CN107162547A - 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
- CN107162547A CN107162547A CN201710310472.0A CN201710310472A CN107162547A CN 107162547 A CN107162547 A CN 107162547A CN 201710310472 A CN201710310472 A CN 201710310472A CN 107162547 A CN107162547 A CN 107162547A
- Authority
- CN
- China
- Prior art keywords
- phosphorus slag
- calcium oxide
- gelling
- full phosphorus
- ardealite
- 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
-
- 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 filler, ardealite, Phosphorus Slag and calcium oxide are included;Wherein, calcium oxide for Phosphorus Slag weight 12% and more than.The invention also discloses the application of described full phosphorus slag gelling filler.In addition, the invention also discloses the method that pernicious gas during a kind of full phosphorus slag consolidated fill of suppression is produced, to comprising in ardealite, the system of Phosphorus Slag add calcium oxide, mixing after mixed with water, generation hydration reaction must fill gelling slurry, be greater than or equal to 10 by calcium oxide regulation and control filling gelling slurry pH.In full phosphorus slag binder materials of the present invention, the described calcium oxide of addition can control described full phosphorus slag binder materials production process, storing process, filling using the whole release without pernicious gas of process, meet strict demand of the current material to environmental protection.
Description
Technical field
The invention belongs to the technical field of binder materials, and in particular to the environmental protection gelling filling comprising Phosphorus Slag, ardealite
Field of material technology.
Background technology
Phosphorus Slag is the industrial residue produced during electric furnace process phosphorus production.The current Phosphorus Slag total amount about 8,100,000 of China
T/a, its earth's surface, which is stored up, can bring serious environmental pollution and related social concern, so utilizing Comprehensive Utilization of Yellow Phosphorus Slag is secondary
Seem particularly urgent.
The main chemical compositions of Phosphorus Slag are silica, calcium oxide, alundum (Al2O3) etc..Utilize this water of Phosphorus Slag
Changing characteristic can be using Phosphorus Slag as cement producting material, or prepares Phosphorus Slag binder materials etc..For example, in the prior art,
Report some Phosphorus Slag and ardealite are used in mixed way for preparing 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 processing procedure, can
The environmental protection that can be brought and the burden of secure context.
For example, Publication No. CN103964804A Chinese patent literature discloses a kind of pumpable ardealite of low bleeding rate
With Phosphorus Slag fill paste, the fill paste is made up of ardealite, Phosphorus Slag, water.Found by studying, ardealite, yellow phosphorus
The filling paste of slag compounding, which is known from experience, produces pernicious gas, and environment is had adverse effect.
The content of the invention
In order to solve existing full phosphorus slag binder materials in use to the defect in terms of environmental protection, the invention provides one
Plant full phosphorus slag binder materials, it is desirable to provide a kind of binder materials with safety and environmental-protecting performance.
The application of filler it is a second object of the invention to provide a kind of described full phosphorus slag is gelled.
Present invention also offers a kind of method that full phosphorus slag consolidated fill process toxic and harmful gas is produced, it is intended to avoids bag
The generation of pernicious gas in the binder materials 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
Weight 12% and more than.
The present inventor is had found by numerous studies, under comprising described ardealite, the component of Phosphorus Slag, is added described heavy
Measure under the calcium oxide under percentage, can unexpectedly solve existing technical staff and never have the environmental issue recognized.
The present inventor has found that process is used in combination to ardealite, Phosphorus Slag in the dosage of described calcium oxide by studying
The inhibition of the pernicious gas of middle generation has considerable influence.
Preferably, calcium oxide is 12~20% with respect to the addition of Phosphorus Slag;More preferably 16~20%.
In the present invention, described Phosphorus Slag is preferred to use Phosphorus Slag made from high pressure water quenching treatment method;Further preferably
The 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, described ardealite, the ratio of Phosphorus Slag can be arbitrary proportion, control oxidation
The dosage of calcium can be advantageously controlled the generation of pernicious gas.However, further investigation is found, described ardealite, Phosphorus Slag
Weight ratio preferably 3: 1-6: 1.Under the ratio, the calcium oxide for contributing to the height described in coordinating to add content coordinates, and keeps
The superperformance of cementing filling material (present invention also referred to as gelling filler).
Full phosphorus slag binder materials of the present invention, except the ardealite comprising the weight content, Phosphorus Slag and calcium oxide
Under, can also add those skilled in the art institute can well known material, such as cement.
