CN106915941B - Half water ardealite mine filling material and preparation method thereof - Google Patents
Half water ardealite mine filling material and preparation method thereof Download PDFInfo
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- CN106915941B CN106915941B CN201510981155.2A CN201510981155A CN106915941B CN 106915941 B CN106915941 B CN 106915941B CN 201510981155 A CN201510981155 A CN 201510981155A CN 106915941 B CN106915941 B CN 106915941B
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- Prior art keywords
- ardealite
- half water
- filling material
- tailing
- water ardealite
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Classifications
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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
- 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
- C04B28/142—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 containing synthetic or waste calcium sulfate cements
- C04B28/143—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 containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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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
- 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)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to a kind of methods for preparing mine filling material using half water ardealite.This method is made after being mixed in a certain ratio using half water ardealite of industrial by-product, phosphorus tailing, cement as raw material.For the present invention using half water ardealite as cementitious material, cement adjusts the pH value of filler, and provides partial intensities, and for phosphorus tailing as aggregate, having prepared has early strength height, and bleeding is good, good fluidity mine filling material.Half water ardealite of the invention and phosphorus tailing are the industrial residue of phosphorous chemical industry production, raw material is easy to get, it is low in cost, ardealite and phosphorus tailing are turned waste into wealth, the pollution and harm of ardealite and phosphorus tailing waste residue to environment are effectively administered, with good environmental benefit, Social benefit and economic benefit.
Description
Technical field
The invention belongs to mine filling Material Fields, and in particular to be filled with mine prepared by half water ardealite of industrial by-products
Filler and preparation method thereof.
Background technique
Ardealite is to produce the solid slag being discharged in process phosphoric acid, 1 ton of P of every production2O54-5 tons of dry slag phosphorus stone can be obtained
Cream.According to the difference of wet method phosphoric acid manufacture process, the ardealite composition of by-product is also different, such as the phosphorus of two water law phosphoric acid process by-products
Gypsum main ingredient is CaSO4·2H2O, the ardealite main ingredient of half water law phosphoric acid process by-product are CaSO4·1/2H2O.Phosphorus
Tailing is that phosphorus ore extracts remaining tailings after concentrate when exploiting and producing phosphorus concentrate, and partial size is smaller, and 90% crosses 200 meshes,
40% crosses 325 meshes, and mainly by calcium carbonate and magnesium carbonate mineral composition, usually secondly High-Mg phosphate tailings are based on dolomite
Collophane.Ardealite and phosphorus tailing are all the solid waste of by-product in phosphorous chemical industry production process, and enterprise will put into greatly every year
Amount fund is stacked, if both wastes can comprehensively utilize, can mitigate very big bear to phosphorous chemical industry enterprise
Load.
Someone carries out the technology of filling in mine in research using phosphogypsum dihydrate as main stuffing in recent years, such as Chinese patent Shen
200710077624.3 please disclose a kind of cement, flyash, the filler that ardealite ratio is 1:1:4-6, this method with
Cement and flyash are cementitious material, and ardealite is filler, can utilize ardealite, but filling intensity obtained is lower, 14 days
Intensity is only 2-3MPa.Chinese patent application 201310731705.6 discloses one kind then with quick lime, ardealite, slag micropowder
The filler of preparation, this method lime provide alkaline environment, and ardealite is the gelling that exciting agent carrys out activated slag micro mist,
And obturation early strength is improved by addition early strength agent, can achieve within 3 days 3MPa, but in being formulated ardealite utilization compared with
It is low, the 35%~45% of total raw material can only be accounted for.
Since half water law phosphoric acid process is at home and abroad applied seldom, double of water ardealite (CaSO4·1/2H2O property)
Energy and application also rarely have research, and exploitation is badly in need of in this field can efficiently use the technology of half water ardealite.
Summary of the invention
The present invention improves the early stage of filler to solve the disadvantage that prepare mine filling material using phosphogypsum dihydrate
Intensity, the technical issues of increasing the utilization of solid waste, provide a kind of new mine filling material, are by half water ardealite
For made of main component.
Half water ardealite mine filling material of the present invention is prepared by the raw material of following parts by weight:
Half water ardealite 49~99
Tailing 0~50
Cement 1~10.
Wherein, half water ardealite described in above-mentioned mine filling material is the by-product that half water law phosphoric acid process produces phosphoric acid
Ardealite.
Further, the crystal water content of half water ardealite described in above-mentioned mine filling material is 6%~12%.
Wherein, tailing described in above-mentioned mine filling material refers to remaining fine grained mine after mineral ore dressing.
Wherein, the average grain diameter of tailing described in above-mentioned mine filling material is 10~75 μm.
Wherein, tailing described in above-mentioned mine filling material is the tailing of phosphorus ore.
Further above-mentioned mine filling material is that above-mentioned being formulated in the half water ardealite, phosphorus tailing and cement of mixing is added
Slurry made from moisture.
Preferably, the solid content of slurry described in above-mentioned mine filling material is 60%~80%.
