CN101684675B - Autoclaved phosphogypsum brick and method for preparing same - Google Patents

Autoclaved phosphogypsum brick and method for preparing same Download PDF

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Publication number
CN101684675B
CN101684675B CN2009103057886A CN200910305788A CN101684675B CN 101684675 B CN101684675 B CN 101684675B CN 2009103057886 A CN2009103057886 A CN 2009103057886A CN 200910305788 A CN200910305788 A CN 200910305788A CN 101684675 B CN101684675 B CN 101684675B
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China
Prior art keywords
ardealite
slag
brick
modifier
autoclaved
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Expired - Fee Related
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CN2009103057886A
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CN101684675A (en
Inventor
蒲中云
陈维贵
马功富
杨守明
罗万林
钟显刚
易遵礼
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SICHUAN HONGDA CO Ltd
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SICHUAN HONGDA CO Ltd
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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14Compositions 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
    • C04B28/142Compositions 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
    • C04B28/143Compositions 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • C04B2201/52High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The invention discloses an autoclaved phosphogypsum brick completely prepared by industrial waste residues and a method for preparing the same and belongs to the technical field of construction materials. The autoclaved phosphogypsum brick is prepared from the following raw materials in part by weight: 60 to 80 parts of phosphogypsum, 3.9 to 7.8 parts of neutralization modifying agent, 15 to 30 parts of activated admixture, 1 to 2 parts of cementing aggregate, 0.1 to 0.2 part of exciting agent and 10 to 15 parts of water, wherein the neutralization modifying agent is carbide slag or lime slag; the activated admixture is one or more of zinc smelting granulated slag, fluidized bed furnace fire coal slag and grate furnace fire coal slag; the cementing aggregate is construction sand; and the exciting agent is glauber salt or sodium sulfate. The compressive strength of the autoclaved phosphogypsum brick disclosed in the invention reaches 15 to 20MPa.

