CN107162547B - A kind of full phosphorus slag gelling filler and its application - Google Patents
A kind of full phosphorus slag gelling filler and its application Download PDFInfo
- Publication number
- CN107162547B CN107162547B CN201710310472.0A CN201710310472A CN107162547B CN 107162547 B CN107162547 B CN 107162547B CN 201710310472 A CN201710310472 A CN 201710310472A CN 107162547 B CN107162547 B CN 107162547B
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- CN
- China
- Prior art keywords
- phosphorus slag
- calcium oxide
- ardealite
- slag
- gelling
- 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.)
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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
- 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
- C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
Abstract
The invention discloses a kind of full phosphorus slag gelling fillers, include ardealite, Phosphorus Slag and calcium oxide；Wherein, calcium oxide is 12% or more of Phosphorus Slag weight.The invention also discloses the applications of full phosphorus slag gelling filler.Furthermore, inhibit the method that pernicious gas generates during full phosphorus slag consolidated fill the invention also discloses a kind of, it is mixed after adding calcium oxide, mixing into the system comprising ardealite, Phosphorus Slag with water, hydration reaction, which occurs, must fill gelling slurry, regulate and control filling gelling slurry pH by calcium oxide and be greater than or equal to 10.In full phosphorus slag cementitious material of the present invention, the calcium oxide is added, the whole release without pernicious gas of the full phosphorus slag cementitious material production process, storing process, filling use process is can control, meets strict demand of the current material to environmental protection.
Description
Technical field
The invention belongs to the technical fields of cementitious material, and in particular to the environmental protection gelling filling comprising Phosphorus Slag, ardealite
Field of material technology.
Background technique
Phosphorus Slag is the industrial residue of generation during electric furnace process phosphorus production.The current Phosphorus Slag total amount about 8,100,000 in China
T/a, earth's surface stockpiling can bring serious environmental pollution and relevant social concern, so by Comprehensive Utilization of Yellow Phosphorus Slag secondary use
Seem especially urgent.
The main chemical compositions of Phosphorus Slag are silica, calcium oxide, aluminum oxide etc..Utilize this water of Phosphorus Slag
Changing characteristic can be using Phosphorus Slag as cement producting material, or prepares Phosphorus Slag cementitious material etc..For example, in the prior art,
It reports some be used in mixed way Phosphorus Slag and ardealite and is used to prepare cement.But now in the art, it is primarily upon yellow phosphorus
The performance of the compound use of slag and ardealite and other adding ingredients, and be seldom concerned about in cementing filling treatment process, it can
The burden of energy bring environmental protection and secure context.
For example, the Chinese patent literature of Publication No. CN103964804A discloses a kind of pumpable ardealite of low bleeding rate
With Phosphorus Slag fill paste, the fill paste is made of ardealite, Phosphorus Slag, water.By the study found that ardealite, yellow phosphorus
The filling paste of slag compounding, which is known from experience, generates pernicious gas, has adverse effect to environment.
Summary of the invention
In order to solve existing full phosphorus slag cementitious material in use to the defect in terms of environmental protection, the present invention provides one
A kind of full phosphorus slag cementitious material of kind, it is desirable to provide cementitious material with safety and environmental-protecting performance.
It is a second object of the invention to provide the application of full phosphorus slag gelling filler described in one kind.
The present invention also provides a kind of methods that full phosphorus slag consolidated fill process toxic and harmful gas generates, it is intended to avoid wrapping
The generation of pernicious gas in the cementitious material mixed process of phosphogypsum and Phosphorus Slag.
A kind of full phosphorus slag gelling filler, includes ardealite, Phosphorus Slag and calcium oxide；Wherein, calcium oxide is Phosphorus Slag
12% or more of weight.
The present inventor is had found by numerous studies, under the component comprising the ardealite, Phosphorus Slag, is added described heavy
It measures under the calcium oxide under percentage, can unexpectedly solve existing technical staff and never have the environmental issue recognized.
Through research, the inventor has found that process is used in combination to ardealite, Phosphorus Slag in the dosage of the calcium oxide
The inhibitory effect of the pernicious gas of middle generation has larger impact.
Preferably, calcium oxide is 12~20% with respect to the additive amount of Phosphorus Slag；Further preferably 16~20%.
In the present invention, the Phosphorus Slag preferably uses Phosphorus Slag made from high pressure water quenching treatment method；Further preferably
For granular Phosphorus Slag made from high pressure water quenching treatment method.The effect of the Phosphorus Slag obtained using the preferred conventional method is more
It is excellent.
The present inventor by research it has also been found that, the ardealite, Phosphorus Slag ratio can be arbitrary proportion, control oxidation
The generation of pernicious gas can be well controllled in the dosage of calcium.However, further investigation discovery, the ardealite, Phosphorus Slag
Weight ratio be preferably 3: 1-6: 1.Under the ratio, facilitates the calcium oxide for cooperating the height to add content cooperation, keep
The superperformance of cementing filling material (present invention is also referred to as the filler that is gelled).
