CN106587673A - Green and environment-friendly type ecological cement - Google Patents
Green and environment-friendly type ecological cement Download PDFInfo
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- CN106587673A CN106587673A CN201611140077.4A CN201611140077A CN106587673A CN 106587673 A CN106587673 A CN 106587673A CN 201611140077 A CN201611140077 A CN 201611140077A CN 106587673 A CN106587673 A CN 106587673A
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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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
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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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
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- 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
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the field of energy conservation and environmental protection, and discloses green and environment-friendly type ecological cement, consisting of the following raw materials in percentage by weight: 20-30% of steel slag powder, 2-8% of phosphogypsum, 2-5% of alkali residues, 10-20% of red mud, 10-20% of zeolite powder, 2-4% of aluminum sulfate residues, 0.2-0.5% of condensed aluminum phosphate, 1-2% of a heavy metal ion curing agent, 1-2% of an excitant, 0.02-0.1% of an organic modifier, and the balance of mineral powder. The main raw materials of the green and environment-friendly type ecological cement are industrial waste residues, so that the ecological cement achieves an effect of turning wastes into treasures, and has good economic and environmental protection benefits.
Description
Technical field
The invention belongs to energy-conserving and environment-protective field, and in particular to a kind of environmental type eco-cement.
Technical background
The process of production grog is that cement industry consumes resource and the most important part that discharges pollutants, and not only needs to consume
The natural resources such as substantial amounts of lime stone, clay, coal and the energy, will also discharge substantial amounts of CO2、SO2、NOXDeng pernicious gas, institute
To reduce the important channel that cement clinker consumption is cement industry energy-saving and emission-reduction.Eco-cement is exactly using various discarded objects, bag
Various industrial wastes, waste residue and domestic waste etc. are included as raw material, fuel making cement.This is to develop a circular economy,
Ensure the Major Strategic measure of National environment security.Current eco-cement, refers mainly to cement with little clinker, usually by slag powders
It is prepared under the collective effect of the alkali-activator such as gypsum and calcium oxide, waterglass with flyash, there are two sides
The problem in face, one is the introducing of a large amount of calcium oxide, easily causes clinker-free cement stability bad, and two is with the valency of all kinds of alkali
Lattice go up, and the production cost of this kind of cement is also higher.
Red mud is that aluminium industry extracts the contaminative waste residue discharged during aluminum oxide, and average often produces 1 ton of aluminum oxide, attached
Band produces 1.0～2.0 tons of red muds.China is up to 30,000,000 tons as alumina producing big country of the world, the red mud of annual discharge.Greatly
The red mud of amount sufficiently effective can not be utilized, and can only be stacked by large-area stockyard, occupy a large amount of soils, and also environment is made
Into serious pollution.The waste residue that ardealite ardealite is discharged when being wet method manufacture phosphoric acid in phosphorous chemical industry, often produces 1 ton of phosphoric acid
(with P2O5Meter) produce about 4.5～5.5 tons of by-product ardealite, about 76,000,000 tons annual of yield of current China's ardealite, together
When China ardealite history for also having about 2.5 hundred million tons store up.The accumulation of substantial amounts of ardealite both land occupation, wastes money again
Source, wherein the material such as the titanium pigment for containing, soluble fluoride is easily polluted to surrounding enviroment.At the same time, slag, alkali
The industrial residues such as slag, aluminium sulfate slag there is also land occupation, the problem of pollution environment.
The content of the invention
It is an object of the invention to provide a kind of environmental type with variety classes industrial residue as primary raw material is ecological
Cement, to reach above-mentioned purpose, the present invention is employed the following technical solutions：
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：
Steel-making slag powder：20%-30%
Ardealite：2%-8%
Alkaline residue：2%-5%
Red mud：10%-20%
Zeolite powder：10%-20%
Aluminium sulfate slag：2%-4%
Condensation of aluminum phosphate：0.2%-0.5%
Heavy metal ion curing agent：1%-2%
Exciting agent：1%-2%
Organic modifiers：0.02%-0.1%
Balance of breeze.
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg。
Ardealite water content≤10%, SO3Content >=40%.
The alkaline residue refers to the alkaline scrap material discharged in ammonia-soda process alkali producing process, and composition is mainly calcium carbonate.
The zeolite powder is to be milled to specific surface area 500m by natural zeolite powder2/kg-600m2What/kg was obtained, the zeolite is
Refer to clinoptilolite or modenite.
The aluminium sulfate slag is to produce the waste residue that aluminum sulfate is discharged using bauxite.
