CN104478256B - Magnesium calcium carbonate Binder Materials and preparation method thereof - Google Patents
Magnesium calcium carbonate Binder Materials and preparation method thereof Download PDFInfo
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- CN104478256B CN104478256B CN201410660848.7A CN201410660848A CN104478256B CN 104478256 B CN104478256 B CN 104478256B CN 201410660848 A CN201410660848 A CN 201410660848A CN 104478256 B CN104478256 B CN 104478256B
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Abstract
Magnesium calcium carbonate Binder Materials and preparation method thereof, described Binder Materials by industrial alkaline waste residue, activated magnesia and cement through CO2Carbonization preparation and obtain, described component by mass percentage, 60%≤industrial alkaline waste residue≤100%, 0≤cement≤20%, 0≤activated magnesia≤20%.Utilize that a large amount of solid waste, environmental protection, cost be low, product rupture strength and comprcssive strength excellent, recycling greenhouse gases CO2, promote the energy-saving and emission-reduction of building material industry.
Description
Technical field
The invention belongs to building material technical field, be specifically related to a kind of magnesium calcium carbonate Binder Materials and preparation method thereof.
Background technology
Reduce CO2Greenhouse gas emission, containment global warming are the focuses that the world today pays close attention to.Cement is the main gelling component of preparation conventional concrete material, its production process CO2Discharge capacity is big, often produces 1t clinker and about discharges 0.7-0.8tCO2.Cement industry CO2Discharge capacity accounts for mankind's activity and produces CO2The 5%-7% of total amount.China's cement output in 2013, up to 2,400,000,000 tons, occupies the first in the world in continuous 27 years.Obviously, China cement industry CO2The situation reduced discharging is severeer.Along with the sustainable development of economic society, the following demand to cement concrete will continue to increase, and how reduce cement industry CO2Discharge has caused countries in the world to pay attention to.Exploitation application green, environmental protection, energy-saving cement, promote that cement concrete construction material sustainable development is extremely urgent.Development of new cement and other low-carbon (LC) Binder Materials are cement industry CO2The effective way reduced discharging.
It practice, cement concrete material is in long service process, it is possible to the CO in air2There is carburizing reagent, thus decreasing the carbon emission when prepared by concrete.But CO under field conditions (factors)2Concentration extremely low (being about 0.04%), reacts slower.Also high concentration CO is utilized2Curing concrete, to form calcium carbonate, can not only quickly improve intensity, and can absorption portion CO2, advantageously reduce CO2Discharge.Even directly use CO2Carbonization trade waste can prepare the building material with good mechanical properties.
Chinese invention CN101058213 proposes calcic solid waste carbonating and prepares construction material, but limits the application of calcium component content low garbage such as flyash.Chinese invention CN103771780 adopts solid waste (slag, slag, flyash, gangue etc.) and alkaline excitation material (carbide slag, portland cement or waste cement) mixing, recarbonizes and prepare construction material after prehydration.Chinese invention CN101423354 adopts paper mill sludge, slag, slag and discarded concrete as main material, mixes 2-10%NaHCO3, waterglass equal excitation agent, accelerated carbonation temperature is 20-150 DEG C, and the accelerated carbonation time is 2-18h.Univ cambridge uk's research worker uses the mixture of extra light calcined magnesia or activated magnesia and flyash, under normal temperature condition, and CO2Accelerated carbonation reactive magnesium oxide cements when concentration is 5%-20%, prepares the building material that intensity is higher, but the required time is 28d.
Summary of the invention
Solve the technical problem that: the present invention provides a kind of magnesium calcium carbonate Binder Materials and preparation method thereof, recycling greenhouse gases CO2, and product rupture strength and comprcssive strength are excellent.
Technical scheme: magnesium calcium carbonate Binder Materials, described Binder Materials by industrial alkaline waste residue, activated magnesia and cement through CO2Carbonization preparation and obtain, described component by mass percentage, 60%≤industrial alkaline waste residue≤100%, 0≤cement≤20%, 0≤activated magnesia≤20%.