Full phosphorus slag cementitious material of the present invention, except the ardealite comprising the weight content, Phosphorus Slag and calcium oxide
Under, it can also add material known to those skilled in the art institute energy, such as cement.
The present invention also provides a kind of application methods of full phosphorus slag gelling filler, and the component is mixed with water,
Gelling slurry (present invention also referred to as be gelled slurry) must be filled after aquation；The filling gelling slurry is used for consolidated fill mistake
Journey.
Preferably, in the described application, ardealite, Phosphorus Slag weight ratio be 3: 1-6: 1；Calcium oxide is with respect to Phosphorus Slag
Additive amount be 16~20%.
Preferably, being greater than or equal to 10 by the pH of the calcium oxide regulation filling gelling slurry.
Application of the invention, may further be embodied as: a kind of to inhibit the side that pernicious gas generates during full phosphorus slag consolidated fill
Method mixes after adding calcium oxide, mixing into the system comprising ardealite, Phosphorus Slag with water, and hydration reaction, which occurs, must fill glue
Solidifying slurry regulates and controls filling gelling slurry pH by calcium oxide and is greater than or equal to 10.
Further preferably, the method that pernicious gas generates during the full phosphorus slag consolidated fill of inhibition, calcium oxide
Additive amount is 12% or more of Phosphorus Slag weight；Further preferably 16~20%.
Preferably, the pernicious gas is PH3、H2S, CO, NH3, NO, PCl3At least one of.
In the present invention, cut down reproducibility toxic and harmful gas hydrogen sulfide, hydrogen phosphide, an oxygen during ardealite consolidated fill
Change carbon, ammonia, nitric oxide and phosphorus trichloride, by controlling the pH of filling slurry, ardealite consolidated fill process is generated
Toxic and harmful gas into prevention and treatment.
Calcium oxide is added in Phosphorus Slag, and ardealite and the Phosphorus Slag for being added to calcium oxide enter hybrid reaction slurry system
Hydration reaction occurs for system, and the add value of calcium oxide must be enough, to guarantee the slurry pH of hybrid reaction system not less than 10.
The present invention theoretically can also be used in it is existing comprising ardealite, Phosphorus Slag cementitious material use process in harmful gas
The release of body, to it is existing comprising ardealite, Phosphorus Slag cementitious material in add calcium oxide under the weight ratio, then
Rehydration uses.
The present inventor has found in numerous studies, when the reducing substances and ardealite of remaining part contact in Phosphorus Slag, meeting
Toxic and harmful gas is released, these, into air, cause air pollution and occupational hazards with certain harmful gases diffusion.Especially
It is for during the ardealite consolidated fill that is carried out using Phosphorus Slag cementitious material as gelling agent, ardealite can to fill
Slurry discharges more PH3And H2S.If poisonous and hazardous reducibility gas is assembled in relatively closed situation, it will bring serious
Poisoning harm.Therefore, toxic in ardealite that those skilled in the art never recognize and Phosphorus Slag gelatinization to solve
Pernicious gas discharges problem, and the present inventor is had found by numerous studies, adds the calcium oxide of the high-content ratio, can solve
The technical problem.
In full phosphorus slag cementitious material of the present invention, the calcium oxide is added, can control the full phosphorus slag gelling
The whole release without pernicious gas of Material Manufacturing Process, storing process, filling use process, meets current material to environmental protection
It is strict with.
Detailed description of the invention
Fig. 1 is the H of Examples 1 to 3 and comparative example 1~32The testing result figure of S；
Fig. 2 is the PH of Examples 1 to 3 and comparative example 1~33Testing result figure；
Fig. 3 is the testing result figure of the CO of Examples 1 to 3 and comparative example 1~3；
Fig. 4 is the NH of Examples 1 to 3 and comparative example 1~33Testing result figure；
Fig. 5 is the testing result figure of the NO of Examples 1 to 3 and comparative example 1~3；
Fig. 6 is the PCl of Examples 1 to 3 and comparative example 1~33Testing result figure；
Specific embodiment
Embodiment 1:
Ardealite and the control of Phosphorus Slag ratio are 5: 1 (dry weights), and the ardealite (dry weight) after weighing is 5.0g, and Phosphorus Slag is
1.0g, deionized water 50ml, aquation obtain slurry；Wherein, calcium oxide is added in Phosphorus Slag, makes calcium oxide with respect to yellow phosphorus ground-slag
Degree is 12% (pH of the slurry of control aquation is 11.68)；Entire hydration process in closed glass container into
Row, entire slurry hybrid reaction simulate the preparation process of filling slurry on site.The generation feelings of hydrogen sulfide are monitored in experimentation
Condition.H2The removing data of S are shown in Fig. 1, as described in Figure 1, H2The removal efficiency of S reaches 99%.
Embodiment 2:
It is compared with embodiment 1, difference is only that, calcium oxide is 16% with respect to the degree of yellow phosphorus ground-slag.
