CN113072311A - Steel slag auxiliary cementing material and preparation method and application thereof - Google Patents
Steel slag auxiliary cementing material and preparation method and application thereof Download PDFInfo
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- CN113072311A CN113072311A CN202110505789.6A CN202110505789A CN113072311A CN 113072311 A CN113072311 A CN 113072311A CN 202110505789 A CN202110505789 A CN 202110505789A CN 113072311 A CN113072311 A CN 113072311A
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- steel slag
- cementing material
- carbon dioxide
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- 239000002893 slag Substances 0.000 title claims abstract description 171
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 170
- 239000010959 steel Substances 0.000 title claims abstract description 170
- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 44
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 41
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229960001484 edetic acid Drugs 0.000 claims description 5
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000004035 construction material Substances 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 25
- 239000004567 concrete Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 13
- 239000004566 building material Substances 0.000 abstract description 6
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000010998 test method Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 239000012467 final product Substances 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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
- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/425—Acids or salts thereof
-
- 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
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/428—Organic materials
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
A steel slag auxiliary cementing material and a preparation method and application thereof are disclosed, (1) crushing and iron selecting original steel slag, and then placing the crushed and iron selected steel slag into a mill for grinding to obtain steel slag particles; (2) placing the steel slag particles into stirring pretreatment equipment, and mixing and uniformly stirring the steel slag and the additive solution; (3) placing the pretreated steel slag particles into a mill for grinding, and introducing carbon dioxide gas to grind the steel slag particles into steel slag micro powder with a certain granularity; (4) putting the steel slag micro powder into a stirring reaction device, and introducing carbon dioxide gas into the reaction device to obtain the stabilized and activated steel slag auxiliary cementing material. The invention can rapidly eliminate free CaO and partial free MgO, thereby solving the problem of poor stability of the steel slag, improving the gelling activity of the steel slag to a great extent, ensuring that the stability of the steel slag auxiliary gelling material is qualified when the steel slag auxiliary gelling material is mixed into cement or concrete, and promoting the application of the steel slag in building materials such as cement, concrete and the like.
Description
Technical Field
The invention belongs to the field of preparation methods of building materials, and particularly relates to a steel slag auxiliary cementing material capable of being rapidly stabilized and activated by carbon dioxide, and a preparation method and application thereof.
Background
The cement production consumes a large amount of resources and simultaneously discharges a large amount of carbon dioxide. The cement industry is the third largest carbon dioxide emission body in China, and the carbon emission accounts for about 14% of the total carbon emission of the industry in China. In 2020, the cement yield in China is up to 23.77 million tons, and about 13 million tons of carbon dioxide are discharged. The carbon emission reduction of the cement industry is related to the realization of the strategic targets of carbon peak reaching and carbon neutralization in China. Therefore, various energy-saving and emission-reducing strategies of the scholars are proposed and adopted in the academic world and the industrial world, such as reducing the using amount of cement in concrete, reducing the using amount of clinker in cement, reducing carbon emission in the production process of cement clinker, adopting novel biomass fuel, capturing, utilizing and storing carbon, and the like. Among them, replacing clinker in cement with more supplementary cementing materials to reduce the clinker content in cement is one of the effective ways to reduce carbon emission in cement industry. In particular, the method of replacing cement clinker with industrial solid waste is very effective, which not only consumes a large amount of solid waste, but also greatly reduces the emission of carbon dioxide, and in addition, the performance of cement-based materials can be improved by adding high-quality auxiliary cementing materials into cement. However, because of the huge production capacity of cement in China, the traditional high-quality auxiliary cementing materials such as slag, fly ash, silica fume and the like are gradually scarce, the requirement of low-carbon cement production is difficult to meet, and a new auxiliary cementing material needs to be found urgently.
Steel slag is a by-product of the steel industry, and the discharge amount of the steel slag accounts for about 15-20% of the total production amount of steel. The steel slag discharge amount per year in China is as high as more than 1 hundred million tons, the accumulated stock amount exceeds 10 hundred million tons, the utilization rate is less than 30 percent, cultivated land is occupied, and the environment is polluted, so a new technology for environment-friendly resource utilization of the steel slag is urgently needed in the steel industry.