The heavy metal ion curing agent is according to 1-5 by vulcanized sodium, sodium carbonate and oxalic acid:1-5:1 mass ratio composition.
Preferably, the heavy metal ion curing agent is according to 3 by vulcanized sodium, sodium carbonate and oxalic acid:3:1 mass ratio group
Into.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 4-8:1-2:1 mass ratio
Composition.
Preferably, the exciting agent by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 6:2:1 matter
Amount is than composition.
The breeze meets GB/T18046-2008《For the ground granulated blast furnace slag in cement and concrete》Middle S95 levels
Breeze is required.
The organic modifiers press 2-6 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:
1 mass ratio composition.
Preferably, the organic modifiers are by γ-methacryloxypropyl trimethoxy silane and oleic acid triethanolamine
Amine presses 3:1 mass ratio composition.
Alkaline residue in the present invention on the one hand can be with the reacting generating complex CaSiO such as steel-making slag powder, ardealite3·CaCO3·Ca
(OH)2·nH2O, on the other hand alkaline matter therein can guarantee system basicity, provide condition for hydration reaction.Contain in red mud
Some β-C2S, unformed aluminosilicate have potential hydraulically active, and free alkali can provide certain basicity, it is ensured that system aquation
Reaction.Zeolite has many cavities and duct, by increasing capacitance it is possible to increase cement stability, the alkali-aggregate reaction of suppression eco-cement, also right
Heavy metal ion in solid waste has certain solidification.Aluminium sulfate slag main component is silica and three oxidations two
Chlorine, with cement performance is improved, digests free calcium oxide in steel slag, improves cement stability, improves the work of cement getting up early intensity
With.There is condensation of aluminum phosphate adhesive solidification to act on, improve system intensity, exciting agent can promotion system hydration reaction.It is organic to change
Property agent can in improvement system inorganic substances boundary condition, promote hydration reaction.
Beneficial effect of the present invention：The environmental type eco-cement of the present invention is mainly with slag, red mud, alkaline residue, aluminum sulfate
Slag, ardealite are raw material, and not only primary raw material utilizes industrial residue, and main exciting agent also utilizes industry byproduct, according to
The chemical compositions such as steel-making slag powder, slag powders, ardealite, red mud, aluminium sulfate slag, the different characteristics of mineral composition, learn from other's strong points to offset one's weaknesses, advantage
It is complementary, reasonably combined, the cooperative effect between additive and different mixing materials is made full use of, in the synergy of various raw materials
Under, produce environmental type eco-cement.
The hydraulicity of cement of the present invention is good, intensity is high.Production process is prepared and sinter leaching two procedures without raw material,
The consumption of the natural energy sources such as a large amount of clays, lime stone, coal and resource is saved, it is to avoid the powder produced during clinker burning
The discharge of dirt, CO2, SO2, NOX etc., and environmental pollution and the land seizure of industrial residue are solved the problems, such as, with good
Environmental benefit.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply to further illustrate the features and advantages of the invention rather than to patent requirements of the present invention
Limit.
The raw materials used chemical group member table 1 below of the present invention：
Table 1 is tested with the chemical composition analysis of all kinds of raw materials
| Raw material | SiO2 | Al2O3 | Fe2O3 | CaO | MgO | loss |
| Alkaline residue | 11.38 | 4.06 | 1.02 | 35.77 | 5.45 | 31.25 |
| Slag powders | 35.70 | 9.08 | 0.83 | 41.42 | 5.41 | -0.7 |
| Steel-making slag powder | 14.79 | 5.35 | 25.67 | 38.87 | 5.72 | 0.23 |
| Aluminium sulfate slag | 62.21 | 19.81 | 1.39 | 2.37 | 1.84 | 0.12 |
| Ardealite | 5.363 | 0.97 | 0.24 | 19.42 | 0.33 | 21.72 |
| Red mud | 19.6 | 8.26 | 8.92 | 38.79 | 1.41 | 16.23 |
Embodiment 1
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 20%, ardealite
2%th, alkaline residue 2%, red mud 10%, zeolite powder 10%, aluminium sulfate slag 2%, condensation of aluminum phosphate 0.2%, heavy metal ion curing agent
1%th, exciting agent 1%, organic modifiers 0.02%, balance of breeze；
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg；
Ardealite water content≤10%, SO3Content >=40%；
The zeolite powder is to specific surface area 500m by clinoptilolite grinding2/kg-600m2What/kg was obtained；
The heavy metal ion curing agent is according to 3 by vulcanized sodium, sodium carbonate and oxalic acid:3:1 mass ratio composition；
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 6:2:1 mass ratio group
Into.
