CN105503116A - Cemented filling material - Google Patents
Cemented filling material Download PDFInfo
- Publication number
- CN105503116A CN105503116A CN201610040283.1A CN201610040283A CN105503116A CN 105503116 A CN105503116 A CN 105503116A CN 201610040283 A CN201610040283 A CN 201610040283A CN 105503116 A CN105503116 A CN 105503116A
- Authority
- CN
- China
- Prior art keywords
- phosphogypsum
- filling material
- lime
- cemented filling
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a cemented filling material which comprises hemihydrated phosphogypsum, crude tailings and lime, wherein the weight ratio of the crude tailings to the hemihydrated phosphogypsum is 1:3-1:4, the weight ratio of the lime to the hemihydrated phosphogypsum is 1.2-2.0%, and the crystalline water content in the hemihydrated phosphogypsum is less than 9.5%. The filling material has the advantages of very low cost, short curing time and high curing strength, is green and environment-friendly, and can be used for downhole filling.
Description
Technical field
The invention belongs to filling in mine field of material technology, be specifically related to a kind of novel cemented filling material.
Background technology
Current domestic Wet Processes of Phosphoric Acid mainly based on two water laws, two water laws produce phosphoric acid time, its by product phosphogypsum dihydrate (CaSO
42H
2o) be widely applied in filling in mine field as a kind of cemented filling material.But when adopting phosphogypsum dihydrate to carry out consolidated fill, there are the following problems:
(1) filling cost is high.Because phosphogypsum dihydrate pectisation is little, therefore when utilizing it to carry out consolidated fill, for ensureing that the rear obturator 3d intensity of solidification and 7d intensity meet mining requirement, generally need to mix the high cement of accounting as gelling material.The gelling material of a kind of fine tailings filling disclosed in patent CN201310035710, need mix the belite sulphoaluminate cement of 15% ~ 40%.Mixing cement then makes filling cost greatly improve.
(2) solidification intensity is low.In order to reduce filling cost, some phosphogypsum dihydrate filling process adopts yellow phosphorus furnace slag to be used as gelling material, as the substitute of the jointing compound such as cement.Though make filling cost reduce, solidification intensity cannot meet mining and require (general 3d strength of filling mass is not less than 1.5MPa, and 7d strength of filling mass is not less than 2.5MPa).A kind of mixture for mine working filling disclosed in patent CN201210411684, the yellow phosphorus furnace slag that need mix 10% ~ 24% substitutes cement as gelling material, and its 28d solidification intensity is only 0.72MPa, is difficult to meet the demands.
(3) set time is long.Disclosed in patent CN200610031428, filling phosphorous gypsum forms the method for solidification obturator in worked-out section, and its set time reaches 28 days, and ultimate compression strength just can reach 1 ~ 1.3MPa.Phosphogypsum disclosed in patent CN200710193247 is used for the method for mine worked-out section consolidated fill, though by the pectisation adding shrend iron (steel) slag and lime optimization cement, but still needing solidification in 5 ~ 8 days, ultimate compression strength just can reach 1.5MPa, and set time is partially long.
Summary of the invention
The present invention is intended to overcome Problems existing in background technology, provides a kind of novel cemented filling material, and this casting resin cost is extremely low, and set time is short, and solidification intensity is high, and environmental protection can be used for underground filling.
Research shows, ordinary Portland cement main component is tricalcium silicate (3CaOSiO
2), Dicalcium Phosphate (Feed Grade) (2CaOSiO
2), mainly generate hydrated calcium silicate (3CaO2SiO after its hydration reaction
23H
2o) gel plays pectisation, and also namely ordinary Portland cement just has pectisation after hydration reaction.
Guizhou Chuan Heng chemical company takes the lead in breakthrough half water law phosphoric acid by wet process complete set technology at home, and half water phosphogypsum is the by product of the method when producing phosphoric acid, and main component is CaSO
41/2H
2o.Can half water phosphogypsum be utilized to carry out consolidated fill, overcome the problems such as phosphogypsum dihydrate consolidated fill cost is high, set time is long, solidification intensity is low, the applicant have carried out large quantity research simultaneously.
Research shows: half water phosphogypsum (CaSO within crystal water content 9.5%
41/2H
2o) meeting after water can fast hydration, the phosphogypsum dihydrate (CaSO of generation
42H
2o) crystal formation cement structure skeleton, has excellent gelling property, and the hydrated calcium silicate gel generated after alternative ordinary Portland cement hydration reaction, plays pectisation.
For realizing the object of the invention, the present invention adopts following technical scheme: a kind of cemented filling material, comprise by half water phosphogypsum of following weight proportion, crude tailings and lime, crude tailings: half water phosphogypsum=1:3 ~ 1:4, lime: half water phosphogypsum=1.2% ~ 2.0%, wherein half water phosphogypsum crystal water-content is within 9.5%.