The chemical composition of the steel slag is similar to that of silicate cement clinker, and the steel slag mainly comprises CaO and SiO2、Al2O3、MgO、Fe2O3And MnO and P2O5Etc., the mineral composition of which mainly comprises calcium silicate (C)3S、α-C2S、γ-C2S, CS), RO phase and a small amount of calcium aluminoferrite (C)4AF), free calcium oxide (f-CaO), free magnesium oxide (f-MgO), and the like. The great discharge amount of the steel slag and the chemical composition and physical characteristics of the steel slag are considered, and the steel slag is used for building materials with large quantity and wide range and is a main way for large-scale resource utilization of the steel slag. Therefore, a great deal of research is carried out at home and abroad, which mainly comprises the following steps: (1) used as roadbed filling. The steel slag is applied to roadbed filling in large quantity in developed regions and countries such as Europe, America, Japan and the likeAnd the utilization rate is higher. (2) It is used as concrete coarse and fine aggregate. The research has been carried out to partially replace natural sandstone aggregate with steel slag to prepare concrete, which improves the mechanical property of concrete, but when the replacement amount of the steel slag aggregate is too large, the stability is poor due to hydration and expansion of free CaO and MgO in the steel slag. In recent years, accidents of poor concrete stability and material structure damage caused by steel slag sandstone aggregate have been reported in China. (3) Used as auxiliary cementing material. Because mineral powder, fly ash and other high-quality auxiliary cementing materials are increasingly in short supply, more and more researches are carried out to grind steel slag into micro powder to replace the traditional high-quality auxiliary cementing materials to be used for concrete. The steel slag contains a small amount of C3S、C2S, etc. minerals having certain hydration and gelling properties, but in which the mineral phase of low hydration activity is such as gamma-C2S, RO phases are more, and the hydration gelling performance is poor. In addition, the components such as Fe and RO contained in the steel slag are difficult to grind, so that the steel slag is poor in grindability, and the grinding energy consumption is higher than that of limestone, fly ash, mineral powder and the like. In conclusion, the fundamental reasons restricting the use of steel slag as auxiliary cementitious material are the difficult grinding property of steel slag, low hydration activity and potential safety hazard.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a steel slag auxiliary cementing material and a preparation method and application thereof, wherein carbon dioxide with a certain concentration is utilized to rapidly eliminate free CaO and MgO under the catalysis of a specific additive, and the free CaO and MgO are subjected to carbonization reaction with calcium and magnesium-containing mineral phases in the steel slag to form active mineral phases, so that the stability of the steel slag is improved, the steel slag cementing property is improved, and the prepared steel slag auxiliary cementing material can be used as a cement mixing material and a concrete admixture.
The technical scheme is as follows: a preparation method of a steel slag auxiliary cementing material comprises the following steps: (1) crushing the undisturbed steel slag, and selecting iron to obtain steel slag particles with the granularity of 0.01-5 mm; (2) putting steel slag particles into stirring pretreatment equipment, mixing the steel slag particles with an additive solution, and uniformly stirring, wherein the additive solution is at least one of polyalcohol, ethylene glycol, diethanol monoisopropanolamine, phosphoric acid, polycarboxylic acid, sulfonic acid, ethylene diamine tetraacetic acid, sodium ethylene diamine tetracetate, sodium carbonate and sodium bicarbonate, and the mass ratio of the additive solution to the steel slag particles is 0.02-0.20; (3) placing the pretreated steel slag particles into a grinding machine for grinding, and introducing carbon dioxide gas to grind the steel slag particles until the granularity is not more than 0.10 mm; (4) and (3) placing the ground steel slag into a stirring reaction device, introducing carbon dioxide gas into the stirring reaction device again, and staying for 1-45min to obtain the stabilized and activated steel slag auxiliary cementing material.
The granularity of the steel slag particles after the crushing and iron selection is 0.02-0.6mm, and the granularity of the steel slag micro powder is 0.01-0.10 mm.
The mass concentration of the additive solution is not more than 30 percent.
The concentration of the carbon dioxide is 3-99.9%.
The reaction pressure is from normal pressure to 0.5 MPa.
The reaction time was 30 min.
Preferably, in the step (2), the mass ratio of the additive solution to the steel slag powder is 0.08, the mass concentration of the additive solution is 0.5%, the additive solution is composed of 99.5 parts of water, 0.1 part of polycarboxylic acid, 0.1 part of ethylene diamine tetraacetic acid, 0.1 part of sulfonic acid and 0.2 part of ethylene glycol, the gas in the step (3) is industrial tail gas with 20% of carbon dioxide concentration, the steel slag particles are ground to be less than 0.05mm in particle size, the gas in the step (4) is industrial tail gas with 20% of carbon dioxide concentration, the reaction pressure is normal pressure, and the reaction time is 30 min.
The steel slag auxiliary cementing material prepared by the method.
The steel slag auxiliary cementing material is applied to the preparation of building materials.
The preparation process is shown in figure 1.
