal sample, and drying the hydrothermal sample to constant weight at 60 ℃ to obtain the finished block.
Comparative example 1
Comparative example 1 was identical to example 3, except that the molar ratio of active calcium to active silicon was 0.16.
Comparative example 2
Comparative example 2 was identical to example 3, except that the molar ratio of active calcium to active silicon was 0.49.
Comparative example 3
Comparative example 3 was identical to example 4, except that the degree of compaction of the block was 80%.
The strength of the blocks prepared in examples 1 to 4 and comparative examples 1 to 3 was measured, and the measurement results are shown in table 1.
TABLE 1
From the data in the table, the relative content of the calcium element and the silicon element has obvious influence on the mechanical property of the hydrothermal curing product, and the active calcium silicon molar ratio index provided by the invention can be used as a key control index for the raw material proportioning design. Fig. 1 and 2 are a flow chart of a raw material proportion design of a water-heat curing product and a flow chart of a method for measuring the content of active calcium and active silicon in the raw material respectively, and compared with other proportion designs, the raw material proportion determined by the method has more excellent mechanical properties. The method can more efficiently and accurately determine the optimal proportion of the raw materials of the water-heating curing product, reduces the consumption of a large amount of manpower and material resources, is simple to operate, and has wide application prospect in actual engineering production.
Meanwhile, more tobermorite exists in the hydrothermal curing product in the electron microscope image shown in fig. 3, which further proves that the generation and growth of the tobermorite structure are main reasons for improving the mechanical properties of the hydrothermal curing product.
Claims (10)
1. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon, comprising the steps of:
step S1, drying, grinding and sieving a plurality of raw materials respectively, and sieving the raw materials to obtain raw material particles with the particle size smaller than 0.15mm respectively;
s2, quantitatively measuring the content of active calcium and the content of active silicon in each raw material particle;
s3, pouring all raw material particles into a container according to a certain proportion, and uniformly mixing to obtain a uniform mixture;
and S4, adding tap water into the uniform mixture, blending the water content of the mixture to the optimal water content, preparing the mixture into a block sample by a pressing mode, performing a hydrothermal curing reaction on the block sample at the temperature of 100-250 ℃ for 0-24 h, and finally preparing the hydrothermal curing body finished product.
2. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon according to claim 1, characterized in that: the raw materials comprise one or more of engineering dregs, industrial solid waste, construction waste and raw material regulator.
3. A method for preparing a high strength hydrothermally curable body with relative amounts of activated calcium and activated silicon according to claim 1, characterized by: in the step S2, the active calcium is specifically calcium element which can participate in hydrothermal reaction under the alkaline environment, the temperature of 100-250 ℃ and the pressure of 0.1-4 MPa; the active silicon is specifically silicon element which can participate in hydrothermal reaction under the alkaline environment and the temperature condition of 100-250 ℃ and the pressure condition of 0.1-4 MPa.
4. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon according to claim 1, characterized in that: the step S2 specifically comprises the following steps:
the raw material particles and the alkaline solution are mixed according to a liquid-solid ratio of 10:1, mixing to obtain a raw material mixed solution, then carrying out digestion, acid washing, dilution and filtration treatment on the raw material mixed solution, and finally measuring the calcium content and the silicon content with hydrothermal reactivity in the raw material mixed solution by utilizing an inductively coupled plasma emission spectrometry.
5. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon according to claim 1, characterized in that: in the step S3, the molar ratio between the active calcium and the active silicon in the mixture obtained by mixing the raw material particles is 0.83.
6. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon according to claim 1, characterized in that: in the step S3, the pH value of the leachate of the mixture is not lower than 11.
7. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon according to claim 2, characterized in that: the engineering slag soil comprises one or more of foundation pit excavation soil, shield slag soil and dehydrated mud cakes; the industrial solid waste comprises one or more of fly ash, slag, fly ash, steel slag, coal gangue, red mud and carbide slag; the construction waste comprises one or more of concrete, brick aggregate, ceramic and glass; the raw material regulator comprises one or more of lime, calcium hydroxide, quartz sand and sodium hydroxide.
8. The method for producing a hydrothermally curable body based on the relative contents of active calcium and active silicon according to claim 4, wherein: the alkaline solution in the step S2 is sodium hydroxide solution, and the concentration of the alkaline solution is not lower than 100g/L.
9. The method for producing a hydrothermally curable body based on the relative contents of active calcium and active silicon according to claim 4, wherein: in the step S2, the specific steps of digestion, acid washing and dilution treatment are as follows:
firstly, sealing the raw material mixed solution in a reaction kettle or a microwave digestion instrument for digestion treatment to obtain digestion solution; then, adding dilute hydrochloric acid solution into the digestion solution, heating the digestion solution to boiling, keeping for 15-20 minutes, cooling to room temperature, and finally adding enough deionized water to dilute the solution.
10. A method for preparing a hydrothermally curable body based on the relative content of active calcium and active silicon according to claim 9, characterized in that: in the step S2, the temperature in the reaction kettle and the microwave digestion instrument is 100-250 ℃, and the digestion treatment time is 0-2 h; the concentration of the dilute hydrochloric acid solution added in the pickling treatment process is 0.5 mol/L-0.7 mol/L.
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