CN102557508A - Composite activating agent for calcium raw material-high-silicon-aluminum industrial residue system - Google Patents
Composite activating agent for calcium raw material-high-silicon-aluminum industrial residue system Download PDFInfo
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- CN102557508A CN102557508A CN2011104538965A CN201110453896A CN102557508A CN 102557508 A CN102557508 A CN 102557508A CN 2011104538965 A CN2011104538965 A CN 2011104538965A CN 201110453896 A CN201110453896 A CN 201110453896A CN 102557508 A CN102557508 A CN 102557508A
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- raw material
- sodium
- activating agent
- industrial residue
- acvator
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Abstract
The invention relates to an activating agent used in the fields of building materials and road materials, in particular to a composite activating agent for a calcium raw material-high-silicon-aluminum industrial residue system. The composite activating agent for the calcium raw material-high-silicon-aluminum industrial residue system is characterized by being prepared by mixing the following components in percentage by mass: 5-85 percent of sulfate of sodium, 0.5-75 percent of a hydroxide of sodium, 0.5-80 percent of sodium silicate and 5-15 percent of sodium aluminate or sodium metaaluminate. The activating agent has the characteristics of high activating efficiency, wide application range, environmental friendliness and low cost.
Description
Technical field
The present invention relates to the acvator in material of construction and the pavement material field, be specifically related to a kind of composite activating agent that is used for calcareous raw material-Gao sial industrial residue system.
Background technology
Calcareous raw material is meant those can provide capacity reaction calcium ion under the situation that has water to exist material, comprises unslaked lime, white lime, carbide slag etc.
High sial industrial residue is meant that those are rich in SiO
2, Al
2O
3The solid industrial residue, particularly those dominance pozzolanic activities are not high, but can dissolve the industrial residue of silicon, aluminium under certain condition, such as flyash inferior, blast-furnace slag, slag, phosphorus slag, chromium slag etc.
Calcareous raw material-Gao sial industrial residue system is meant by containing the quicklime material and high sial industrial residue mixes compsn and the hardened product thereof that constitutes according to a certain ratio.
Calcareous raw material-Gao sial industrial residue system has obtained using comparatively widely at material of construction and pavement material field.Many non-burning brick, building block and dry-mix like building material field all are made up of this system; The pavement material field has corresponding national regulation with lime-flyash as the roadbed binder.Calcareous raw material-Gao sial industrial residue system can be as the principle of material of construction and pavement material: the Ca that provides of calcareous raw material under certain condition
2+SiO with stripping in the high sial industrial residue
2, Al
2O
3Water generation reaction Calucium Silicate powder, drated calcium aluminate etc., thus make whole system sclerosis produce intensity.Because the SiO in most waste residues
2, Al
2O
3Dissolution rate is slower, makes calcareous raw material-Gao sial industrial residue system in application, exist strength development slow, particularly early strength shortcoming on the low side.For improving early strength, people have taked multiple measure, and adding acvator is one of method wherein.The acvator role increases SiO in the high sial industrial residue through chemical process exactly
2, Al
2O
3Dissolution rate and stripping quantity, thereby reach the purpose of raising system early strength.CN201010110505 (a kind of activator that is used for material of construction) discloses a kind of acvator that is used to activate flyash, slag, and how form by sodium sulfonate, acetonformaldehyde condensate sulfonates, Starso, sodium sulfate and salt of wormwood by butyl for this acvator; CN200910237542 discloses a kind of slag composite exciting agent, and has used it for the concrete preparation; CN200810197295 discloses the enhancing anti-fissuring agent of a kind of lime, flyash class material, this acvator by tricalcium silicate content greater than 55% silicate mineral powder, gypsum (or phosphogypsum) with contain SO
3The basic metal material is formed; CN96116121 discloses a kind of activated slag agent of being made up of the plaster of Paris and ripe alunite, and uses it for the early strength that improves slag cement; This external CN02113380 (high performance mineral concrete additive); CN200310109275 (a kind of concrete is used complex mineral blending material); CN200410010073 (novel masonry dry powder); CN200410014380 (heat-insulating mortar dry powder material and preparation method); CN200410018187 (heat preservation mortar for outer wall of buildings); CN200510020423 (heat insulating material for external surface of wall); CN200710024410 (a kind of calcination-free porous heat-insulation brick); CN200710190065 (a kind of catalytic gluing carbide slag brick); CN200810061627 (a kind of technology) with waste residue of smelting chromium irons brickmaking; All related to acvator in the CN01127324 patents such as (light porous building-brick and complete processings thereof).