The invention is mainly characterized in that under the acceleration action of the additive, carbon dioxide and slag mineral phases containing calcium and magnesium, free CaO and MgO are utilized to quickly carry out carbonization reaction to digest the free CaO and MgO and form active mineral phases, thereby improving the stability of the slag, improving the gelling activity of the slag and preparing the high-activity slag auxiliary gelling material which can be used as a cement admixture and a concrete admixture. Wide application range of carbon dioxide concentration, high reaction speed, good steel slag performance, capability of using normal-pressure and normal-temperature flue gas and simple process.
Has the advantages that: (1) under the catalytic action of the additive, free CaO and partial free MgO are quickly eliminated within 0.5 hour, and the free CaO is reduced to be below 0.2 percent, so that the problem of poor stability of the steel slag is thoroughly solved, the steel slag auxiliary cementing material is ensured to be qualified in stability when being doped into cement or concrete, and the application of the steel slag in building materials such as cement, concrete and the like is promoted. (2) The combined action of the carbonization treatment and the additive can obviously improve the reaction activity of the steel slag, the activity index can be improved by 22.8 percent in 28 days, the addition of the steel slag auxiliary cementing material in cement and concrete materials can be increased, and the addition can be improved by 15-30 percent. (3) Can absorb carbon dioxide, can possibly trap, solidify and store the carbon dioxide, has wide application range (3-99.9 percent) of carbon dioxide concentration, and can be directly suitable for various low-concentration carbon dioxide industrial flue gases. Normal pressure and normal temperature flue gas can be used. (4) Simple process, low cost, short treatment time and high efficiency, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a flow chart of a process for preparing a supplementary cementitious material using carbon dioxide to rapidly stabilize and activate steel slag;
FIG. 2 is a scanned image of backscattered electrons of a carbon dioxide treated steel slag supplementary cementitious material;
FIG. 3 is a transmission electron diagram of a carbon dioxide treated steel slag supplementary cementitious material.
Detailed Description
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claimsAmong them. The reference to normal temperature and pressure herein means: pressure of 10 ═ c5Pa; the temperature was 20 ℃.
Example 1
A steel slag auxiliary cementing material rapidly stabilized and activated by carbon dioxide and a preparation method thereof comprise the following steps:
(1) taking 1200g of steel slag particles (with the particle size of 0.02-0.6mm) after crushing and iron selection, and putting the steel slag particles into stirring pretreatment equipment;
(2) uniformly spraying 96g of water (namely the concentration of the additive solution is 0%) on the surface of the steel slag, and uniformly stirring;
(3) placing the pretreated steel slag particles into a grinding machine for grinding, and simultaneously introducing carbon dioxide gas with the concentration of 99% to grind the steel slag particles to be less than 0.10 mm;
(4) putting the steel slag micro powder into a stirring reaction device, introducing carbon dioxide gas with the concentration of 99 percent into the reaction device, and keeping the reaction device for 30min under normal pressure to obtain the stabilized and activated steel slag auxiliary cementing material.
Example 2
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the steps for preparing the finished product of the steel slag auxiliary cementing material in the embodiment and the embodiment 1 is that 240g of water is uniformly sprayed in the step (2), and the step (4) is kept for 45min under normal pressure.
Example 3
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the steps of preparing the finished product of the steel slag auxiliary cementing material in the embodiment and the embodiment 1 is that the gas in the steps (3) and (4) is industrial tail gas with the carbon dioxide concentration of about 20%.
Example 4
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the steps of the present example for preparing the steel slag supplementary cementitious material finished product and the example 1 is that the gas in the steps (3) and (4) is industrial tail gas with a carbon dioxide concentration of about 9.5%.
Example 5
The steel slag used in this example and the test method were the same as those in example 3.
The difference between the steps of preparing the finished product of the steel slag auxiliary cementing material in the embodiment and the embodiment 3 is that the pressure is increased to 0.25MPa and kept for 30min after the reaction equipment is sealed and stirred in the step (4).
Example 6
The steel slag used in this example and the test method were the same as those in example 3.
The difference between the step of preparing the finished product of the steel slag supplementary cementitious material in the embodiment and the embodiment 3 is that the steel slag particles in the step (3) are ground to be less than 0.05 mm.
Example 7
The steel slag used in this example and the test method were the same as those in example 6.
The difference between the step of preparing the steel slag supplementary cementitious material finished product in the embodiment and the embodiment 6 is that 96g of additive solution is uniformly sprayed on the surface of the steel slag in the step (2), the concentration of the additive solution is 0.5%, and the additive solution is composed of 99.5 parts of water, 0.1 part of polycarboxylic acid, 0.1 part of ethylene diamine tetraacetic acid, 0.1 part of sulfonic acid and 0.2 part of ethylene glycol.
