CN102936121A - Composite material used in mine roadway filling - Google Patents
Composite material used in mine roadway filling Download PDFInfo
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- CN102936121A CN102936121A CN2012104098654A CN201210409865A CN102936121A CN 102936121 A CN102936121 A CN 102936121A CN 2012104098654 A CN2012104098654 A CN 2012104098654A CN 201210409865 A CN201210409865 A CN 201210409865A CN 102936121 A CN102936121 A CN 102936121A
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- yellow phosphorus
- slag
- agent
- properties
- compound material
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Abstract
The invention discloses a composite material used in mine roadway filling. The material is prepared by well mixing the components of: yellow phosphorus slag powder, an activating agent, and a modifying agent according to a ratio of (19-22):(10-17):(1-4). A preparation method comprises the steps that: yellow phosphorus slag, the activating agent, and the modifying agent are respectively dried and crushed until a fineness is 200-300 meshes, wherein a sieve margin of the powders is smaller than 5%; the materials are weighed according to the mass ratio; yellow phosphorus slag powder is well mixed with the activating agent, and the modifying agent is added; 2-4 times by volume of water is added, and the mixture is well mixed by stirring, such that the composite material is obtained. The material provided by the invention has good fluidity. A solidification time satisfies a requirement. According to the material, early-stage strength is high, and late-stage strength is improved. During a production process, the composite material is placed in an original cement chamber, such that production can be carried out. Therefore, production is easy to organize. The material can be used for replacing cement and fly ash, and cement and cement clinker are not needed to be adopted as raw materials, such that production cost is reduced to a maximal extent, and enterprise economic benefit is improved.
Description
Technical field
The present invention relates to the compound material of a kind of mine working filling, belong to mine working packing technique field.
Background technology
Along with developing rapidly of chemical industry, the quantity of phosphatization factory annual discharging yellow phosphorus furnace slag constantly increases, in order rationally to utilize yellow phosphorus furnace slag, at present existing Large-scale Phosphorus chemical plant begins to utilize yellow phosphorus furnace slag to replace cement and the flyash of the cementing usefulness of filling phosphorous gypsum, thereby greatly saved cement consumption, reduce production costs, improve Business Economic Benefit.But adopt yellow phosphorus furnace slag to cooperate dehydration property relatively poor with phosphogypsum, setting time is long, and intensity is low, and meets water and easily soften.Though add the material such as water glass as exciting agent after, substantially can satisfy dehydration in early stage, the setting time requirement of filling because water glass is liquid, under the present appointed condition of Filling Station, carry out commerical test, organize production difficulty large.
The mechanism of action of composite furnace ground-slag and phosphogypsum is:
Phosphogypsum has promoter action to the aquation of composite furnace ground-slag, and the composite furnace ground-slag is dissolved in the water, and OH is provided
-, at OH
-Effect under, the Al-O in the vitreum reticulated structure, Si-O chain are opened, and along with the Vitrea dissolving of disintegrating gradually, following reaction occur in the liquid phase:
SiO
2+yCa(OH)
2+(n-yH
2O)=xCaO·SiO
2·nH
2O
Al
2O
3+xCa(OH)
2+(m-xH
2O)=xCaO·Al
2O
3·mH
2O
The initial drated calcium aluminate that generates is with C
3AH
6Form exist, in the alkaline environment that the composite furnace ground-slag provides, C
3AH
6Be converted to C
4AH
13, again with liquid phase in gypsum react and generate ettringite (AFt):
4CaO·Al
2O
3·13H
2O＋3CaSO
4·2H
2O＋14H
2O＝
3CaSO
4·Al
2O
3·3CaSO
4·31H
2O(AFt)
The ettringite that generates is water-fast needle-like crystal, is adsorbed on vitreous surface.Aquation is proceeded, and vitreum dissolves gradually, and hydrated product increases gradually.