Present invention also offers a kind of application process of full phosphorus slag gelling filler, described component is mixed with water,
Gelling slurry (slurry of the invention that is also referred to as gelled) must be filled after aquation;Described filling gelling slurry is used for consolidated fill mistake
Journey.
Preferably, in described application, ardealite, the weight ratio of Phosphorus Slag are 3: 1-6: 1;Calcium oxide is with respect to Phosphorus Slag
Addition be 16~20%.
Preferably, the pH for regulating and controlling described filling gelling slurry by calcium oxide is more than or equal to 10.
The application of the present invention, may further be embodied as:The side that pernicious gas is produced during a kind of full phosphorus slag consolidated fill of suppression
Method, to comprising being mixed after calcium oxide, mixing are added in ardealite, the system of Phosphorus Slag with water, glue must be filled by occurring hydration reaction
Solidifying slurry, is greater than or equal to 10 by calcium oxide regulation and control filling gelling slurry pH.
Further preferably, the method that pernicious gas is produced during the described full phosphorus slag consolidated fill of suppression, calcium oxide
Addition for Phosphorus Slag weight 12% and more than;More preferably 16~20%.
Preferably, described 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 produced
The preventing and treating that toxic and harmful gas enters.
Calcium oxide is added in Phosphorus Slag, and ardealite enters hybrid reaction slurry system with the addition of the Phosphorus Slag of calcium oxide
System, occurs hydration reaction, the add value of calcium oxide must be enough, is not less than 10 with the slurry pH for ensureing hybrid reaction system.
The present invention can be additionally used in the existing harmful gas included during ardealite, the binder materials use of Phosphorus Slag in theory
The release of body, adds calcium oxide under the part by weight, then to existing include in ardealite, the binder materials of Phosphorus Slag
Rehydration is used.
The present inventor has found in numerous studies, when the reducing substances of the part remained in Phosphorus Slag is contacted with ardealite, meeting
Toxic and harmful gas is discharged, these have certain harmful gases diffusion into air, cause air pollution and occupational hazards.Especially
It is for during the ardealite consolidated fill that is carried out using Phosphorus Slag binder materials as gelling agent, ardealite can cause filling
Slurry discharges more PH3And H2S.If poisonous and hazardous reducibility gas is assembled in the case of relatively closed, it will bring serious
Poisoning harm.Therefore, it is poisonous in the ardealite and Phosphorus Slag gelatinization never recognized for solution those skilled in the art
Pernicious gas discharges problem, and the present inventor is had found by numerous studies, the calcium oxide of the described high content ratio of addition, can solve
The technical problem.
In full phosphorus slag binder materials of the present invention, the described calcium oxide of addition can control described full phosphorus slag gelling
Material Manufacturing Process, storing process, filling meet current material to environmental protection using the whole release without pernicious gas of process
It is strict with.
Brief description of the drawings
Fig. 1 is the H of embodiment 1~3 and comparative example 1~32S testing result figure;
Fig. 2 is the PH of embodiment 1~3 and comparative example 1~33Testing result figure;
Fig. 3 is the CO of embodiment 1~3 and comparative example 1~3 testing result figure;
Fig. 4 is the NH of embodiment 1~3 and comparative example 1~33Testing result figure;
Fig. 5 is the NO of embodiment 1~3 and comparative example 1~3 testing result figure;
Fig. 6 is the PCl of embodiment 1~3 and comparative example 1~33Testing result figure;
Embodiment
Embodiment 1:
Ardealite and Phosphorus Slag ratio control to be 5: 1 (dry weights), and the ardealite (dry weight) after weighing is 5.0g, and Phosphorus Slag is
1.0g, deionized water 50ml, aquation obtains slurry;Wherein, calcium oxide is added in Phosphorus Slag, makes calcium oxide with respect to yellow phosphorus ground-slag
Degree is 12% (pH for controlling the slurry of aquation is 11.68);Whole hydration process enters in closed glass container
OK, whole slurry hybrid reaction is simulated in the preparation process of live filling slurry.The generation feelings of hydrogen sulfide are monitored in experimentation
Condition.H2S removing data are shown in Fig. 1, as described in Figure 1, H2S removal efficiency reaches 99%.
Embodiment 2:
Compare, differ only in embodiment 1, calcium oxide is 16% with respect to the degree of yellow phosphorus ground-slag.
