CN105399353B - A kind of alkali-excited cement and preparation method thereof using discarded clay brick powder - Google Patents
A kind of alkali-excited cement and preparation method thereof using discarded clay brick powder Download PDFInfo
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- CN105399353B CN105399353B CN201510741635.1A CN201510741635A CN105399353B CN 105399353 B CN105399353 B CN 105399353B CN 201510741635 A CN201510741635 A CN 201510741635A CN 105399353 B CN105399353 B CN 105399353B
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- clay brick
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
Abstract
The invention discloses a kind of alkali-excited cements, including basic components and composite chemical additive；The basic components are made of the component of following mass percentage: discarded clay brick powder 10%~30%；High-calcium fly ass 70%~90%；The additional amount of the composite chemical additive accounts for the 10%~15% of the basic components quality, with the Na of introducing2O content meter.The invention also discloses a kind of preparation methods of above-mentioned alkali-excited cement: the discarded clay brick powder that mass percent is 10%~30% is mixed with the high-calcium fly ass that mass percent is 70%~90%, the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%~15% is added, the control of system water-solid ratio is 0.28~0.32, is mixed to get the alkali-excited cement.What the present invention utilized is trade waste high-calcium fly ass and discarded clay brick powder, provides approach to the utilization of waste, reduces costs.
Description
Technical field
The invention belongs to the technical fields of cement preparation, are related to a kind of alkali-excited cement and preparation method thereof.
Background technique
Cement is a kind of traditional cementitious material, is made that tremendous contribution for human economic development and social progress, however
The in short supply of portland cement raw material has been the global very urgent practical problem that must be faced, just will consumption in the middle of this century
To the greatest extent.In addition, portland cement not only consumes high-energy source, but also its production process is the process of a high carbon emission, produces 1 ton of water
Mud will discharge about 1 ton of greenhouse gases.Therefore, various countries launch respectively the development of corresponding measure limitation cement industry scale, together
When, since there is an urgent need to the green cementing materials of, various countries also successive Development of Novel for national economic development, to replace this tradition
Cementitious material cement, make cementitious material be unlikely to cause serious burden to environment while benefiting for the mankind.
Clay brick is as traditional construction material, although some areas at home have disabled or limited the use of, national each
Still there are mass production and use in ground, in particular with the quickening of urban construction and urban renewal, the Old building of some brick mix structures
Object generates largely discarded clay brick after removing, according to statistics, discard the quantum of output of clay brick substantially at annual 52000000 tons or so,
Therefore, how effectively to discard clay brick using these is a urgent problem.Flyash is thermal power plant discharge
One kind out is with sial industry byproduct as main component.Ordinary fly ash is bituminous coal as power fuel, is emitted
Calcium oxide be the very low Class F fly ash of content.With the rapid development of power industry and the exhaustion of coal resources, there is height
The lignite and ub-bituminous coal of volatile matter lead to a large amount of discharges of more and more high-calcium fly ass used also as power fuel, and by
It is high in its free calcium oxide content, it is difficult to be utilized effectively in cement-based material, form new pollution sources after accumulation, need
It is subject to treatment and use.Relative to Class F fly ash, in high-calcium fly ass in addition to containing a large amount of sa ingredient, also containing certain
Calcareous ingredient.
Geopolymer is one of alkali-excited cement.Geopolymer is to be gathered using silica-aluminum materials as raw material by mineral
Contracting reaction and generate a kind of low energy consumption, the long-life, without CO2The high-performance inorganic polymer of discharge.As the mankind protect environment
The progress for protecting reinforcement and the research work of consciousness prepares the raw material of geopolymer and has also widened from natural mineral raw as can benefit
Solid waste.The research of fly ash-based geopolymer concentrates on Class F fly ash at present, this contains relatively pure with it
Sa ingredient it is related.It is largely tiny nature of glass spherical particle in high-calcium fly ass, when high-calcium fly ass is chemical
When exciting agent excites, part aluminium silicon is mutually from the dissolution of the spherical shell of high-calcium fly ass and spot polymerization reaction, this and alkali-activated carbonatite low calcium
Flyash is similar.It is CaO, SiO that the main component of brick powder is discarded made of discarded clay brick grinding under demolishing buildings2、
Al2O3Deng partial size is thinner, has and is used to prepare the fundamental property of geopolymer.Utilize discarded clay brick powder, flyash
Geopolymer is prepared, the raw material sources of solid waste based geopolymer are on the one hand extended, has pushed the development in geopolymer field；Separately
On the one hand it solves waste and stacks occupied ground and pollution problem, create new way to preserve the ecological environment.