Summary of the invention
The object of the present invention is to provide a kind of composite activating agent that is used for calcareous raw material-Gao sial industrial residue system, the early strength of adding the system of this acvator obviously increases.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: be used for the composite activating agent of calcareous raw material-Gao sial industrial residue system, it is characterized in that: it is formed by the mass percent mix by following component:
The vitriol of sodium (be called for short: component A): 5%～85%, can be any one industrial raw material that Sodium sulfate anhydrous.min(99), saltcake, SODIUM SULPHATE ANHYDROUS 99PCT etc. contain the sodium sulfate composition, but being sulphate content with sodium in these industrial raw material, its metering is as the criterion;
The oxyhydroxide of sodium (be called for short: B component): 0.5～75%, can be any one industrial raw material that sheet alkali, caustic alkali etc. contain the sodium hydroxide composition, but being oxyhydroxide content with sodium in these industrial raw material, its metering is as the criterion;
Water glass (be called for short: component C): 0.5～80%, can nine water water glass, anhydrous sodium metasilicate etc. contains any one industrial raw material of water glass composition, but being content with these industrial raw material mesosilicic acid sodium, its metering is as the criterion;
Sodium aluminate or sodium metaaluminate (be called for short: component D): 5%～15%, be industrial sodium aluminate or sodium metaaluminate, its metering is as the criterion with sodium aluminate content.
The above-mentioned production technique that is used for the composite activating agent of calcareous raw material-Gao sial industrial residue system is: according to the set of dispense ratio; Each raw material in the accurate weighing acvator; Its adding is had in the mixing machine of whipping appts, stir the composite activating agent that just obtained being used for calcareous raw material-Gao sial industrial residue system in 30-80 minute.
If raw material has caking, agglomeration earlier they to be pulverized remix.Because of said acvator is easy to make moist, should seal preservation.In order to guarantee the homogeneity of acvator, during use the water-soluble calcareous raw material-Gao sial industrial residue system that adds again of acvator is mixed and stirred.The addition of acvator is counted the 1%-4% of calcareous raw material-Gao sial industrial residue system by quality.
The present invention has following beneficial effect:
1) activation efficiency is high: in each of said activator formed, sodium hydroxide can significantly improve system basicity, but promotes oxidn silicon and aluminum oxide dissolve fast, thereby the raising early strength; Sodium sulfate is met the SO of water generates
4 2-Can generate ettringite with the aluminum oxide of dissolving generation and the quicklime reaction of adding rapidly, significantly improve the system early strength; When the aluminum oxide of early stage stripping in the system or silicon oxide were not enough, water glass and sodium aluminate in the acvator can be used as compensation, increase the ettringite growing amount, thereby guarantee early strength, and composition has guaranteed high activation efficiency from the inherence for all these.In addition,, often mix and stir inhomogeneously, have a strong impact on activation effect because the acvator addition is few.But acvator according to the invention is soluble in water, with adding after its dissolving, can realize the uniform mixing of acvator and other material of system during use again, has guaranteed high activation efficiency from external technology.
2) applied range: can see from the composition of said acvator; No matter be applied to the system that aluminum oxide is easier to stripping; Or silicon oxide is easier to the system of stripping; Or both all can receive the system of activation stripping can reach the purpose that improves getting up early intensity, therefore have the advantage of applied range.