Above-mentioned cemented filling material water makes filling slurry.Preferably make the filling slurry of mass concentration 69% ~ 73%.
Preferably, half water phosphogypsum crystal water-content 5.3 ~ 8.63%, further preferably, 5.3 ~ 6.7%.
Preferably, lime: half water phosphogypsum=1.2% ~ 1.6%.
Preferably, described crude tailings is the by product that single reverse floatation process produces phosphorus concentrate.
Described lime is unslaked lime or white lime.
The preparation method of above-mentioned cemented filling material half water phosphogypsum, crude tailings and lime is added water by described proportioning mix and stir.
The present invention has following unusual effect:
1) filling cost is low.The present invention makes full use of the excellent gelling characteristic of half water phosphogypsum, is used as jelling agent without the need to mixing cement, flyash or yellow phosphorus furnace slag.To the crude tailings of factory's output be selected to be used as filling aggregate, half water phosphogypsum of phosphorizing treatment output be used as gelling material, and mix the lime of minute quantity, filling cost is extremely low.
2) set time is short, intensity is high.This filling mixture is filled with dead zone, and after solidification in 3 days, obturator ultimate compression strength can reach 1.8MPa ~ 4.53MPa, and after solidification in 7 days, obturator ultimate compression strength can reach 2.7MPa ~ 11.87MPa.Significantly shorten pack period, improve mining efficiency, be applicable to various mining technology and all types of Filling mine-out area.
3) environmental protection.Directly crude tailings and half water phosphogypsum are used as compaction material, being filled to dead zone, down-hole, without the need to arranging Tailings Dam and ardealite storage yard, there is not Tailings Dam, phosphogypsum storehouse safety problem, Economization on land in earth's surface.Filling mixture does not produce CO
2, H
2s, PH
3, SO
2toxic and harmful.Toxicity leaching experiment is carried out to the obturator after solidification, does not detect heavy metal, and PO
4 3-, sulfide, F, As equal size all meet relevant criterion requirement.
Embodiment
Embodiment 1 ~ 7: the half water phosphogypsum (crystal water weight content 5.3 ~ 8.63%) of the crude tailings and phosphorizing treatment half water Wet-process phosphoric acid (WPPA) output of producing phosphorus concentrate output by selecting the single reverse floatation process of factory by butt than 1:3 ~ 1:4, lime presses butt than 1.2% ~ 2.0% with half water phosphogypsum, add water mixing again and pour horizontal mortar mixer stirring 3min into, stir to the filling slurry of mass concentration 69% ~ 73%, obtain underground filling or test filling slurry used, each embodiment data are in table 1.Filling slurry need stir and can be delivered to dead zone, down-hole, solidify to form high strength cemented fill.
By GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard ", get filling slurry mixture and carry out slump mensuration, feeding slurry is filled in 70.7mm × 70.7mm × 70.7mm standard die trial simultaneously.In down-hole, obturator often can be subject to drenching water mitigation.Therefore, in order to press close to subsurface environment as far as possible, at ambient temperature test specimen is regularly sprinkled water maintenance.Adopt the WEW-Y2000B type pressure experiment machine testing test specimen uniaxial compressive strength of 3 days, 7 days, get 3 test blocks each length of time, first first will test the unit weight of these 3 test blocks, then survey its uniaxial compressive strength with pressing machine.Uniaxial compressive strength value is the mean value of 3 test blocks.The results are shown in Table 1.
Table 1 filling mixture proportioning and performance perameter
As shown in Table 1, though cement is not mixed in the casting resin in embodiment, its set time is short and intensity is high, and two samples are after solidification, and within 3 days, intensity can reach 1.8MPa ~ 4.53MPa; Within 7 days, intensity can reach 2.7MPa ~ 11.87MPa.
Poisonous gas detection experiment: to CO issuable in filling slurry mixture
2, H
2s, PH
3, SO
2toxic and harmful detects.The distilling flask that filling slurry mixture is housed connects successively copper-bath, the barium chloride solution of nitric acid acidifying and the absorption bottle of aqua calcis is housed.Gas is by after copper-bath, and blackening indicates H
2s (also can directly Lead acetate paper), has red solid to produce and indicates PH
3, gas, by the barium chloride solution of nitric acid acidifying, becomes muddy and indicates SO
2, gas becomes muddy by aqua calcis and indicates CO
2.Experiment finds that the distilling flask that filling slurry mixture is housed is in still-process, and each absorption bottle, all without phenomenon, shows that filling slurry mixture does not produce CO
2, H
2s, PH
3, SO
2toxic and harmful.This is the lime accounting for phosphogypsum weight 1.2% ~ 2.0% owing to mixing in casting resin, has neutralized the free acid (after testing pH=2.04) in phosphogypsum, has eliminated CO
2, H
2s, PH
3, SO
2the generation of toxic and harmful.