Described industrial alkaline waste residue is at least one in ground slag, carbide slag, slag, flyash, magnesium slag, cement flue Dust.
The specific surface area of described activated magnesia is not less than 20m2/ kg, activity index is not more than 400s, and grain diameter is less than 80 microns.
The preparation method of above-mentioned magnesium calcium carbonate Binder Materials, industrial alkaline waste residue, activated magnesia and cement are through CO2Carbonization, wherein CO during carbonization2Concentration is 15%-99.9%, and pressure is 0.1-3.0MPa, and carburizing temperature is 20-60 DEG C, CO2The time of maintenance is 3h-14d.
Described industrial alkaline waste residue is carbide slag and slag, and by percentage to the quality, carbide slag accounts for 10%, slag accounts for 90%.
Described CO2Concentration is 99.9%, and pressure is 0.5MPa, and carburizing temperature is 30 DEG C, reacts through 24 hours.
Know-why: in conjunction with more industrial residue, more quickly developing intensity, the present invention adopts high-concentration industrial CO2And improve CO2Pressure, accelerates CO2Quickly spreading in test specimen, accelerated carbonation also improves carbonizing degree.Employed technical scheme comprise that employing activated magnesia, alkalescence industrial residue, cement etc. are as raw material, employing pressure is 0.1-3.0MPa, concentration is the industrial CO of 15%-99.9%2Carrying out maintenance, temperature is 20-60 DEG C, accelerated carbonation, obtains the novel gelled material using calcium carbonate, magnesium calcium carbonate and series carbonic acid magnesium salt as main cementing component.
Will be enriched in the alkaline industrial residue of magnesium calcium, activated magnesia, a small amount of cement mix with appropriate water, make the goods of definite shape, stand 1-3 days, the demoulding, are then placed in special carbonizing plant, pass into CO2Gas carries out maintenance, obtains magnesium calcium carbonate gelled material product.
Alkaline industrial residue involved in the present invention mainly includes at least one in ground slag, carbide slag, slag, flyash, magnesium slag, cement flue Dust etc..
The chemical reaction forming magnesium calcium carbonate in the present invention mainly has:
CO2(g)+H2O(aq)→CO3 2-(aq)+2H+(aq)Eq(1)
Ca2+(aq)+CO3 2-(aq)→CaCO3(s)Eq(2)
Ca2+(aq)+Mg2+(aq)+CO3 2-(aq)→CaxMg(1-x)CO3(s)Eq(3)
Mg2+(aq)+CO3 2-(aq)+xH2O(aq)→MgCO3·xH2O(s)Eq(4)
The present invention is mainly characterized by, and in the forming process of calcium carbonate, forms magnesium calcium carbonate, changes crystal morphology and bonding, make microstructure finer and close, and Binder Materials mechanical strength is better.High pressure CO2So that it is diffusion is faster.Absorb CO simultaneously2, prepare the carbonate gel rubber material of low-carbon (LC).
Beneficial effect: utilize that a large amount of solid waste, environmental protection, cost be low, product rupture strength and comprcssive strength excellent, recycling greenhouse gases CO2, promote the energy-saving and emission-reduction of building material industry.
Accompanying drawing explanation
Fig. 1 is the SEM figure of concrete example magnesium calcium carbonate product.This figure is test specimen prepared by flyash, activated magnesia and a small amount of cement, through 99.9% concentration C O2After carbonized maintaining, test specimen forms the SEM shape appearance figure of magnesium calcium carbonate product.As seen from the figure, defining a large amount of close-connected Spherical magnesium carbonate calcium product, between product, bonding closely, is conducive to the raising of mechanical strength.
Fig. 2 is magnesium calcium carbonate product backscattered electron figure；(MC: magnesium calcium carbonate, Fa: flyash, Br: magnesium hydroxide)；
Fig. 3 is magnesium calcium carbonate product backscattered electron figure；(S: slag, MC: magnesium calcium carbonate, N: magnesium carbonate trihydrate)；
Fig. 2 is activated magnesia, flyash and a small amount of cement admixture, through CO2After carbonized maintaining, define substantial amounts of magnesium calcium carbonate product, flyash is cemented together.Fig. 3 is activated magnesia, slag and a small amount of cement admixture, through CO2After carbonized maintaining, define substantial amounts of magnesium calcium carbonate product and magnesium carbonate trihydrate product, formation tight structure cementing with slag.