The present invention additionally provides a kind of method of above-mentioned half water ardealite mine filling material simultaneously.This method includes following step
It is rapid: by half water ardealite, phosphorus tailing, cement according to the ratio require metering after, be uniformly mixed to get.Filling material made from this method
Filling base-material can also be called, there is certain storage period, can be used being configured to slurry i.e. using preceding plus water.
In addition, the present invention also provides another 9, prepare half water ardealite mine filling described in claim 5 or 6
The method of material, it is characterised in that the following steps are included: after half water ardealite, phosphorus tailing, cement are required metering according to the ratio, mixing
Uniformly, be added moisture, be prepared into the slurry of solid content 60%-80% to get.
Meanwhile the present invention also provides the methods for preparing half above-mentioned water ardealite mine filling material.This method includes following
Step: it after half water ardealite, phosphorus tailing, cement are required metering according to the ratio, is uniformly mixed, additional amount moisture, is prepared into containing solid
Measure 60%-80% slurry to get.
The beneficial effects of the present invention are: the present invention is cementitious material using half water ardealite of industrial by-product, and it is appropriate to be added
PH regulator excite half water ardealite gelling property, and select phosphorus ore flotation tailing be filler, the mine filling of preparation
Material, early strength is high, good fluidity, and bleeding is good.The present invention is substituted in the prior art using half water ardealite of industrial by-product
Cement as main cementitious material, greatly reduce filling cost.In addition, the half water phosphorus of main material that the present invention uses
Gypsum and phosphorus tailing are all the solid waste of phosphorous chemical industry enterprise by-product, and raw material is simple and easy to get, and the utilization rate of solid waste reaches
90% or more, if control can be used only 1% or so in cement additive amount with fresh half water ardealite, then solid waste
Utilization rate can achieve 99%.
Specific embodiment
The present invention by the basic research of early period, half water ardealite of discovery due to its pattern is synneusis and non-alpha gypsum
Short cylinder, and contain a small amount of acid impurities, cause its solubility in water lower, CaSO4·1/2H2The opposite CaSO of O4·
2H2O inversion of phases is very slow, and without gelling property, filler can only be used as phosphogypsum dihydrate if modification is not added
Or exciting agent uses.
But by the hardening mechanism of half water ardealite of further research, find the hardening process of half water ardealite
The process that mainly half water ardealite is converted to phosphogypsum dihydrate, in this course, the Leaching Properties of Soluble Phosphorus contained in gypsum, soluble fluorine
Equal impurity play very strong deferred action, and therefore, the present invention considers in the case where not changing crystal morphology, in alkaline matter
With the Leaching Properties of Soluble Phosphorus in ardealite, the impurity such as soluble fluorine may play the speed for promoting half water ardealite to convert to phosphogypsum dihydrate,
Excite gelling property.
So, if it is possible to find suitable exciting agent, it is likely that without modification, and directly excite half water ardealite
Potential gelling, it is possible to preparation is used for the filling material of mine filling.It is not only the possibility to that then two water phosphorus stones can be overcome
Disadvantage of the cream as mine filling material, it is also possible to open up new approach for the consumption utilization of half water ardealite.
In addition, research of the invention also found, half water ardealite is a kind of metasable state substance, fresh half just produced
Water phosphogypsum crystal water content is 6%~7%, can (theoretical crystal water content is to phosphogypsum dihydrate in stacking process
20.93%) slowly conversion, gradually loses potential gelling, therefore its crystal water content is lower, can inspire gelling and get over
It is good.
Finally, the present invention has selected cement as exciting agent.Wherein the type of cement and label are required there is no special,
As long as being capable of providing alkaline environment；Cement is also improved filling when providing alkaline environment and playing the role of exciting agent simultaneously
The effect of the strength of materials.If control can be used only 1% or so in cement additive amount, then solid is useless with fresh half water ardealite
The utilization rate of gurry can achieve 99%.
Generally speaking, the formula for the half water ardealite mine filling material that present invention research obtains is by following parts by weight
Raw material is prepared:
Half water ardealite 49~99
Tailing 0~50
At least one of mud or lime 1~10.
Wherein, half water ardealite described in above-mentioned mine filling material is the by-product that half water law phosphoric acid process produces phosphoric acid
Ardealite.The crystal water content of the half water ardealite is 6%~12%.
Wherein, tailing described in above-mentioned mine filling material refers to remaining fine grained mine after mineral ore dressing.The tail
The average grain diameter of mine is 10~75 μm.Due to being to handle half water ardealite in phosphorus chemical industry, it is clear that be using phosphorite tailings
One selection simple and easy to get.
Above-mentioned without another external adding water, the filling material being directly uniformly mixed so as to obtain by raw material can also be called filling base-material, have one
Fixed storage period, can be used being configured to slurry i.e. using preceding plus water.
And further above-mentioned mine filling material, can also by half water ardealite of the formula mixing, phosphorus tailing and
Moisture is added in cement, slurry is made.Preferably, the solid content of the slurry is 60%~80%.Add filling obtained after water
Expect that the resting period is short, it is therefore desirable to be sent to mine worked-out section use as early as possible.