Embodiment 3:
It is compared with embodiment 1, difference is only that, calcium oxide is 20% with respect to the degree of yellow phosphorus ground-slag.
Comparative example 1:
It is compared with embodiment 1, difference is only that, does not add calcium oxide.
Comparative example 2:
It is compared with embodiment 1, difference is only that, calcium oxide is 4% with respect to the degree of yellow phosphorus ground-slag.
Comparative example 3:
It is compared with embodiment 1, difference is only that, calcium oxide is 8% with respect to the degree of yellow phosphorus ground-slag.
The H of Examples 1 to 3 and comparative example 1~32The testing result of S is as shown in Figure 1.
The PH of Examples 1 to 3 and comparative example 1~33Testing result as shown in Figure 2.
The testing result of the CO of Examples 1 to 3 and comparative example 1~3 is as shown in Figure 3.
The NH of Examples 1 to 3 and comparative example 1~33Testing result as shown in Figure 4.
The testing result of the NO of Examples 1 to 3 and comparative example 1~3 is as shown in Figure 5.
The PCl of Examples 1 to 3 and comparative example 1~33Testing result see Fig. 6.
As shown in Fig. 1~5, in embodiment 1, H2The removal efficiency of S is 99%；PH3Removal efficiency be 98.6%；The removing of CO
Rate is 99.4%；NH3Removal efficiency be 100%；The removal efficiency of NH3 is 100%；PCl3Removal efficiency be 100%.2 He of embodiment
3 each pernicious gas is controlled in 0 discharge.Experiment effect of the invention is much better than comparative example.
From the result of study of above embodiments and comparative example show technical solution of the present invention can solve it is existing such as
The pernicious gas problem generated in ardealite and Phosphorus Slag the joint filling process that CN103964804A is pointed out.
Claims (2)
1. a kind of inhibit the method that pernicious gas generates during full phosphorus slag consolidated fill, which is characterized in that comprising ardealite,
It is mixed after adding calcium oxide, mixing in the system of Phosphorus Slag with water, hydration reaction, which occurs, must fill gelling slurry, pass through calcium oxide
Regulation filling gelling slurry pH is greater than or equal to 10；
The additive amount of calcium oxide is the 12% or 16% of Phosphorus Slag weight.
2. inhibiting the method that pernicious gas generates during full phosphorus slag consolidated fill as described in claim 1, which is characterized in that
The pernicious gas is PH3、H2S、CO、NH3、NO、PCl3At least one of.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710310472.0A CN107162547B (en) | 2017-05-04 | 2017-05-04 | A kind of full phosphorus slag gelling filler and its application |
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| CN201710310472.0A CN107162547B (en) | 2017-05-04 | 2017-05-04 | A kind of full phosphorus slag gelling filler and its application |
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| CN107162547A CN107162547A (en) | 2017-09-15 |
| CN107162547B true CN107162547B (en) | 2019-11-26 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107764820A (en) * | 2017-11-21 | 2018-03-06 | 长沙湘朴科技有限公司 | A kind of toxic and harmful gas detection means and method for mine filling |
| CN107989651B (en) * | 2017-11-27 | 2019-07-19 | 固岩科技发展有限公司 | A kind of method in foam phosphorus slag material filling mine |
| CN113603441A (en) * | 2021-08-26 | 2021-11-05 | 昆明理工大学 | Method for preparing phosphogypsum-based gelled filling material by CaO phosphorus fixation |
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| CN103626462A (en) * | 2013-11-01 | 2014-03-12 | 贵州开磷（集团）有限责任公司 | Autoclaved yellow phosphorus slag pavement brick and making method thereof |
| 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 |
| CN104725013A (en) * | 2015-02-04 | 2015-06-24 | 贵州开磷集团股份有限公司 | Phosphogypsum base material marble-imitated floor tile and preparation method thereof |
| CN104761226A (en) * | 2015-02-04 | 2015-07-08 | 贵州开磷集团股份有限公司 | Marble-texture-imitation decorative board and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11292578A (en) * | 1998-04-06 | 1999-10-26 | Hisamitsu Tsuyuki | Belite slag |
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2017
- 2017-05-04 CN CN201710310472.0A patent/CN107162547B/en active Active
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| CN103626462A (en) * | 2013-11-01 | 2014-03-12 | 贵州开磷（集团）有限责任公司 | Autoclaved yellow phosphorus slag pavement brick and making method thereof |
| 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 |
| CN104725013A (en) * | 2015-02-04 | 2015-06-24 | 贵州开磷集团股份有限公司 | Phosphogypsum base material marble-imitated floor tile and preparation method thereof |
| CN104761226A (en) * | 2015-02-04 | 2015-07-08 | 贵州开磷集团股份有限公司 | Marble-texture-imitation decorative board and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 黄磷渣充填胶凝材料激发剂的选择与优化;廖国燕等;《金属矿山》;17-19，99;20100331(第405期);第11--13,19页 * |
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