The aquation of yellow phosphorus furnace slag from outward appearance to inner essence occurs gradually, the C in the initial composite furnace ground-slag
3S, C
2S and water react rapidly and generate Ca (OH)
2Saturated solution, and therefrom separate out Ca (OH)
2Crystal, gypsum also enters solution and C very soon simultaneously
3The A reaction generates tiny ettringite, and at this one-phase, because the hydrated product size is tiny, quantity is few, not the webbed coherent structure of shape.Along with proceeding of hydration reaction, generate more Ca (OH)
2And ettringite, grow the fibrous gel of C-S-H on the composite furnace ground-slag particle simultaneously, because growing up and a large amount of formation of C-S-H of ettringite, contact with each other and produce point of contact, each particle is tentatively connected into network structure, along with the increase of point of contact number, reticulated structure is constantly strengthened, the corresponding increase of intensity.When maintenance finished, most yellow phosphorus furnace slags had been finished aquation, each hydrated product such as C-S-H, Ca (OH)
2, C
3AH
6, C
4(A, F) H
13Constantly increase etc. quantity, structure is fine and close gradually, forms the coherent structure with intensity.
CN102234191A discloses a kind of early-strength type mine working cementing filling material, is prepared from by the certain weight ratio mixing by blast-furnace slag, aluminosulfate cement (perhaps sulphoaluminate cement clinker) and exciting agent water glass.CN102381847A discloses a kind of mine working filling blast furnace water quenching slag gelling material, is comprised of by certainweight per-cent ordinary portland cement clinker powder, Water Quenching Slag powder, anhydrite powder and unslaked lime powder.Although above scheme has realized the blast-furnace slag comprehensive utilization, but still used cement or cement clinker as raw material.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, the invention provides the compound material of a kind of mine working filling, solved the problem that mine working Filling Cementation material dewatering is relatively poor, setting time is long, intensity is low or difficult tissue is produced, and can be raw material without cement or cement clinker.
The objective of the invention is to be achieved by the following technical programs.
The compound material of a kind of mine working filling is characterized in that: by Yellow phosphorus furnace ground-slag, exciting agent and properties-correcting agent according to (19～22): (10～17): after the mass ratio of (1～4) mixed, the water that adds 2～4 times of volumes stirred and makes;
Described exciting agent refers to any or several combination in phosphogypsum, limestone, fluorite or the calcareous shale;
Described properties-correcting agent refers to any or several combination in water glass, Sodium Silicofluoride, sodium hydroxide, Trisodium Citrate, unslaked lime or the slaked lime.
Described exciting agent is that fineness is 200～300 orders, screen over-size less than 5% flour, preferred phosphogypsum and calcareous shale;
Described properties-correcting agent is that fineness is 200～300 orders, screen over-size less than 5% flour, preferred water glass, Sodium Silicofluoride and slaked lime;
Described Yellow phosphorus furnace ground-slag is that fineness is 200～300 orders, screen over-size less than 5% flour.
Above-mentioned mine working filling is with the preparation method of compound material, respectively through oven dry with to be crushed to fineness be 200～300 orders, screen over-size less than 5% meal with yellow phosphorus furnace slag, exciting agent and properties-correcting agent, then take by weighing respectively in mass ratio for subsequent use, first Yellow phosphorus furnace ground-slag and exciting agent are mixed, then add properties-correcting agent, the water that adds at last 2～4 times of volumes stirs and gets final product.
Yellow phosphorus furnace slag is the industry byproduct that utilizes after Rock Phosphate (72Min BPL) is produced yellow phosphorus, is the industrial residue that electric furnace process produces when producing yellow phosphorus, the about 11t yellow phosphorus furnace slag of every production 1t yellow phosphorus discharging.In smelting process, the yellow phosphorus furnace slag that is under the molten state cools off through shrend, and its main component is the silicate glass body, SiO
2Nearly 90% with the CaO total content, have potential hydration activity.
Exciting agent among the present invention is the high silicon matter of high calcium.Under the effect of exciting agent, glassy phase in the yellow phosphorus furnace slag accelerates to disperse and decompose, more pulverized slag surface is contacted with water, promoted slag to participate in the quantity of reaction, generate more C-S-H gel, the reaction of generation hydration and hardening, thus early strength improved, and later strength is also improved largely simultaneously.In addition, exciting agent can improve the basicity of liquid phase in early days, promotes the Ca (OH) that generates in the composite furnace ground-slag hydration process
2Crystallization nucleation and the growth of crystal, accelerate the early hydration speed of silicate minerals, also early strength is had contribution.
Properties-correcting agent among the present invention can promote that exciting agent plays a role, and reacts with exciting agent, produces more C-S-H gel, and increases folding strength and the ultimate compression strength of compound material.
Beneficial effect of the present invention: good fluidity, the setting time composite demand, early strength is higher, and later strength is improved, and can produce in the former cement bin that only needs in process of production compound material to be packed into, and tissue is produced easily.Can replace cement and flyash,, reduce production costs to greatest extent as raw material without cement and cement clinker, improve Business Economic Benefit.