Detailed description of the invention
Following example further illustrate present disclosure, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the amendment that the inventive method, step or condition are made and replacement, belong to the scope of the present invention.If not specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Embodiment 1
Selecting flyash, activated magnesia and cement is primary raw material.By percentage to the quality, flyash accounts for 50%, activated magnesia accounts for 20%, cement accounts for 30%.The activity index of activated magnesia is 50s, and specific surface area is 55m2/ g.Cement is portland cement, and specific surface area is 420m2/ kg.Flyash takes from thermal power plant, Nanjing, and CaO content is 4.8% (mass ratio).By above-mentioned three kinds of raw material Homogeneous phase mixing, adding water, uniform slurry is made in stirring, builds molding 40 × 40 × 40mm test specimen.Adopt CO2Maintenance, CO2Concentration is 99.9%, and pressure is 1.5MPa, and carburizing temperature is 40 DEG C, reacts through 3 hours.After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 11%, and test specimen rupture strength is 4.9MPa, and comprcssive strength is 45MPa.
Embodiment 2
Selecting ground slag, activated magnesia (with embodiment 1) and cement (with embodiment 1) is primary raw material.Ground slag specific surface area is 450m2/ kg, CaO content is 36%, content of MgO is 12% (mass ratio).By percentage to the quality, slag accounts for 60%, activated magnesia accounts for 20%, cement accounts for 20%.By above-mentioned three kinds of raw material Homogeneous phase mixing, adding water, uniform slurry is made in stirring, builds molding 40 × 40 × 40mm test specimen.Adopt CO2Maintenance, CO2Concentration is 99.9%, and pressure is 1.0MPa, and carburizing temperature is 40 DEG C, reacts through 6 hours.
After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 13%, and test specimen rupture strength is 5.3MPa, and comprcssive strength is 51MPa.
Embodiment 3
Selecting slag, activated magnesia (with embodiment 1) and cement (with embodiment 1) is primary raw material.In slag, CaO content is 42%, and content of MgO is 11%.By percentage to the quality, slag accounts for 80%, activated magnesia accounts for 10%, cement accounts for 10%.By above-mentioned three kinds of raw material Homogeneous phase mixing, adding water, uniform slurry is made in stirring, builds molding 40 × 40 × 40mm test specimen.Adopt CO2Maintenance, CO2Concentration is 99.9%, and pressure is 2.0MPa, and carburizing temperature is 50 DEG C, reacts through 3 hours.
After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 16%, and test specimen rupture strength is 5.9MPa, and comprcssive strength is 57MPa.
Embodiment 4
Selecting carbide slag and slag (with embodiment 3) is primary raw material.In carbide slag, CaO content is 60% (mass ratio).By percentage to the quality, carbide slag accounts for 10%, slag accounts for 90%.By above-mentioned two kinds of raw material Homogeneous phase mixing, adding water, uniform slurry is made in stirring, builds molding 40 × 40 × 40mm test specimen.Adopt CO2Maintenance, CO2Concentration is 99.9%, and pressure is 0.5MPa, and carburizing temperature is 30 DEG C, reacts through 24 hours.After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 19%, and test specimen rupture strength is 6.7MPa, and comprcssive strength is 65MPa.
Embodiment 5
Selecting carbide slag (with embodiment 4), magnesium slag and cement flue Dust is primary raw material.In magnesium slag, CaO content is 43%, and content of MgO is 17% (mass ratio).In cement flue Dust, CaO content is 45%, and content of MgO is 2% (mass ratio).By percentage to the quality, carbide slag accounts for 20%, magnesium slag accounts for 60%, cement flue Dust accounts for 20%.By above-mentioned three kinds of raw material Homogeneous phase mixing, adding water, uniform slurry is made in stirring, builds molding 40 × 40 × 40mm test specimen.Adopt CO2Maintenance, CO2Concentration is 20%, and pressure is 0.1MPa, and carburizing temperature is 30 DEG C, reacts through 24 hours.After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 20%, and test specimen rupture strength is 6.3MPa, and comprcssive strength is 60MPa.