Example 8
The procedure for preparing the final product of the steel slag supplementary cementitious material in this example is the same as that of example 7.
The steel slag auxiliary cementing material which is not processed by the method and is only ground, the steel slag auxiliary cementing material processed by the method and cement are mixed according to the mass ratio of 50:50 to form a mortar test piece.
Example 9
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the procedure for preparing the final product of the steel slag supplementary cementitious material in this example and that in the procedure of example 1 is that in the procedure (4), the steel slag supplementary cementitious material is maintained at normal pressure for 45 min.
Example 10
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the procedure of this example for preparing a final product of steel slag supplementary cementitious material and that of example 1 is that the procedure of step (4) is carried out under normal pressure for 16 min.
Example 11
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the step of preparing the finished product of the steel slag auxiliary cementing material in the embodiment and the step of preparing the finished product of the steel slag auxiliary cementing material in the embodiment 1 is that the grain diameter of steel slag particles in the step (1) is 0.6-4 mm. In the step (2), the concentration of the additive solution is 1%, and the additive solution consists of 99 parts of water, 0.7 part of sodium bicarbonate, 0.2 part of sodium ethylene diamine tetracetate and 0.1 part of diethanol monoisopropanolamine.
Example 12
The steel slag used in this example and the test method were the same as those in example 11.
The difference between the step of preparing the steel slag supplementary cementitious material finished product in the embodiment and the embodiment 11 is that in the step (2), the concentration of the additive solution is 10%, and the additive solution consists of 90 parts of water, 7 parts of sodium bicarbonate, 2 parts of sodium ethylene diamine tetracetate and 1 part of diethanol monoisopropanolamine.
Example 13
The steel slag used in this example was different from that of example 1 in that the initial free calcium oxide content was 1.25%. The procedure for preparing the final product of the steel slag supplementary cementitious material is the same as in example 1.
Example 14
The steel slag used in this example and the test method were the same as those of example 13.
The procedure for preparing a final product of the steel slag supplementary cementitious material in this example is different from that in example 13 in that step (4) is performed under normal pressure for 16 min.
Example 15
The steel slag used in this example and the test method were the same as those of example 13.
The procedure for preparing a final product of the steel slag supplementary cementitious material in this example is different from that in example 13 in that step (4) is performed under normal pressure for 45 min.
Example 16
The steel slag used in this example and the test method were the same as those in example 1.
The difference between the steps of preparing the steel slag auxiliary cementing material finished product in the embodiment and the embodiment 1 is that in the step (2), 36g of water is uniformly sprayed on the surface of the steel slag (namely, the concentration of the additive solution is 0%), and in the step (3) and the step (4), industrial tail gas with the carbon dioxide concentration of about 9.5% is introduced.
Example 17
The steel slag used in this example and the test method were the same as those in example 16.
The difference between the procedure for preparing the final product of steel slag supplementary cementitious material in this example and that in example 16 is that 60g of water is uniformly sprayed in step (2).
Example 18
The steel slag used in this example and the test method were the same as those in example 17.
The procedure for preparing a final product of a steel slag supplementary cementitious material in this example is different from that in example 17 in that the pressure in step (4) is increased to 0.45 MPa.
Example 19
The steel slag used in this example and the test method were the same as those in example 17.
The difference between the procedure for preparing the steel slag supplementary cementitious material of this example and that of example 17 is that the concentration of the admixture in step (2) is 0.5%, and the solution ratio of the admixture is the same as that in example 7.
Example 20
The steel slag used in this example and the test method were the same as those in example 17.
The step of preparing the steel slag auxiliary cementing material finished product in the embodiment is different from the embodiment 17 in that the concentration of the additive solution in the step (2) is 20%, the additive solution is composed of 80 parts of water, 14 parts of sodium bicarbonate, 4 parts of sodium ethylene diamine tetracetate and 2 parts of diethanol monoisopropanolamine, industrial tail gas with the carbon dioxide concentration of about 20% is introduced in the steps (3) and (4), and the reaction pressure is normal pressure.
