CN104478256A - Calcium-magnesium carbonate gel material and preparation method thereof - Google Patents
Calcium-magnesium carbonate gel material and preparation method thereof Download PDFInfo
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- CN104478256A CN104478256A CN201410660848.7A CN201410660848A CN104478256A CN 104478256 A CN104478256 A CN 104478256A CN 201410660848 A CN201410660848 A CN 201410660848A CN 104478256 A CN104478256 A CN 104478256A
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- slag
- cement
- calcium carbonate
- preparation
- magnesium
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- 239000000463 material Substances 0.000 title claims abstract description 29
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004568 cement Substances 0.000 claims abstract description 39
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims description 44
- 239000010881 fly ash Substances 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 9
- 238000012423 maintenance Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003500 flue dust Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 5
- 239000005431 greenhouse gas Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000004567 concrete Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000005255 carburizing Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- NEKPCAYWQWRBHN-UHFFFAOYSA-L magnesium;carbonate;trihydrate Chemical compound O.O.O.[Mg+2].[O-]C([O-])=O NEKPCAYWQWRBHN-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000003469 silicate cement Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical class [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a calcium-magnesium carbonate gel material and a preparation method thereof. The gel material is prepared from the following components in percentage by mass: not smaller than 60% and not greater than 100% of industrial alkaline wastes, not smaller than 0 and not greater than 20% of cement and not smaller than 0 and not greater than 20% of active magnesium oxide through CO2 carbonization. According to the calcium-magnesium carbonate gel material and the preparation method thereof disclosed by the invention, a great deal of solid wastes is utilized, so that the calcium-magnesium carbonate gel material is environmentally friendly, low in cost, excellent in breaking strength and compressive strength; and the greenhouse gas CO2 is recycled to promote the energy conservation and emission reduction in the building material industry.
Description
Technical field
The invention belongs to building material technical field, be specifically related to a kind of magnesium calcium carbonate gelling material and preparation method thereof.
Background technology
Reduce CO
2greenhouse 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 CO
2quantity discharged is large, often produces 1t cement clinker and about discharges 0.7-0.8tCO
2.Cement industry CO
2quantity discharged accounts for mankind's activity and produces CO
2the 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 CO
2the situation reduced discharging is severeer.Along with the sustainable development of economic society, future will continue to increase the demand of cement concrete, how reduce Cement industry CO
2discharge has caused countries in the world to pay attention to.Application and Development green, environmental protection, energy-saving cement, promote that the Sustainable development of cement concrete material of construction is extremely urgent.Development of new cement and other low-carbon (LC) gelling material are Cement industry CO
2the effective way reduced discharging.
In fact, cement concrete material, can with the CO in air in long service process
2there is carburizing reagent, thus decrease 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 utilized
2curing concrete, can not only Quick high strength to form calcium carbonate, and can absorption portion CO
2, be conducive to reducing CO
2discharge.Even directly use CO
2carbonization trade waste can prepare the building material made with good mechanical properties.
Chinese invention CN101058213 proposes calcic solid waste carbonating and prepares material of construction, but limits the low waste of calcium component content as the application of flyash.Chinese invention CN103771780 adopts solid waste (slag, slag, flyash, coal gangue etc.) and alkaline excitation material (carbide slag, silicate cement or waste cement) to mix, and recarbonizes and prepare material of construction after prehydration.Chinese invention CN101423354 adopts paper mill sludge, slag, slag and discarded concrete as main raw, mixes 2-10%NaHCO
3, the agent of water glass equal excitation, accelerated carbonation temperature is 20-150 DEG C, and the accelerated carbonation time is 2-18h.Univ cambridge uk researchist uses the mixture of extra light calcined magnesia or activated magnesia and flyash, under normal temperature condition, and CO
2concentration is accelerated carbonation reactive magnesium oxide cements under 5%-20% condition, prepares the building material made that intensity is higher, but the required time is 28d.
Summary of the invention
The technical problem solved: the invention provides a kind of magnesium calcium carbonate gelling material and preparation method thereof, recycling greenhouse gases CO
2, and product folding strength and ultimate compression strength excellence.
Technical scheme: magnesium calcium carbonate gelling material, described gelling material by industrial alkaline waste residue, activated magnesia and cement through CO
2carbonization 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 20m
2/ 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 gelling material, industrial alkaline waste residue, activated magnesia and cement are through CO
2carbonization, wherein CO during carbonization
2concentration is 15%-99.9%, and pressure is 0.1-3.0MPa, and carbonization temperature is 20-60 DEG C, CO
2the 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 CO
2concentration was 99.9%, and pressure is 0.5MPa, and carbonization temperature is 30 DEG C, through reaction in 24 hours.