Embodiment
Form is described in further detail content of the present invention by the following examples, but that claimed scope is not limited to is described.
Embodiment 1-8
Getting phosphogypsum is exciting agent, the aqueous solution of water glass is properties-correcting agent 1, Sodium Silicofluoride is properties-correcting agent 2, slaked lime is properties-correcting agent 3, respectively through oven dry with to be crushed to fineness be 200 orders, screen over-size less than 5% meal, then takes by weighing respectively in mass ratio for subsequent use yellow phosphorus furnace slag, exciting agent and each properties-correcting agent, according to the proportioning shown in the table 1, first Yellow phosphorus furnace ground-slag and exciting agent are mixed, then add properties-correcting agent, add entry by the water consumption of standard shown in the table 3 at last and stir; Be filled in respectively 70.7mm * 70.7mm * 70.7mm standard die trial, after test specimen is made in the laboratory (20 ± 5 ℃, humidity 60%) but lower maintenance to the demoulding, then to the form removal of test specimen numbering.Putting into immediately temperature after the form removal is 20 ± 2 ℃, relative humidity is that maintenance detects 7d, 14d, 28d and later strength thereof in the standard curing room more than 95%, the cement mortar strength detected result sees Table 2, and water consumption detected result time of coagulation sees Table 3, and filling mixed slurry laboratory strength detected result sees Table 4.
The proportioning of the compound material of table 1
The compound material intensity detection of table 2 table
Table 3 water consumption time of coagulation
Table 4 filling mixed slurry laboratory strength detects table
As shown in Table 2, the compound material of the present invention all has stronger cement mortar strength.Wherein, embodiment 1,3,5,7 early strength and later strength are best, namely when properties-correcting agent be slaked lime, in the time of the combination of the perhaps combination of slaked lime and sodium hydroxide, or slaked lime and water glass, intensity effect is best.
As shown in Table 3, the standard water consumption of the compound material of the present invention is more or less the same, and short presetting period and final setting time are all arranged.Wherein, embodiment 3,4,7, presetting period of 8 are shorter, and embodiment 2,3,4,8 final setting time are shorter; Namely when properties-correcting agent be the combination of sodium hydroxide and slaked lime, perhaps during the combination of water glass and slaked lime, the presetting period is the shortest; When properties-correcting agent is slaked lime, the perhaps combination of slaked lime and sodium hydroxide, perhaps during the combination of water glass and slaked lime, final setting time is the shortest.
As shown in Table 4, the compound material of the present invention all has preferably intensity as the filling mixed slurry.Wherein, embodiment 1,5,7,8 early strength are best, and embodiment 1,2,6,7 later strengths are best; Namely when properties-correcting agent be slaked lime, perhaps during the combination of water glass and slaked lime, early stage, intensity and later strength were best.
In sum, the compound material of the present invention all has preferably intensity and short setting time as glue sand and filling compound.Wherein, when properties-correcting agent is slaked lime, in the time of the combination of the perhaps combination of slaked lime and sodium hydroxide, or slaked lime and water glass, intensity effect is best; When properties-correcting agent is the combination of sodium hydroxide and slaked lime, perhaps during the combination of water glass and slaked lime, the presetting period is the shortest; When properties-correcting agent is slaked lime, the perhaps combination of slaked lime and sodium hydroxide, perhaps during the combination of water glass and slaked lime, final setting time is the shortest.
Claims (5)
1. compound material of mine working filling is characterized in that: by Yellow phosphorus furnace ground-slag, exciting agent and properties-correcting agent according to (19～22): (10～17): after the mass ratio of (1～4) mixed, the water that adds 2～4 times of volumes stirred and makes;
Described exciting agent refers to any or several combination in phosphogypsum, limestone, fluorite or the calcareous shale;
Described properties-correcting agent refers to any or several combination in water glass, Sodium Silicofluoride, sodium hydroxide, Trisodium Citrate, unslaked lime or the slaked lime.
2. the compound material of a kind of mine working filling according to claim 1 is characterized in that: described exciting agent is that fineness is 200～300 orders, screen over-size less than 5% flour, preferred phosphogypsum and calcareous shale.