Toxicity leaching experiment is carried out to obturator test specimen.Reference standard GB5085.3-2007, adopts the U.S. to produce TCLP type leaching plant, solidifies the obturator test specimen of 7d in Example, respectively with water, sulfuric acid+nitric acid for digestion agent, by liquid-solid ratio 10:1, soak 72h, sampling filtering is analyzed.Leaching experiment the results are shown in Table 2, and heavy metal does not detect, and As, F are all lower than the requirement of GB 8978-1996 and GB GB5085.3-2007, and therefore phosphogypsum, tailings belong to general industry refuse, without Leaching.
Table 2 obturator leaching experiment result
From poisonous gas test experience and toxicity leaching experiment result, this filling slurry does not produce any toxic and harmful, and the obturator formed after solidification is without Leaching, and indices all meets standard-required, environmental protection.
Claims (9)
1. a cemented filling material, it is characterized in that comprising by half water phosphogypsum of following weight proportion, crude tailings and lime, crude tailings: half water phosphogypsum=1:3 ~ 1:4, lime: half water phosphogypsum=1.2% ~ 2.0%, wherein half water phosphogypsum crystal water-content is within 9.5%.
2. cemented filling material according to claim 1, is characterized in that making filling slurry with water.
3. cemented filling material according to claim 2, is characterized in that the filling slurry making mass concentration 69% ~ 73%.
4. cemented filling material according to claim 1, is characterized in that half water phosphogypsum crystal water-content 5.3 ~ 8.63%.
5. cemented filling material according to claim 4, is characterized in that half water phosphogypsum crystal water-content 5.3 ~ 6.7%.
6. the cemented filling material according to claim 1,4 or 5, is characterized in that lime: half water phosphogypsum=1.2% ~ 1.6%.
7. cemented filling material according to claim 1, is characterized in that described crude tailings is the by product that single reverse floatation process produces phosphorus concentrate.
8. cemented filling material according to claim 1, is characterized in that described lime is unslaked lime or white lime.
9. a preparation method for cemented filling material described in claim 1, it is characterized in that adds water half water phosphogypsum, crude tailings and lime by described proportioning mixes and stirs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610040283.1A CN105503116A (en) | 2016-01-21 | 2016-01-21 | Cemented filling material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610040283.1A CN105503116A (en) | 2016-01-21 | 2016-01-21 | Cemented filling material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105503116A true CN105503116A (en) | 2016-04-20 |
Family
ID=55711495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610040283.1A Pending CN105503116A (en) | 2016-01-21 | 2016-01-21 | Cemented filling material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105503116A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298569A (en) * | 2017-08-08 | 2017-10-27 | 合肥工业大学 | A kind of Modified soil blank material material and the traditional rowlock wall body construction method of filling |
| CN107555927A (en) * | 2017-08-23 | 2018-01-09 | 贵州川恒化工股份有限公司 | Half water filling phosphorous gypsum material and preparation method thereof |
| CN108152453A (en) * | 2017-12-11 | 2018-06-12 | 飞翼股份有限公司 | The detection method of poisonous gas produced by a kind of filling in mine ardealite |
| CN109956730A (en) * | 2019-04-24 | 2019-07-02 | 山东佳运环保科技有限公司 | Modified gypsum is native and its as the application and construction method in basic engineered packings |
Citations (5)
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|---|---|---|---|---|
| CN1273222A (en) * | 1999-05-06 | 2000-11-15 | 北京市高水矿山工程与材料研究所 | Filler for concretion of sandy soil and production and application method |
| CN101439954A (en) * | 2007-11-25 | 2009-05-27 | 铜陵化学工业集团有限公司 | Method for using phosphogypsum in mine goaf consolidated filling |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298569A (en) * | 2017-08-08 | 2017-10-27 | 合肥工业大学 | A kind of Modified soil blank material material and the traditional rowlock wall body construction method of filling |
| CN107298569B (en) * | 2017-08-08 | 2019-09-13 | 合肥工业大学 | A kind of Modified soil blank material material and filling traditional empty wall body construction method |
| CN107555927A (en) * | 2017-08-23 | 2018-01-09 | 贵州川恒化工股份有限公司 | Half water filling phosphorous gypsum material and preparation method thereof |
| CN108152453A (en) * | 2017-12-11 | 2018-06-12 | 飞翼股份有限公司 | The detection method of poisonous gas produced by a kind of filling in mine ardealite |
| CN109956730A (en) * | 2019-04-24 | 2019-07-02 | 山东佳运环保科技有限公司 | Modified gypsum is native and its as the application and construction method in basic engineered packings |
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| PB01 | Publication | ||
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Application publication date: 20160420 |