Summary of the invention
Aiming at the problem that how to efficiently use discarded clay brick powder in the prior art, the object of the present invention is to provide one kind with
Discarded clay brick powder (WBP) and high-calcium fly ass (CFA) are used as silicon and aluminum source raw material, are compound with sodium silicate and sodium hydroxide
Alkali-activator, a kind of alkali-excited cement for novel low carbon discharge being prepared.
It is a further object to provide a kind of preparation methods of above-mentioned alkali-excited cement.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of alkali-excited cement, including basic components and composite chemical additive；The basic components are by following quality
The component of percentage composition is made:
Discarded clay brick powder 10%~30%；
High-calcium fly ass 70%~90%；
The additional amount of the composite chemical additive accounts for the 10%~15% of the basic components quality, with the Na of introducing2O
Content meter.
The discarded clay brick powder is made of discarded clay brick through grinding, and specific surface area is 500~700m2/kg。
The high-calcium fly ass is fly ash in electric power plant, and II grades of ashes, specific surface area is 350~450m2/kg。
The modulus M of the composite chemical additive is 1.5~2.0, in which: that M is indicated is SiO2Molal quantity and Na2O's
The ratio of molal quantity.
The composite chemical additive is formulated by sodium silicate and sodium hydroxide.The initial modulus of sodium silicate is
2.32, solid content 42.7% adjusts sodium silicate using NaOH, to obtain certain modulus (M=n (SiO2)/n(Na2O))
Composite chemical additive.The addition content of NaOH is calculated by formula (1), and the sodium silicate indices for adjusting front and back are shown in Table 1.
G2=[80G1×N×(M1-M2)]/(62M2×P) (1)
In formula (1), G1To be taken sodium silicate quality, Na2O content is N；M1For the initial modulus of sodium silicate；M2It is compound
The preparation modulus of chemical admixture；P is NaOH purity；G2For the addition content of NaOH.
1 sodium silicate of table adjusts main component content before and after modulus
The water-solid ratio that the alkali-excited cement uses is 0.28~0.32, in which: the water in water-solid ratio includes sodium silicate
When water contained by solution and additional water, i.e. control system water-solid ratio are 0.28~0.32, except contained by sodium silicate solution
Other than water, insufficient part is supplied by additional water；Consolidating in water-solid ratio refers to discarded clay brick powder and high-calcium fly ass
Quality sum.
A kind of preparation method of above-mentioned alkali-excited cement, comprising the following steps:
The high calcium for being 70%~90% with mass percent by the discarded clay brick powder that mass percent is 10%~30%
Flyash mixing, is added the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%~15%,
With the Na of introducing2O content meter, the control of system water-solid ratio are 0.28~0.32, are mixed to get the alkali-excited cement.
Due to the adoption of the above technical scheme, the invention has the advantages that and advantage:
The present invention makes the system using discarded clay brick powder and high-calcium fly ass as primary raw material in certain care environments
With preferable performance, it can partially replace in a certain range or be used better than cement.
What the present invention utilized is trade waste high-calcium fly ass and discarded clay brick powder, is provided to the utilization of waste
Approach alleviates the burden of environment, reduces costs, reduces resource consumption, meets energy-saving and emission-reduction and meets China's national situation
It is required that；Meanwhile it is a kind of clinker-free cement, has saved energy consumption；This novel geopolymer only has a small amount of greenhouse gases
Discharge, be a kind of cementitious material of the environment-friendly type of low-carbon emission.It, can be in addition, it can replace cement to a certain extent
The production of cement is reduced, that is, reduces high resource, the energy consumption in cement production process, high carbon emission decreases
Its immense pressure caused by environment.So the alkali-excited cement of this low-carbon emission is a kind of gelling material of environmental type
Material meets the trend of current social development, with good economic efficiency and social benefit.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
Percentage used in the embodiment of the present invention is mass percent.