3. the compound material of a kind of mine working filling according to claim 1 is characterized in that: described properties-correcting agent is that fineness is 200～300 orders, screen over-size less than 5% flour, preferred water glass, Sodium Silicofluoride and slaked lime.
4. the compound material of a kind of mine working filling according to claim 1 is characterized in that: described Yellow phosphorus furnace ground-slag is that fineness is 200～300 orders, screen over-size less than 5% flour.
5. a kind of mine working filling according to claim 1 is with the preparation method of compound material, it is characterized in that: with yellow phosphorus furnace slag, exciting agent and properties-correcting agent respectively through oven dry with to be crushed to fineness be 200～300 orders, screen over-size less than 5% meal, then take by weighing respectively in mass ratio for subsequent use, first Yellow phosphorus furnace ground-slag and exciting agent are mixed, then add properties-correcting agent, the water that adds at last 2～4 times of volumes stirs and gets final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104098654A CN102936121A (en) | 2012-10-24 | 2012-10-24 | Composite material used in mine roadway filling |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104098654A CN102936121A (en) | 2012-10-24 | 2012-10-24 | Composite material used in mine roadway filling |
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| Publication Number | Publication Date |
|---|---|
| CN102936121A true CN102936121A (en) | 2013-02-20 |
Family
ID=47695057
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|---|---|---|---|
| CN2012104098654A Pending CN102936121A (en) | 2012-10-24 | 2012-10-24 | Composite material used in mine roadway filling |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864455A (en) * | 2014-03-14 | 2014-06-18 | 昆明理工大学 | Method for yellow phosphorus slag base aerated building blocks |
| CN103964804A (en) * | 2014-05-12 | 2014-08-06 | 中南大学 | Low-bleeding-rate pumpable phosphogypsum and yellow phosphorus slag filling paste and preparation method of paste |
| CN107445503A (en) * | 2017-09-13 | 2017-12-08 | 贵州开磷磷石膏综合利用有限公司 | A kind of antifreeze slow setting calcium phosphate Si-Mg cement and preparation method thereof |
| CN113233796A (en) * | 2021-06-30 | 2021-08-10 | 湖北理工学院 | Tailing filling full-solid waste cementing material and preparation method thereof |
| CN114276083A (en) * | 2021-12-25 | 2022-04-05 | 郴州中祁工程材料有限公司 | Environment-friendly concrete containing waste phosphorus slag and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415567A (en) * | 2002-12-24 | 2003-05-07 | 清华大学 | binary mixed coagulated stones and wet cement and method for production, deposit, transportation use and application |
| CN102211917A (en) * | 2011-03-29 | 2011-10-12 | 湖南科技大学 | High water-containing mud curing agent for mine filling and using method thereof |
-
2012
- 2012-10-24 CN CN2012104098654A patent/CN102936121A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415567A (en) * | 2002-12-24 | 2003-05-07 | 清华大学 | binary mixed coagulated stones and wet cement and method for production, deposit, transportation use and application |
| CN102211917A (en) * | 2011-03-29 | 2011-10-12 | 湖南科技大学 | High water-containing mud curing agent for mine filling and using method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864455A (en) * | 2014-03-14 | 2014-06-18 | 昆明理工大学 | Method for yellow phosphorus slag base aerated building blocks |
| CN103864455B (en) * | 2014-03-14 | 2015-06-03 | 昆明理工大学 | Method for yellow phosphorus slag base aerated building blocks |
| CN103964804A (en) * | 2014-05-12 | 2014-08-06 | 中南大学 | Low-bleeding-rate pumpable phosphogypsum and yellow phosphorus slag filling paste and preparation method of paste |
| CN103964804B (en) * | 2014-05-12 | 2016-01-20 | 中南大学 | A kind of low bleeding rate can pumping phosphogypsum and Phosphorus Slag fill paste and preparation method |
| CN107445503A (en) * | 2017-09-13 | 2017-12-08 | 贵州开磷磷石膏综合利用有限公司 | A kind of antifreeze slow setting calcium phosphate Si-Mg cement and preparation method thereof |
| CN113233796A (en) * | 2021-06-30 | 2021-08-10 | 湖北理工学院 | Tailing filling full-solid waste cementing material and preparation method thereof |
| CN114276083A (en) * | 2021-12-25 | 2022-04-05 | 郴州中祁工程材料有限公司 | Environment-friendly concrete containing waste phosphorus slag and preparation method thereof |
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Application publication date: 20130220 |