3) environmental friendliness, with low cost: said acvator is inorganic industrial raw material and forms; The various ions that can produce in peripheral soil and water body environment, have; As long as the heavy metal content of the industrial raw material that uses is qualified; Can not bring extra mineral ion after the use, more can not cause Organic pollutants to environment.Compare the inorganic raw material price with organic raw material relatively low, thereby guaranteed the with low cost of said acvator.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
In order to characterize the activation effect of acvator, 7 days ultimate compression strength after the present invention does not add activator and adds activator with system are as evaluation index, and concrete evaluation method is following:
1) prepares acvator according to aforementioned acvator production technique, with calcareous raw material and the oven dry of high sial industrial residue;
2) weighing Ca raw material, high sial industrial residue, water and prepared acvator according to a certain ratio;
3) acvator is dissolved in certain water gaging, calcareous raw material and the dry mixing of high sial industrial residue is even, add and dissolved the water of acvator and continued uniform mixing, obtain compound;
4) with the 20MPa forming pressure above-mentioned compound is pressed into the cylindrical sample of φ 50mm * 50mm, the sample of each proportioning of moulding is no less than 3 at least; At 20 ℃ ± 2 ℃, under relative humidity >=95% condition with moulding sample maintenance 7 days; Take out the back in room temperature held 1 day, carry out intensity test then, loading rate is got 1mm/min during test.The last test result representes with the MV of 3 above samples;
5) according to step 3)-4) preparation, the test control samples.Control samples is not except that adding the acvator, and all proportionings are consistent with test specimens.The control samples of same proportioning is quite a few in 3, and the last test value is represented with their MV.
6) intensity and the comparison sample intensity of acvator sample is added in contrast, has played activation if intensity has improved then explanation, and it is high more to improve many more activation efficiencies.
Below all embodiment all adopt the aforesaid method evaluation, but the calcareous raw material that each embodiment was directed against-Gao sial industrial residue system is different, or the acvator proportioning is different, or volume is different.
Embodiment 1-4:
Embodiment 1-4 is to carbide slag-flyash system inferior.Carbide slag is the industrial residue (calcareous raw material) that produces when producing acetylene with calcium carbide, and effective CaO content only has 54wt%; Flyash inferior is the outer red flyash (being high sial industrial residue) such as grade that coal fired power generation produced.
In embodiment 1-4; The mass ratio of carbide slag and flyash inferior is 40: 60; Amount of water is 9.5% of carbide slag and a flyash total mass inferior, and 7 days ultimate compression strength that do not add the acvator control samples are 5.5MPa, and 7 days intensity of the proportioning of acvator, addition and sample are listed in the table below 1:
Table 1
In the table 1, component A is a Sodium sulfate anhydrous.min(99); B component is a sheet alkali; Component C is nine water water glass; Component D is an industrial sodium aluminate.According to the set of dispense ratio, accurately each raw material in the weighing acvator has its adding in the mixing machine of whipping appts, stirs the composite activating agent that just obtained being used for calcareous raw material-Gao sial industrial residue system in 30-80 minute.
In the table 1, the composite activating agent volume is the 1-4% of carbide slag, flyash inferior and water total mass.Composite activating agent with mix with carbide slag, flyash inferior again after water mixes, stir, obtain calcareous raw material-Gao sial industrial residue system (carbide slag-flyash system inferior).
Data can be seen from table 1; 7 days intensity of sample are significantly improved behind the interpolation acvator; Minimumly improved 82%, the highlyest be doubled manyly, shown that the disclosed acvator of the present invention has good activation effect for carbide slag-flyash system inferior.