Below by way of specific embodiment, the present invention is further detailed.Cement used in embodiment is general
Lead to commercially available, the average grain diameters of phosphorite tailings is 10~75 μm.
Embodiment 1
75 parts of half water ardealite, 24 parts of phosphorite tailings by crystal water content for 6.1%, are added water and are configured to by 1 part of cement
The slurry that solid content is 69%.Up to mine filling material.
Embodiment 2
75 parts of half water ardealite, 24 parts of phosphorite tailings by crystal water content for 6.1%, are added water and are configured to by 1 part of cement
The slurry that solid content is 71%.Up to mine filling material.
Embodiment 3
99 parts of half water ardealite, 1 part of cement by crystal water content for 6.1%, it is 71% that water, which is added, and is configured to solid content
Slurry.Up to mine filling material.
Embodiment 4
70 parts of half water ardealite, 24 parts of phosphorite tailings by crystal water content for 8.5%, are added water and are configured to by 6 parts of cement
The slurry that solid content is 71%.Up to mine filling material.
Embodiment 5
10 parts of cement, water configuration is added in 70 parts of half water ardealite, 20 parts of phosphorite tailings by crystal water content for 11.5%
The slurry for being 71% at solid content.Up to mine filling material.
The performance of filling in mine material prepared by example 1~5 is as shown in table 1.
Table 1
Example 2 is some more compared with the addition moisture content of example 1, therefore slump is big, and bleeding rate is high, but the two intensity is similar；
Phosphorus tailing is not added for example 3, and intensity is higher than the embodiment 2 of addition phosphorus tailing；Example 2, example 4 and example 5 are with different knots
Half water ardealite of brilliant water content is that raw material prepares filler, the results showed that crystal water content is higher, can be by increasing cement
The additional amount of amount meets requirement to increase the intensity of filler.
Claims (7)
1. a kind of half water ardealite mine filling material, it is characterised in that: be mixed with by the raw material of following parts by weight:
Half water ardealite 49~99
Tailing 0~50
Cement 1~10
The half water ardealite be half water law phosphoric acid process produce phosphoric acid by-product ardealite, crystal water content be 6%~
12%.
2. half water ardealite mine filling material according to claim 1, it is characterised in that: the tailing refers to that mineral select
Remaining fine grained mine after mine, average grain diameter are 10~75 μm.
3. half water ardealite mine filling material according to claim 1, it is characterised in that: the tailing refers to phosphorus ore
Tailing.
4. described in any item half water ardealite mine filling material according to claim 1~3, it is characterised in that: for by formula
Slurry made from moisture is added in mixed cement, half water ardealite and tailing.
5. half water ardealite mine filling material according to claim 4, it is characterised in that: the solid content of the slurry
It is 60%~80%.
6. prepare the described in any item half water ardealite mine filling material of claims 1 to 3 method, it is characterised in that including with
Lower step: by cement, half water ardealite and tailing according to the ratio require metering after, be uniformly mixed to get.
7. the method for preparing half water ardealite mine filling material described in claim 3 or 4, it is characterised in that including following step
It is rapid: after cement, half water ardealite and tailing are required metering according to the ratio, to be uniformly mixed, moisture is added, is prepared into solid content
The slurry of 60%-80% to get.
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| CN201510981155.2A CN106915941B (en) | 2015-12-24 | 2015-12-24 | Half water ardealite mine filling material and preparation method thereof |
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| CN201510981155.2A CN106915941B (en) | 2015-12-24 | 2015-12-24 | Half water ardealite mine filling material and preparation method thereof |
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| CN106915941B true CN106915941B (en) | 2019-11-19 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109967488A (en) * | 2019-02-28 | 2019-07-05 | 西南科技大学 | A kind of phosphate ore flotation tailings cooperate with harmless disposal method with ardealite |
| CN112934906A (en) * | 2019-12-11 | 2021-06-11 | 西南科技大学 | Method for innocent treatment of phosphorus tailings and phosphogypsum by burning raw materials |
| CN113956011B (en) * | 2021-12-07 | 2023-03-10 | 贵州川恒化工股份有限公司 | Semi-hydrated phosphogypsum-based filling aggregate and preparation method thereof |
| CN114133199A (en) * | 2021-12-21 | 2022-03-04 | 贵州川恒化工股份有限公司 | Semi-hydrated phosphogypsum based geopolymer cemented phosphorus tailing filling material and method for filling mine by using same |
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| 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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| CN104591663A (en) * | 2014-11-17 | 2015-05-06 | 华唯金属矿产资源高效循环利用国家工程研究中心有限公司 | Method for fast preparing mine tailing underground filling material |
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2015
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101008316A (en) * | 2007-01-31 | 2007-08-01 | 贵州开磷（集团）有限责任公司 | Phosphogypsum cementing and post-filling mining method and pulping technology thereof |
| 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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