Know-why: in conjunction with more industrial residue, develop intensity more fast, the present invention adopts high-concentration industrial CO
2and improve CO
2pressure, accelerates CO
2rapid diffusion in test specimen, accelerated carbonation also improves carbonizing degree.The technical scheme adopted adopts activated magnesia, alkaline industrial residue, cement etc. as starting material, the industrial CO that employing pressure is 0.1-3.0MPa, concentration is 15%-99.9%
2carry out maintenance, temperature is 20-60 DEG C, accelerated carbonation, obtains the novel gelled material using calcium carbonate, magnesium calcium carbonate and serial carbonic acid magnesium salts as main cementing component.
The alkaline industrial residue, the activated magnesia, on a small quantity cement that are rich in magnesium calcium are mixed with appropriate water, make the goods of definite shape, leave standstill 1-3 days, the demoulding, then puts into special carbonizing plant, passes into CO
2gas carries out maintenance, obtains magnesium calcium carbonate gelled material product.
Alkaline industrial residue involved in the present invention mainly comprises 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 contains:
CO
2(g)+H
2O(aq)→CO
3 2-(aq)+2H
+(aq) Eq(1)
Ca
2+(aq)+CO
3 2-(aq)→CaCO
3(s) Eq(2)
Ca
2+(aq)+Mg
2+(aq)+CO
3 2-(aq)→Ca
xMg
(1-x)CO
3(s) Eq(3)
Mg
2+(aq)+CO
3 2-(aq)+xH
2O(aq)→MgCO
3·xH
2O(s) Eq(4)
Principal feature of the present invention is, in the forming process of calcium carbonate, form magnesium calcium carbonate, change crystal morphology and bonding, make microtexture finer and close, gelling material mechanical strength is better.High pressure CO
2, make it spread faster.Simultaneously stability CO
2, prepare the carbonate gelatinous material of low-carbon (LC).
Beneficial effect: utilize that a large amount of solid waste, environmental protection, cost are low, product folding strength and ultimate compression strength excellent, recycling greenhouse gases CO
2, 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.The test specimen that this figure is flyash, prepared by activated magnesia and a small amount of cement, through 99.9% concentration C O
2after carbonized maintaining, in test specimen, form the SEM shape appearance figure of magnesium calcium carbonate product.As seen from the figure, define 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 CO
2after carbonized maintaining, define a large amount of magnesium calcium carbonate products, flyash is cemented together.Fig. 3 is activated magnesia, slag and a small amount of cement admixture, through CO
2after carbonized maintaining, define a large amount of magnesium calcium carbonate products and magnesium carbonate trihydrate product, formation imporosity cementing with slag.
Embodiment
Following examples further illustrate content of the present invention, 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 do the inventive method, step or condition and replacement, all belong to scope of the present invention.If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
Embodiment 1
Flyash, activated magnesia and cement is selected to be main 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 55m
2/ g.Cement is silicate cement, and specific surface area is 420m
2/ kg.Flyash takes from fuel-burning power plant, Nanjing, and CaO content is 4.8% (mass ratio).By above-mentioned three kinds of starting material Homogeneous phase mixing, add water, stir and make uniform slurry, build shaping 40 × 40 × 40mm test specimen.Adopt CO
2maintenance, CO
2concentration was 99.9%, and pressure is 1.5MPa, and carbonization temperature is 40 DEG C, through reaction in 3 hours.After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 11%, and test specimen folding strength is 4.9MPa, and ultimate compression strength is 45MPa.
Embodiment 2
Ground slag, activated magnesia (with embodiment 1) and cement (with embodiment 1) is selected to be main raw material.Ground slag specific surface area is 450m
2/ 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 starting material Homogeneous phase mixing, add water, stir and make uniform slurry, build shaping 40 × 40 × 40mm test specimen.Adopt CO
2maintenance, CO
2concentration was 99.9%, and pressure is 1.0MPa, and carbonization temperature is 40 DEG C, through reaction in 6 hours.
After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 13%, and test specimen folding strength is 5.3MPa, and ultimate compression strength is 51MPa.
Embodiment 3
Slag, activated magnesia (with embodiment 1) and cement (with embodiment 1) is selected to be main 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 starting material Homogeneous phase mixing, add water, stir and make uniform slurry, build shaping 40 × 40 × 40mm test specimen.Adopt CO
2maintenance, CO
2concentration was 99.9%, and pressure is 2.0MPa, and carbonization temperature is 50 DEG C, through reaction in 3 hours.
After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 16%, and test specimen folding strength is 5.9MPa, and ultimate compression strength is 57MPa.
Embodiment 4
Carbide slag and slag (with embodiment 3) is selected to be main 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 starting material Homogeneous phase mixing, add water, stir and make uniform slurry, build shaping 40 × 40 × 40mm test specimen.Adopt CO
2maintenance, CO
2concentration was 99.9%, and pressure is 0.5MPa, and carbonization temperature is 30 DEG C, through reaction in 24 hours.After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 19%, and test specimen folding strength is 6.7MPa, and ultimate compression strength is 65MPa.