Main raw material(s) in test of the embodiment of the present invention: discarded clay brick powder is the discarded clay brick warp under demolishing buildings
Grinding is made, specific surface area 608m2/kg；High-calcium fly ass is derived from certain power plant, II grades of ashes, specific surface area 410m2/kg.It is useless
The main component for abandoning clay brick powder and high-calcium fly ass is as shown in table 2.
Sodium hydroxide used is the NaOH that purity is 99.2% in test；Sodium silicate solid content is 38.3%, is contained
9.1% Na2O, 29.2% SiO2With 61.7% water.
Table 2
| Raw material | SiO2 | A12O3 | Fe2O3 | MgO | CaO | K2O | Na2O | L.O.I. | Total |
| High-calcium fly ass | 50.30 | 22.00 | 7.10 | 1.85 | 11.33 | 3.42 | 1.28 | 1.72 | 98.97 |
| Discarded clay brick powder | 42.80 | 10.30 | 6.91 | 3.36 | 26.30 | 2.11 | 1.34 | 6.58 | 99.70 |
Embodiment 1
The percentage of raw material used is as follows: discarded brick powder: volume 20%；High-calcium fly ass: volume 80%；(discarded brick
100%) powder and high-calcium fly ass quality sum are
Composite chemical additive modulus: 1.5；Composite chemical admixture dosage (is mixed) outside: 10%；
Water-solid ratio: 0.30；
The discarded clay brick powder that mass percent is 20% is mixed with the high-calcium fly ass that mass percent is 80%, is added
Enter the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%；System water-solid ratio is 0.30,
In water include water contained by sodium silicate solution and additional water two parts composition, i.e., control system water-solid ratio be 0.30,
In addition to the water contained by the sodium silicate solution, insufficient part is supplied by additional water；Mixing, molding, demoulding, it is wet to support to survey
Determine age, detects the performance of the alkali-excited cement.
Wherein: composite chemical additive is mixed by sodium silicate and sodium hydroxide, by sodium silicate and sodium hydroxide
Mixing, control its modulus M be 1.5 (M indicate be SiO2Molal quantity and Na2The ratio of the molal quantity of O), it is prepared compound
Chemical admixture.Sodium silicate solid content is 38.3%, contains 9.1% Na2O, 29.2% SiO2With 61.7% water；Hydrogen
Sodium oxide molybdena is the sodium hydroxide that purity is 99.2%.
Embodiment 2
The percentage of raw material used is as follows: discarded brick powder: volume 30%；High-calcium fly ass: volume 70%；(discarded brick
100%) powder and high-calcium fly ass quality sum are
Composite chemical additive modulus: 1.5；Composite chemical admixture dosage (is mixed) outside: 10%；
Water-solid ratio: 0.28；
The discarded clay brick powder that mass percent is 30% is mixed with the high-calcium fly ass that mass percent is 70%, is added
Enter the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%；System water-solid ratio is 0.28,
In water include water contained by sodium silicate solution and additional water two parts composition, i.e., control system water-solid ratio be 0.28,
In addition to the water contained by the sodium silicate solution, insufficient part is supplied by additional water；Mixing, molding, demoulding, it is wet to support to survey
Determine age, detects the performance of the alkali-excited cement.
Wherein: composite chemical additive is mixed by sodium silicate and sodium hydroxide, by sodium silicate and sodium hydroxide
Mixing, control its modulus M be 1.5 (M indicate be SiO2Molal quantity and Na2The ratio of the molal quantity of O), it is prepared compound
Chemical admixture.Sodium silicate solid content is 38.3%, contains 9.1% Na2O, 29.2% SiO2With 61.7% water；Hydrogen
Sodium oxide molybdena is the sodium hydroxide that purity is 99.2%.
Embodiment 3
The percentage of raw material used is as follows: discarded brick powder: volume 30%；High-calcium fly ass: volume 70%；(discarded brick
100%) powder and high-calcium fly ass quality sum are
Composite chemical additive modulus: 1.5；Composite chemical admixture dosage (is mixed) outside: 10%；
Water-solid ratio: 0.30.