Claims (2)
1. the preparation method of magnesium calcium carbonate Binder Materials, it is characterised in that described Binder Materials by industrial alkaline waste residue, activated magnesia and cement through CO2Carbonization is prepared and is obtained, and described industrial alkaline waste residue is at least one in ground slag, carbide slag, slag, flyash, magnesium slag, cement flue Dust；The specific surface area of described activated magnesia is not less than 20m2/ kg, activity index is not more than 400s, and grain diameter is less than 80 microns；Described component by mass percentage, 60%≤industrial alkaline waste residue≤100%, 0≤cement≤20%, 0≤activated magnesia≤20%；Wherein CO during carbonization2Concentration is 15%-99.9%, and pressure is 0.1-3.0MPa, and carburizing temperature is 20-60 DEG C, CO2The time of maintenance is 3h-14d.
2. the preparation method of magnesium calcium carbonate Binder Materials according to claim 1, it is characterised in that described Binder Materials is industrial alkaline waste residue, and described industrial alkaline waste residue is carbide slag and slag, by percentage to the quality, carbide slag accounts for 10%, slag accounts for 90%；In slag, CaO content is 42%, and content of MgO is 11%；In carbide slag, CaO mass is 60% than content, during carbonization, and CO2Concentration is 99.9%, and pressure is 0.5MPa, and carburizing temperature is 30 DEG C, reacts through 24 hours.
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| CN107056202B (en) * | 2017-05-31 | 2019-11-08 | 盐城工学院 | Carbonization slag cement prepares the promotor and its application method of low-carbon cementitious material |
| CN109485360B (en) * | 2018-12-28 | 2020-11-10 | 西安交通大学 | Building forming material produced by taking waste residues generated in magnesium smelting by silicothermic process as raw materials and method thereof |
| CN109704698A (en) * | 2019-01-21 | 2019-05-03 | 北京科技大学 | A method of utilizing the standby low cost carbonization building materials of prepared from steel slag |
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| CN111892363B (en) * | 2020-07-28 | 2021-10-19 | 西安交通大学 | Magnesium slag cementing material and forming process method thereof |
| CN113321477B (en) * | 2021-06-16 | 2022-07-15 | 乌海市东孚水泥有限责任公司 | Carbonate building material and preparation method thereof |
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| CN115724643B (en) * | 2022-11-01 | 2024-02-20 | 辽宁科技大学 | High-fire-resistance magnesium phosphate cement-based material capable of controlling hydration reaction and prolonging setting time and preparation method thereof |
| CN116102272A (en) * | 2023-01-06 | 2023-05-12 | 湖北工业大学 | Green gel material capable of realizing carbon reduction and carbon fixation and preparation method thereof |
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| CN101058213A (en) * | 2007-06-01 | 2007-10-24 | 济南大学 | Method for preparing building material with carbonization maintenance waste |
| CN101357829A (en) * | 2008-08-28 | 2009-02-04 | 济南大学 | Strengthening agent for construction material prepared by carbonizing curing waste |
| CN101343155B (en) * | 2008-08-29 | 2011-07-27 | 济南大学 | Regeneration aggregate made of carbonized maintaining castoff |
| US9212093B2 (en) * | 2011-06-30 | 2015-12-15 | NTH Consultants, Ltd. | Hybrid magnesium cement and method of manufacture |
| CN103771780A (en) * | 2014-01-01 | 2014-05-07 | 大连理工大学 | Method for preparing building material products through hydration-carbonation coupling technique |
| CN104045251B (en) * | 2014-05-29 | 2016-06-29 | 湖南大学 | A kind of method of carbon dioxide intensifying regenerating aggregate |
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