Embodiment 3:
Compare, differ only in embodiment 1, calcium oxide is 20% with respect to the degree of yellow phosphorus ground-slag.
Comparative example 1:
Compare, differ only in embodiment 1, without calcium oxide.
Comparative example 2:
Compare, differ only in embodiment 1, calcium oxide is 4% with respect to the degree of yellow phosphorus ground-slag.
Comparative example 3:
Compare, differ only in embodiment 1, calcium oxide is 8% with respect to the degree of yellow phosphorus ground-slag.
The H of embodiment 1~3 and comparative example 1~32S testing result is as shown in Figure 1.
The PH of embodiment 1~3 and comparative example 1~33Testing result as shown in Figure 2.
The CO of embodiment 1~3 and comparative example 1~3 testing result is as shown in Figure 3.
The NH of embodiment 1~3 and comparative example 1~33Testing result as shown in Figure 4.
The NO of embodiment 1~3 and comparative example 1~3 testing result is as shown in Figure 5.
The PCl of embodiment 1~3 and comparative example 1~33Testing result see Fig. 6.
As shown in Fig. 1~5, in embodiment 1, H2S removal efficiency is 99%;PH3Removal efficiency be 98.6%;CO removing
Rate is 99.4%;NH3Removal efficiency be 100%;NH3 removal efficiency is 100%;PCl3Removal efficiency be 100%.The He of embodiment 2
3 each pernicious gas is controlled in 0 discharge.The experiment effect of the present invention is much better than comparative example.
Show from the result of study of above example and comparative example, technical solution of the present invention can solve it is existing such as
The pernicious gas problem produced in ardealite and Phosphorus Slag the joint filling process that CN103964804A is pointed out.
Claims (10)
1. a kind of full phosphorus slag gelling filler, it is characterised in that include ardealite, Phosphorus Slag and calcium oxide;Wherein, calcium oxide
For Phosphorus Slag weight 12% and more than.
2. full phosphorus slag gelling filler as claimed in claim 1, it is characterised in that addition of the calcium oxide with respect to Phosphorus Slag
For 12~20%.
3. full phosphorus slag gelling filler as claimed in claim 1, it is characterised in that addition of the calcium oxide with respect to Phosphorus Slag
For 16~20%.
The application process of filler 4. the full phosphorus slag as described in any one of claims 1 to 3 is gelled, it is characterised in that by institute
The component stated is mixed with water, and gelling slurry must be filled after aquation;Described filling gelling slurry is used for consolidated fill process.
The application process of filler 5. full phosphorus slag as claimed in claim 4 is gelled, it is characterised in that regulated and controled by calcium oxide
The pH of described filling gelling slurry is more than or equal to 10.
6. a kind of suppress the method that pernicious gas during full phosphorus slag consolidated fill is produced, it is characterised in that to comprising ardealite,
Mixed after calcium oxide, mixing are added in the system of Phosphorus Slag with water, gelling slurry must be filled by occurring hydration reaction, pass through calcium oxide
Regulation and control filling gelling slurry pH is greater than or equal to 10.
7. suppress the method that pernicious gas is produced during full phosphorus slag consolidated fill as claimed in claim 6, it is characterised in that
The addition of calcium oxide for Phosphorus Slag weight 12% and more than.
8. suppress the method that pernicious gas is produced during full phosphorus slag consolidated fill as claimed in claim 7, it is characterised in that
The addition of calcium oxide is the 12~20% of Phosphorus Slag weight.
9. suppress the method that pernicious gas is produced during full phosphorus slag consolidated fill as claimed in claim 7, it is characterised in that
The addition of calcium oxide is the 16~20% of Phosphorus Slag weight.
10. suppressing the method that pernicious gas is produced during full phosphorus slag consolidated fill as claimed in claim 6, its feature exists
In described pernicious gas is PH3、H2S, CO, NH3, NO, PCl3At least one of.
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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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CN107162547B CN107162547B (en) | 2019-11-26 |
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Cited By (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 |
CN107989651A (en) * | 2017-11-27 | 2018-05-04 | 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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JPH11292578A (en) * | 1998-04-06 | 1999-10-26 | Hisamitsu Tsuyuki | Belite slag |
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 |
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JPH11292578A (en) * | 1998-04-06 | 1999-10-26 | Hisamitsu Tsuyuki | Belite slag |
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 |
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Cited By (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 |
CN107989651A (en) * | 2017-11-27 | 2018-05-04 | 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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