The discarded clay brick powder that mass percent is 30% is mixed with the high-calcium fly ass that mass percent is 70%, is added
Enter the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%；System water-solid ratio is 0.30,
In water include water contained by sodium silicate solution and additional water two parts composition, i.e., control system water-solid ratio be 0.30,
In addition to the water contained by the sodium silicate solution, insufficient part is supplied by additional water；Mixing, molding, demoulding, it is wet to support to survey
Determine age, detects the performance of the alkali-excited cement.
Wherein: composite chemical additive is mixed by sodium silicate and sodium hydroxide, by sodium silicate and sodium hydroxide
Mixing, control its modulus M be 1.5 (M indicate be SiO2Molal quantity and Na2The ratio of the molal quantity of O), it is prepared compound
Chemical admixture.Sodium silicate solid content is 38.3%, contains 9.1% Na2O, 29.2% SiO2With 61.7% water；Hydrogen
Sodium oxide molybdena is the sodium hydroxide that purity is 99.2%.
Embodiment 4
The percentage of raw material used is as follows:
Discarded brick powder: volume 30%；High-calcium fly ass: volume 70%；(discarded brick powder and high-calcium fly ass quality sum are
100%)
Composite chemical additive modulus: 1.5；Composite chemical admixture dosage (is mixed) outside: 10%；
Water-solid ratio: 0.32.
The discarded clay brick powder that mass percent is 30% is mixed with the high-calcium fly ass that mass percent is 70%, is added
Enter the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%；System water-solid ratio is 0.32,
In water include water contained by sodium silicate solution and additional water two parts composition, i.e., control system water-solid ratio be 0.32,
In addition to the water contained by the sodium silicate solution, insufficient part is supplied by additional water；Mixing, molding, demoulding, it is wet to support to survey
Determine age, detects the performance of the alkali-excited cement.
Wherein: composite chemical additive is mixed by sodium silicate and sodium hydroxide, by sodium silicate and sodium hydroxide
Mixing, control its modulus M be 1.5 (M indicate be SiO2Molal quantity and Na2The ratio of the molal quantity of O), it is prepared compound
Chemical admixture.Sodium silicate solid content is 38.3%, contains 9.1% Na2O, 29.2% SiO2With 61.7% water；Hydrogen
Sodium oxide molybdena is the sodium hydroxide that purity is 99.2%.
Embodiment 5
The percentage of raw material used is as follows:
Discarded brick powder: volume 10%；High-calcium fly ass: volume 90%；(discarded brick powder and high-calcium fly ass quality sum are
100%)
Composite chemical additive modulus: 1.5；Composite chemical admixture dosage (is mixed) outside: 10%；
Water-solid ratio: 0.30；
The discarded clay brick powder that mass percent is 10% is mixed with the high-calcium fly ass that mass percent is 90%, is added
Enter the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%；System water-solid ratio is 0.30,
In water include water contained by sodium silicate solution and additional water two parts composition, i.e., control system water-solid ratio be 0.30,
In addition to the water contained by the sodium silicate solution, insufficient part is supplied by additional water；Mixing, molding, demoulding, it is wet to support to survey
Determine age, detects the performance of the alkali-excited cement.
Wherein: composite chemical additive is mixed by sodium silicate and sodium hydroxide, by sodium silicate and sodium hydroxide
Mixing, control its modulus M be 1.5 (M indicate be SiO2Molal quantity and Na2The ratio of the molal quantity of O), it is prepared compound
Chemical admixture.Sodium silicate solid content is 38.3%, contains 9.1% Na2O, 29.2% SiO2With 61.7% water；Hydrogen
Sodium oxide molybdena is the sodium hydroxide that purity is 99.2%.
The basic performance of the alkali-excited cement of Examples 1 to 5 preparation is as shown in table 3, each it can be seen from the data of table 3
Item performance indicator meets normal silicate in existing national standards " common portland cement " (GB 175-2007/XG1-2009)
The performance requirement of strength of cement grade 42.5 can replace ordinary portland cement to apply to Practical Project in a certain range.