Absorption of solidified CO in the samples of the examples2Amount of (A), Activity indexThe free calcium oxide content and stability were measured, and the results are shown in the following table. After the treatment of carbon dioxide, the steel slag absorbs and solidifies CO2，CO2The solidification absorption of the steel slag reaches 11.53 percent (accounting for the steel slag), and the f-CaO and the calcium silicate phase in the steel slag react with carbon dioxide to form a calcium carbonate product. Meanwhile, the components with poor stability caused by f-CaO and the like in the steel slag are rapidly reduced or even eliminated, the content of free CaO is lower than 0.2 percent, and the stability of the steel slag can be ensured. The steel slag auxiliary cementing material treated by the method has better activity than the untreated steel slag at all ages and mixing amounts. The content of free calcium oxide in the steel slag after being treated by the carbon dioxide gas is greatly reduced, and the reduction range is larger along with the increase of the treatment time and the particle fineness. In addition, the additive can obviously improve the CO content of the steel slag2The solidified amount is absorbed, the content of free calcium oxide is greatly reduced, and the activity index of the steel slag is improved, which shows that the additive can accelerate the stabilization and activation of the steel slag. Fig. 2 is a back-scattered electron scan of the steel slag supplementary cementitious material treated with carbon dioxide in example 1, which shows that more carbonized products are formed around the steel slag after carbonization, and fig. 3 is a transmission electron scan of the steel slag supplementary cementitious material treated with carbon dioxide in example 3, which shows that more amorphous products are formed after carbonization of the steel slag, and these products are beneficial to improvement of hydration activity.
The activity index refers to GB/T20491-2017 steel slag powder for cement and concrete
The method for preparing the auxiliary cementing material by rapidly stabilizing and activating the steel slag by using the carbon dioxide under the acceleration action of the additive in the embodiment can rapidly improve the problems of poor stability and poor cementing activity of the steel slag, so that the steel slag can be used as the auxiliary cementing material to be applied to the cement and concrete industries, and the method is favorable for solving the problems of large discharge of the steel slag, low utilization rate and environmental pollution. In addition, the method canRapid and permanent absorption of solidified CO2The carbon dioxide is efficiently captured, stored and utilized, and the carbon emission of the steel and building material industry is reduced. The method has the advantages of simple operation, low cost and high efficiency.
Claims (9)
1. A preparation method of a steel slag auxiliary cementing material is characterized by comprising the following steps: (1) crushing the undisturbed steel slag, and selecting iron to obtain steel slag particles with the granularity of 0.01-5 mm; (2) putting steel slag particles into stirring pretreatment equipment, mixing the steel slag particles with an additive solution, and uniformly stirring, wherein the additive solution is at least one of polyalcohol, ethylene glycol, diethanol monoisopropanolamine, phosphoric acid, polycarboxylic acid, sulfonic acid, ethylene diamine tetraacetic acid, sodium ethylene diamine tetracetate, sodium carbonate and sodium bicarbonate, and the mass ratio of the additive solution to the steel slag particles is 0.02-0.20; (3) placing the pretreated steel slag particles into a grinding machine for grinding, and introducing carbon dioxide gas to grind the steel slag particles until the granularity is not more than 0.10 mm; (4) and (3) placing the ground steel slag into a stirring reaction device, introducing carbon dioxide gas into the stirring reaction device again, and staying for 1-45min to obtain the stabilized and activated steel slag auxiliary cementing material.
2. The preparation method of the steel slag auxiliary cementing material of claim 1, wherein the granularity of the steel slag particles after the crushing and iron selection is 0.02-0.6mm, and the granularity of the steel slag micro powder is 0.01-0.10 mm.
3. The method for preparing the steel slag auxiliary cementing material of claim 1, wherein the mass concentration of the additive solution is not more than 30 percent.
4. The method for preparing the steel slag auxiliary cementing material of claim 1, wherein the concentration of the carbon dioxide is 3 to 99.9 percent.
5. The method for preparing the steel slag auxiliary cementing material of claim 1, wherein the reaction pressure is between normal pressure and 0.5 MPa.
6. The method for preparing the steel slag auxiliary cementing material of claim 1, wherein the reaction time is 30 min.
7. The method for preparing the steel slag auxiliary cementing material according to the claim 1, characterized in that, preferably, the mass ratio of the additive solution to the steel slag powder in the step (2) is 0.08, the mass concentration of the additive solution is 0.5%, the additive solution is composed of 99.5 parts of water, 0.1 part of polycarboxylic acid, 0.1 part of ethylene diamine tetraacetic acid, 0.1 part of sulfonic acid and 0.2 part of ethylene glycol, the gas in the step (3) is industrial tail gas with 20% of carbon dioxide concentration, the steel slag particles are ground to have a particle size of less than 0.05mm, the gas in the step (4) is industrial tail gas with 20% of carbon dioxide concentration, the reaction pressure is normal pressure, and the reaction time is 30 min.
8. The steel slag auxiliary cementing material prepared by the method of any one of claims 1 to 7.
9. The use of the steel slag supplementary cementitious material of claim 8 in the preparation of construction materials.
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