Embodiment 5-8:
What embodiment 5-8 was directed against is lime-flyash system inferior.In embodiment 5-8, lime is commercial commodity lime (being calcareous raw material), active CaO content 61%, and flyash inferior is identical with previous embodiment.The mass ratio of in evaluation, getting lime and flyash inferior is 30: 70; The water volume is 12.0% of lime and a flyash total mass inferior; The control samples that does not add acvator, its 7 days ultimate compression strength are 7.1MPa, 7 days intensity of the proportioning of acvator, addition and sample are listed in the table below 2:
Table 2
In the table 2, component A is a saltcake; B component is a caustic alkali; Component C is an anhydrous sodium metasilicate; Component D is a sodium metaaluminate.According to the set of dispense ratio, accurately each raw material in the weighing acvator has its adding in the mixing machine of whipping appts, stirs the composite activating agent that just obtained being used for calcareous raw material-Gao sial industrial residue system in 30-80 minute.
In the table 2, the composite activating agent volume is the 1-4% of lime, flyash inferior and water total mass.Composite activating agent with mix with lime, flyash inferior again after water mixes, stir, obtain calcareous raw material-Gao sial industrial residue system (lime-flyash system inferior).
Data can be seen from table 2, add that the intensity of sample is significantly improved behind the acvator, have minimumly improved 39%, have the highlyest improved 72%, show that said acvator has activation effect preferably for lime-flyash system inferior.
Embodiment 9-12:
What embodiment 9-12 was directed against is white lime-flyash system inferior.In embodiment 9-12, white lime is the desciccate (calcareous raw material) behind the commercial quicklime slaking, the active CaO content 61% of the unslaked lime of purchasing; Flyash inferior is identical with embodiment 1.The mass ratio of in experiment, getting white lime and flyash inferior is 35: 65; The water volume is 8.5% of white lime and a flyash total mass inferior; The control samples that does not add acvator, its 7 days ultimate compression strength are 6.2MPa, 7 days intensity of the proportioning of acvator, addition and sample are listed in the table below 3:
Table 3
In the table 3, component A is a SODIUM SULPHATE ANHYDROUS 99PCT; B component is a caustic alkali; Component C is an anhydrous sodium metasilicate; Component D is a sodium metaaluminate.According to the set of dispense ratio, accurately each raw material in the weighing acvator has its adding in the mixing machine of whipping appts, stirs the composite activating agent that just obtained being used for calcareous raw material-Gao sial industrial residue system in 30-80 minute.
In the table 3, the composite activating agent volume is the 1-4% of white lime, flyash inferior and water total mass.Composite activating agent with mix with white lime, flyash inferior again after water mixes, stir, obtain calcareous raw material-Gao sial industrial residue system (white lime-flyash system inferior).
Data can be seen from table 3, add that the intensity of sample is significantly improved behind the acvator, have minimumly improved 61%, have the highlyest improved 81%, show that said acvator has obvious activation effect for lime-flyash system inferior.
Embodiment 13-14:
What embodiment 13-14 was directed against is carbide slag-blast-furnace slag system.Wherein, carbide slag is identical with embodiment 1, and blast-furnace slag is the waste residue (high sial industrial residue) of from blast furnace, discharging when smelting the pig iron, behind ball milling, crosses the product of 100 mesh sieves, has apparent pozzolanic activity.The mass ratio of power taking rock ballast and blast-furnace slag is 15: 85 in experiment; The water volume is 11.5% of carbide slag and a blast-furnace slag total mass; The control samples that does not add acvator, its 7 days ultimate compression strength are 8.7MPa, 7 days intensity of the proportioning of acvator, addition and sample are listed in the table below 4:
Table 4
In the table 4, component A is a Sodium sulfate anhydrous.min(99); B component is a caustic alkali; Component C is nine water water glass; Component D is a sodium metaaluminate.According to the set of dispense ratio, accurately each raw material in the weighing acvator has its adding in the mixing machine of whipping appts, stirs the composite activating agent that just obtained being used for calcareous raw material-Gao sial industrial residue system in 30-80 minute.
In the table 4, the composite activating agent volume is 1%, 3% of carbide slag, blast-furnace slag and a water total mass.Composite activating agent with mix with carbide slag, blast-furnace slag again after water mixes, stir, obtain calcareous raw material-Gao sial industrial residue system (carbide slag-blast-furnace slag system).