Table 3
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (3)
1. a kind of alkali-excited cement, it is characterised in that: including basic components and composite chemical additive；The basic components be by
The component of following mass percentage is made:
Discarded clay brick powder 10%~30%；
High-calcium fly ass 70%~90%；
The ingredient of the discarded clay brick powder are as follows: 42.80% SiO2, 10.30% Al2O3, 6.91% Fe2O3, 3.36%
MgO, 26.30% CaO, 2.11% K2O, 1.34% Na2O, 6.58% loss on ignition；The discarded clay brick powder is to build
The discarded clay brick built under object is removed is made through grinding, specific surface area 608m2/kg；
The ingredient of the high-calcium fly ass are as follows: 50.30% SiO2, 22.00% Al2O3, 7.10% Fe2O3, 1.85%
MgO, 11.33% CaO, 3.42% K2O, 1.28% Na2O, 1.72% loss on ignition；The high-calcium fly ass is derived from power plant
II grade ash, specific surface area 410m2/kg；
The additional amount of the composite chemical additive accounts for the 10%~15% of the basic components quality, with the Na of introducing2O content
Meter；
The composite chemical additive is formulated by sodium silicate and NaOH；The addition content of NaOH is calculated by formula (1)；
G2=[80G1×N×(M1-M2)]/(62M2×P) (1)
In formula (1), G1To be taken sodium silicate quality, Na2O content is N；M1For the initial modulus of sodium silicate；M2For composite chemical
The preparation modulus of additive；P is the purity of NaOH；G2For the addition content of NaOH；The initial modulus of sodium silicate is 2.32, admittedly contain
Amount is 42.7%, and each component content is Na2O 13.15%, SiO229.58% and H2O 57.27%；
The water-solid ratio that the alkali-excited cement uses is 0.28~0.32, in which: the water in water-solid ratio includes sodium silicate solution
Contained water and additional water；Consolidating in water-solid ratio refers to the quality sum of discarded clay brick powder and high-calcium fly ass.
2. alkali-excited cement according to claim 1, it is characterised in that: the modulus M of the composite chemical additive is 1.5
~2.0, in which: that M is indicated is SiO2Molal quantity and Na2The ratio of the molal quantity of O.
3. a kind of preparation method of alkali-excited cement of any of claims 1 or 2, it is characterised in that: the following steps are included:
The high calcium fine coal for being 70%~90% with mass percent by the discarded clay brick powder that mass percent is 10%~30%
Ash mixing, is added the composite chemical additive for accounting for discarded clay brick powder and high-calcium fly ass quality sum 10%~15%, to draw
The Na entered2O content meter, water-solid ratio are 0.28~0.32, are mixed to get the alkali-excited cement.
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| CN106045393B (en) * | 2016-05-26 | 2018-05-25 | 甘肃德龙生态建材有限公司 | A kind of production equipment of eco-concrete |
| CN106045412B (en) * | 2016-05-26 | 2018-11-02 | 甘肃德龙生态建材有限公司 | A kind of eco-concrete |
| CN105948545A (en) * | 2016-05-26 | 2016-09-21 | 甘肃德龙生态建材有限公司 | Production technology of ecological concrete |
| CN107954640A (en) * | 2017-12-12 | 2018-04-24 | 安徽宇瑞环保建设有限公司 | A kind of method for preparing foam cement using discarded clay brick |
| CN108264283A (en) * | 2018-02-01 | 2018-07-10 | 济南大学 | A kind of discarded clay brick base polymers building block and preparation method thereof |
| CN108863131B (en) * | 2018-08-20 | 2021-04-06 | 沈阳建筑大学 | Preparation method of recycled aggregate enhancer based on waste clay brick powder |
| CN109516739A (en) * | 2018-12-17 | 2019-03-26 | 东南大学 | A kind of clay brick powder cement mortar of alkali-activated carbonatite |
| CN116283078B (en) * | 2023-01-19 | 2024-01-09 | 长安大学 | Clay brick powder-steel slag-fly ash base polymer material and preparation method thereof |
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