The organic modifiers press 2 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Embodiment 2
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 30%, ardealite
8%th, alkaline residue 5%, red mud 20%, zeolite powder 20%, aluminium sulfate slag 4%, condensation of aluminum phosphate 0.5%, heavy metal ion curing agent
2%th, exciting agent 2%, organic modifiers 0.1%, balance of breeze；
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg；
Ardealite water content≤10%, SO3Content >=40%；
The zeolite powder is to specific surface area 500m by modenite grinding2/kg-600m2What/kg was obtained；
The heavy metal ion curing agent is according to 1 by vulcanized sodium, sodium carbonate and oxalic acid:5:1 mass ratio composition；
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 4:2:1 mass ratio group
Into.
The organic modifiers press 6 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Embodiment 3
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 25%, ardealite
5%th, alkaline residue 3%, red mud 15%, zeolite powder 15%, aluminium sulfate slag 3%, condensation of aluminum phosphate 0.3%, heavy metal ion curing agent
1.5%th, exciting agent 1.8%, organic modifiers 0.05%, balance of breeze；
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg；
Ardealite water content≤10%, SO3Content >=40%；
The zeolite powder is to be milled to specific surface area 500m by natural zeolite powder2/kg-600m2What/kg was obtained；
The heavy metal ion curing agent is according to 5 by vulcanized sodium, sodium carbonate and oxalic acid:1:1 mass ratio composition.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 8:1:1 mass ratio group
Into.
The organic modifiers press 3 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Embodiment 4
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 21%, ardealite
6%th, alkaline residue 4%, red mud 16%, zeolite powder 17%, aluminium sulfate slag 2.8%, the solidification of condensation of aluminum phosphate 0.4%, heavy metal ion
Agent 1.2%, exciting agent 1.3%, organic modifiers 0.08%, balance of breeze.
The heavy metal ion curing agent is according to 3 by vulcanized sodium, sodium carbonate and oxalic acid:3:1 mass ratio composition.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 6:2:1 mass ratio group
Into.
The organic modifiers press 5 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Embodiment 5
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 26%, ardealite
5%th, alkaline residue 4%, red mud 13%, zeolite powder 14%, aluminium sulfate slag 3.5%, the solidification of condensation of aluminum phosphate 0.45%, heavy metal ion
Agent 1.8%, exciting agent 1.2%, organic modifiers 0.04%, balance of breeze.
The heavy metal ion curing agent is according to 3 by vulcanized sodium, sodium carbonate and oxalic acid:2:1 mass ratio composition.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 5:2:1 mass ratio group
Into.
The organic modifiers press 4 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Comparative example 1
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 25%, ardealite
5%th, alkaline residue 3%, red mud 15%, zeolite powder 15%, aluminium sulfate slag 3%, heavy metal ion curing agent 1.5%, exciting agent
1.8%th, organic modifiers 0.05%, balance of breeze；
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg；
Ardealite water content≤10%, SO3Content >=40%；
The zeolite powder is to be milled to specific surface area 500m by natural zeolite powder2/kg-600m2What/kg was obtained；
The heavy metal ion curing agent is according to 5 by vulcanized sodium, sodium carbonate and oxalic acid:1:1 mass ratio composition.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 8:1:1 mass ratio group
Into.
The organic modifiers press 3 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Comparative example 2
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 25%, ardealite
5%th, red mud 15%, zeolite powder 15%, aluminium sulfate slag 3%, condensation of aluminum phosphate 0.3%, heavy metal ion curing agent 1.5%, swash
Send out agent 1.8%, organic modifiers 0.05%, balance of breeze；
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg；
Ardealite water content≤10%, SO3Content >=40%；
The zeolite powder is to be milled to specific surface area 500m by natural zeolite powder2/kg-600m2What/kg was obtained；
The heavy metal ion curing agent is according to 5 by vulcanized sodium, sodium carbonate and oxalic acid:1:1 mass ratio composition.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 8:1:1 mass ratio group
Into.
The organic modifiers press 3 by γ-methacryloxypropyl trimethoxy silane and triethanolamine oleate:1
Mass ratio composition.
Comparative example 3
A kind of environmental type eco-cement, comprises the following raw materials by weight percent：Steel-making slag powder 25%, ardealite
5%th, alkaline residue 3%, red mud 15%, zeolite powder 15%, aluminium sulfate slag 3%, condensation of aluminum phosphate 0.3%, heavy metal ion curing agent
1.5%th, exciting agent 1.8%, balance of breeze；
The specific surface area of the steel-making slag powder is 400m2/kg-550m2/kg；
Ardealite water content≤10%, SO3Content >=40%；
The zeolite powder is to be milled to specific surface area 500m by natural zeolite powder2/kg-600m2What/kg was obtained；
The heavy metal ion curing agent is according to 5 by vulcanized sodium, sodium carbonate and oxalic acid:1:1 mass ratio composition.
The exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 8:1:1 mass ratio group
Into.
Performance test
The environmental type eco-cement obtained to embodiment 1-5 carries out performance test with comparative example 1-3, and cement standard is thick
Degree water consumption, setting time determine presses GB/T1346-2001《Cement normal consistency water consumption, setting time, stability inspection party
Method》Carry out；Strength of cement mortar is determined and presses GB/T17671-1999《Test method for strength of hydraulic cement mortar (ISO methods)》Carry out, knot
Fruit see the table below 2.
The environmental type eco-cement performance of table 2
The specific embodiment of the present invention is described above, but the present invention is not limited to above description.For this
For the technical staff in field, any is all at this to the equal modifications and substitutions that a kind of environmental type eco-cement is carried out
Among bright scope.Therefore, impartial conversion done without departing from the spirit and scope of the invention and modification, all should cover
Within the scope of the invention.
Claims (8)
1. a kind of environmental type eco-cement, it is characterised in that comprise the following raw materials by weight percent：Steel-making slag powder
20%-30%, ardealite 2%-8%, alkaline residue 2%-5%, red mud 10%-20%, zeolite powder 10%-20%, aluminium sulfate slag
It is 2%-4%, condensation of aluminum phosphate 0.2%-0.5%, heavy metal ion curing agent 1%-2%, exciting agent 1%-2%, organically-modified
The balance of breezes of agent 0.02%-0.1%；
The heavy metal ion curing agent is according to 1-5 by vulcanized sodium, sodium carbonate and oxalic acid:1-5:1 mass ratio composition；It is described
Exciting agent is by sodium thiosulfate, potassium permanganate, pentamethyl-diethylenetriamine according to 4-8:1-2:1 mass ratio composition.
2. environmental type eco-cement according to claim 1, it is characterised in that the alkaline residue refers to ammonia-soda process alkaline
During discharge alkaline scrap material.
3. environmental type eco-cement according to claim 1, it is characterised in that the zeolite powder is by natural zeolite
Grinding is to specific surface area 500m2/kg-600m2What/kg was obtained.
4. environmental type eco-cement according to claim 3, it is characterised in that the zeolite refer to clinoptilolite or
Person's modenite.
5. environmental type eco-cement according to claim 1, the heavy metal ion curing agent is by vulcanized sodium, carbon
Sour sodium and oxalic acid are according to 3:3:1 mass ratio composition.
6. environmental type eco-cement according to claim 1, it is characterised in that the exciting agent is by thiosulfuric acid
Sodium, potassium permanganate, pentamethyl-diethylenetriamine are according to 6:2:1 mass ratio composition.
7. environmental type eco-cement according to claim 1, it is characterised in that the organic modifiers are by γ-first
Base acryloxypropyl trimethoxy silane and triethanolamine oleate press 2-6:1 mass ratio composition.
8. environmental type eco-cement according to claim 1, it is characterised in that the organic modifiers are by γ-first
Base acryloxypropyl trimethoxy silane and triethanolamine oleate press 3:1 mass ratio composition.
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| CN201611140077.4A CN106587673A (en) | 2016-12-12 | 2016-12-12 | Green and environment-friendly type ecological cement |
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| CN201611140077.4A CN106587673A (en) | 2016-12-12 | 2016-12-12 | Green and environment-friendly type ecological cement |
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Family
ID=58598793
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164169A (en) * | 2018-01-23 | 2018-06-15 | 东南大学 | A kind of red mud-slag compound ground oligomer gel material for reinforcing soft foundation |
| CN114560672A (en) * | 2022-03-25 | 2022-05-31 | 贵州理工学院 | Preparation method of ultrahigh water material, ultrahigh water material and application |
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| CN102557566A (en) * | 2011-12-31 | 2012-07-11 | 中建商品混凝土成都有限公司 | Composite modified gypsum type high-performance ecological cement and preparation method thereof |
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| CN1094382A (en) * | 1993-04-24 | 1994-11-02 | 湖南省建筑材料研究设计院 | Slag alkali cement and manufacture method thereof |
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| CN114560672A (en) * | 2022-03-25 | 2022-05-31 | 贵州理工学院 | Preparation method of ultrahigh water material, ultrahigh water material and application |
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Application publication date: 20170426 |