Data can be seen from table 4, and the intensity of sample is significantly improved behind the interpolation acvator, and the raising rate is 45%-58%, shows that said acvator has obvious activation effect for carbide slag-blast-furnace slag system.
Embodiment 15-16:
What embodiment 15-16 was directed against is carbide slag-slag system.Wherein, carbide slag is identical with embodiment 1, the waste residue (being high sial industrial residue) that slag steel-making produces.Having passed through ball milling and screening before the use, is product under 100 mesh sieves, has apparent pozzolanic activity.The mass ratio of power taking rock ballast and blast-furnace slag is 15: 85 in experiment; The water volume is 11.0% of carbide slag and a slag total mass; The control samples that does not add acvator, its 7 days ultimate compression strength are 8.8MPa, 7 days intensity of the proportioning of acvator, addition and sample are listed in the table below 5:
Table 5
In the table 5, component A is a saltcake; B component is a sheet alkali; Component C is nine water water glass; Component D is an industrial sodium aluminate.According to the set of dispense ratio, accurately each raw material in the weighing acvator has its adding in the mixing machine of whipping appts, stirs the composite activating agent that just obtained being used for calcareous raw material-Gao sial industrial residue system in 30-80 minute.
In the table 5, the composite activating agent volume is 1%, 3% of carbide slag, slag and a water total mass.Composite activating agent with mix with carbide slag, slag again after water mixes, stir, obtain calcareous raw material-Gao sial industrial residue system (carbide slag-slag system).
Data can be seen from table 5, and the intensity of sample is significantly improved behind the interpolation acvator, and the raising rate is 44%-68%, shows that said acvator has obvious activation effect for carbide slag-slag system.
Comprehensive the foregoing description, acvator according to the invention can significantly improve the early strength of various calcareous raw materials-Gao sial industrial residue system, has efficiently general characteristics.The upper lower limit value of each component can both be realized among the present invention simultaneously, does not enumerate embodiment one by one at this.
Claims (4)
1. be used for the composite activating agent of calcareous raw material-Gao sial industrial residue system, it is characterized in that: it is formed by the mass percent mix by following component:
The vitriol of sodium: 5%～85%;
The oxyhydroxide of sodium: 0.5～75%;
Water glass: 0.5～80%;
Sodium aluminate or sodium metaaluminate: 5%～15%.
2. the composite activating agent that is used for calcareous raw material-Gao sial industrial residue system according to claim 1, it is characterized in that: the vitriol of sodium is any one in Sodium sulfate anhydrous.min(99), saltcake, the SODIUM SULPHATE ANHYDROUS 99PCT.
3. the composite activating agent that is used for calcareous raw material-Gao sial industrial residue system according to claim 1, it is characterized in that: the oxyhydroxide of sodium is any one in sheet alkali, the caustic alkali.
4. the composite activating agent that is used for calcareous raw material-Gao sial industrial residue system according to claim 1, it is characterized in that: water glass is any one in nine water water glass, the anhydrous sodium metasilicate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936315A (en) * | 2014-03-31 | 2014-07-23 | 江苏融达新材料股份有限公司 | Preparation method of modified active slag powder |
| CN104030592A (en) * | 2014-07-01 | 2014-09-10 | 把正春 | Method for preparing environment-friendly activation mineral material addition exciting agent of ferrochrome slag |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121590A (en) * | 2007-07-10 | 2008-02-13 | 武汉理工大学 | Steel slag coal ash self-cementing material |
-
2011
- 2011-12-30 CN CN2011104538965A patent/CN102557508A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121590A (en) * | 2007-07-10 | 2008-02-13 | 武汉理工大学 | Steel slag coal ash self-cementing material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936315A (en) * | 2014-03-31 | 2014-07-23 | 江苏融达新材料股份有限公司 | Preparation method of modified active slag powder |
| CN104030592A (en) * | 2014-07-01 | 2014-09-10 | 把正春 | Method for preparing environment-friendly activation mineral material addition exciting agent of ferrochrome slag |
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Application publication date: 20120711 |