Embodiment 5
Carbide slag (with embodiment 4), magnesium slag and cement flue Dust is selected to be main 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 starting material Homogeneous phase mixing, add water, stir and make uniform slurry, build shaping 40 × 40 × 40mm test specimen.Adopt CO
2maintenance, CO
2concentration was 20%, and pressure is 0.1MPa, and carbonization temperature is 30 DEG C, through reaction in 24 hours.After carburizing reagent, weight increases (i.e. absorbing carbon dioxide) about 20%, and test specimen folding strength is 6.3MPa, and ultimate compression strength is 60MPa.
Claims (6)
1. magnesium calcium carbonate gelling material, is characterized in that described gelling material by industrial alkaline waste residue, activated magnesia and cement through CO
2carbonization preparation and obtain, described component by mass percentage, 60%≤industrial alkaline waste residue≤100%, 0≤cement≤20%, 0≤activated magnesia≤20%.
2. magnesium calcium carbonate gelling material according to claim 1, is characterized in that described industrial alkaline waste residue is at least one in ground slag, carbide slag, slag, flyash, magnesium slag, cement flue Dust.
3. magnesium calcium carbonate gelling material according to claim 1, is characterized in that the specific surface area of described activated magnesia is not less than 20m
2/ kg, activity index is not more than 400 s, and grain diameter is less than 80 microns.
4. the preparation method of magnesium calcium carbonate gelling material described in claim 1, is characterized in that industrial alkaline waste residue, activated magnesia and cement are through CO
2carbonization, wherein CO during carbonization
2concentration is 15%-99.9%, and pressure is 0.1-3.0MPa, and carbonization temperature is 20-60 DEG C, CO
2the time of maintenance is 3h-14d.
5. the preparation method of magnesium calcium carbonate gelling material according to claim 4, is characterized in that industrial alkaline waste residue is carbide slag and slag, and by percentage to the quality, carbide slag accounts for 10%, slag accounts for 90%.
6. the preparation method of magnesium calcium carbonate gelling material according to claim 4, is characterized in that CO
2concentration was 99.9%, and pressure is 0.5 MPa, and carbonization temperature is 30 DEG C, through reaction in 24 hours.
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|---|---|---|---|
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Cited By (14)
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| CN107056202A (en) * | 2017-05-31 | 2017-08-18 | 盐城工学院 | Carbonization slag cement prepares accelerator and its application process of low-carbon binder materials |
| CN107324753A (en) * | 2017-04-10 | 2017-11-07 | 南京工业大学 | A kind of carbonate binder materials and preparation method thereof |
| CN109485360A (en) * | 2018-12-28 | 2019-03-19 | 西安交通大学 | A kind of building moulding material produced using magnesium-smelting silicothermic process waste residue as raw material and its method |
| 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 |
| CN110818356A (en) * | 2019-12-02 | 2020-02-21 | 武汉理工大学 | Preparation method of high-performance carbonized reinforced concrete |
| CN111892363A (en) * | 2020-07-28 | 2020-11-06 | 西安交通大学 | Magnesium slag cementing material and forming process method thereof |
| CN113321477A (en) * | 2021-06-16 | 2021-08-31 | 乌海市东孚水泥有限责任公司 | Carbonate building material and manufacturing method thereof |
| CN113929326A (en) * | 2021-11-25 | 2022-01-14 | 青岛海泰能源科学技术研究院 | Preparation method and preparation system of cement |
| CN113968750A (en) * | 2021-10-28 | 2022-01-25 | 山东汉博昱洲新材料有限公司 | Based on deposition method and CO2Artificial stone for driving consolidation and preparation method thereof |
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| CN115466093A (en) * | 2022-10-18 | 2022-12-13 | 江苏科技大学 | Method for carbonizing and curing heavy metal in fly ash based on EDTA (ethylene diamine tetraacetic acid) -calcium-silicon solid waste-light-burned magnesium oxide |
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| CN107324753A (en) * | 2017-04-10 | 2017-11-07 | 南京工业大学 | A kind of carbonate binder materials and preparation method thereof |
| CN107324753B (en) * | 2017-04-10 | 2020-01-17 | 南京工业大学 | Carbonate cementing material and preparation method thereof |
| 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 |
| CN107056202A (en) * | 2017-05-31 | 2017-08-18 | 盐城工学院 | Carbonization slag cement prepares accelerator and its application process of low-carbon binder materials |
| 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 |
| CN109485360A (en) * | 2018-12-28 | 2019-03-19 | 西安交通大学 | A kind of building moulding material produced using magnesium-smelting silicothermic process waste residue as raw material and its method |
| 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 |
| CN110818356A (en) * | 2019-12-02 | 2020-02-21 | 武汉理工大学 | Preparation method of high-performance carbonized reinforced concrete |
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