Description

A kind of autoclaved phosphogypsum brick and manufacturing approach thereof
Technical field
The invention discloses a kind of autoclaved phosphogypsum brick that adopts the industrial residue manufacturing fully and preparation method thereof, belong to building material technical field.
Background technology
In smelting or chemical process, can produce a large amount of industrial residues; Like the ardealite that phosphorus chemical industry produces, the zinc of zinc smelting device by-product is smelted grain slag, the carbide slag of calcium carbide factory's by-product; The coal-fired slag of fluidized bed furnace that coal-fired fluidized-bed kiln is residual, the coal-fired slag of chain grate furnace that coal-fired chain grate furnace is residual etc.The comprehensive utilization of industrial residue is a huge and complicated system engineering, and along with the continuous development of chemical industry, the processing pressure of industrial residue is increasing, wherein especially with the processing pressure of ardealite for.Because the composition of ardealite is with CaSO 42H 2O is main (its quality percentage composition about 85%95%), also contains P 2O 5, small amount of impurities such as fluoride and iron, aluminium, magnesium, silicon, so its comprehensive utilization difficulty relatively.
China's comprehensive utilization of phosphogypsum research was carried out since the sixties, and the method for comprehensive utilization ardealite mainly contains ardealite system producing sulfuric acid and jointly cement, producing cement from phosphor retarding agent, ardealite producing building land plaster, ardealite system gypsum plank, the gypsum block of ardealite system etc.All there be the shortcoming high to the ardealite quality requirements in above-mentioned ardealite development scheme, and most of ardealite can not use, and makes its limited use.Thereby the ardealite of present most phosphorous chemical industry enterprise all do not obtain a large amount of development and use, and volume of cargo in storage is huge day by day, and the ardealite that pile up like a mountain takies a large amount of soils, also brings a series of environmental protection pressures simultaneously.
In order to address the above problem, people have begun the research of ardealite as constructional materials.The technology that with the ardealite is the main material production building brick at present mainly contains two kinds, and a kind of is earlier ardealite to be carried out the steam-cured preliminary treatment of Denging, or with CaSO 42H 2O is processed into CaSO 41/2H 2O adds industrial wastes such as slag, machine-shaping more according to a certain percentage; Another kind method is that bonding agents such as ardealite and cement are mixed back moulded section.Adopt these two kinds of method synthesis to utilize ardealite all to exist the high deficiency of cost, and the compressive strength of the building block of producing is lower, generally is difficult to reach 10MPa, is difficult to adapt to the requirement of modern architecture constructional materials.
Summary of the invention
The objective of the invention is to overcome the deficiency that cost is high, ardealite brick intensity is low that exists in the existing ardealite comprehensive utilization technique, the autoclaved phosphogypsum brick that a kind of cost is low, intensity is high is provided.Another object of the present invention is to provide the preparation method of this autoclaved phosphogypsum brick.
In order to realize the foregoing invention purpose, the technical scheme below the present invention has adopted:
A kind of autoclaved phosphogypsum brick is got by the feedstock production of following weight portion:
Ardealite 60-80 part, in modifier 3.9-7.8 part, active fusion material 15-30 part; Glued aggregate 1-2 part, exciting agent 0.1-0.2 part, water 10-15 part; In said with modifier be carbide slag or lime mud; Said active fusion material is that zinc is smelted any one or a few in grain slag, the coal-fired slag of fluidized bed furnace, the coal-fired slag of chain grate furnace, and said glued aggregate is building sand, and said exciting agent is saltcake or glauber salt.
Said building sand is preferably the building sand of particle diameter<2mm, with the intensity of guaranteeing that autoclaved phosphogypsum brick is required.
The preparation method of said ardealite brick may further comprise the steps:
(1), gets the raw materials ready: mass percentage content<5% that ardealite is dried to its free moisture; With in be dried to the mass percentage content of its free moisture<2% back grinding respectively with modifier, active fusion material and become the fine powder of 80 order fineness;
(2), batching: with ardealite in the step (1), in and modifier, active fusion material and exciting agent by following weight portion batching: ardealite 60-80 part, in and modifier 3.9-7.8 part, active fusion material 15-30 part, exciting agent 0.1-0.2 part;
(3), grind: step (2) gained batching is placed ball mill, grind, mix;
(4), stir: in step (3) gained batching, add glued aggregate 1-2 part and stir; Add water 10-15 part again, stir;
(5), brickmaking: place brickmaking machine to be pressed into adobe step (4) gained batching;
(6), maintenance: with the adobe that makes in pressure is the steam-cured still of 0.4~1.5MPa with saturated vapour maintenance 7-10h, make finished product.
Among the preparation method of above-mentioned autoclaved phosphogypsum brick, add water from step (4) and be stirred to the time of processing adobe and preferably be controlled in the 15min, in order to avoid the batching partially hardened influences the building brick moulding.
Autoclaved phosphogypsum brick disclosed by the invention is to be main base-material with ardealite, is prepared from modifier, active fusion material, glued aggregate, exciting agent and water in the cooperation.The main component of ardealite is CaSO 42H 2O contains P in addition 2O 5, small amount of impurities such as fluoride and iron, aluminium, magnesium, silicon.Because water-soluble P 2O 5, fluoride can have a negative impact to the intensity of brick, thereby the inventor in prescription, add carbide slag or lime mud as in and modifier, in ardealite in water-soluble P 2O 5, F, reduce its negative effect, thereby reach the effect that improves autoclaved phosphogypsum brick body intensity.In addition, also add zinc in the prescription and smelt in grain slag, the coal-fired slag of fluidized bed furnace, the coal-fired slag of chain grate furnace any one or a few, excite the Fe that contains in these waste residues through steam-cured as active fusion material 2O 3, AL 2O 3, CaO, MgO or SiO 2With ardealite generation hydration reaction, for steam-pressing brisk provides intensity.(the Fe in the coal-fired slag of fluidized bed furnace 2O 3, AL 2O 3, CaO, MgO, SiO 2The quality percentage composition be respectively 5.26%, 29.71%, 3.72%, 1.88%, 51.66%; Zinc is smelted the Fe of grain slag 2O 3, AL 2O 3, CaO, MgO, SiO 2The quality percentage composition be respectively 29.71%, 15.26%, 7.72%, 1.88%, 36.35%, the Fe of the coal-fired slag of chain grate furnace 2O 3, AL 2O 3, CaO, MgO, SiO 2Quality percentage composition respectively 6.13%, 21.36%, 8.81%, 2.00%, 45.97%).For exciting the aquation of quickening active fusion material, improve the reaction speed of ardealite brick in steam-cured process, improve the early strength of brick, select for use saltcake or glauber salt as exciting agent.
Autoclaved phosphogypsum brick disclosed by the invention; In the preparation process with ardealite, in and modifier, exciting agent, active fusion material carry out sufficient homogenizing with ball mill and mix; Make the steady quality of finished bricks; Grinding can destroy the crystal habit of material, improves the reactivity of material, thereby improves the intensity of finished bricks.
Compared with prior art, the present invention has following beneficial effect: autoclaved phosphogypsum brick disclosed by the invention, and its compressive strength can reach 15~30MPa, and this is because the present invention distinctive material component prescription and preparation method produce.Autoclaved phosphogypsum brick of the present invention can also be by user's requirement customization.The finished product that makes can reach the requirement of the above intensity level quality index of MU15 of GB13544-2000 Fired perforated bricks, GB13545-92 Fired hollow bricks and blocks, GB11945-1999 Autoclaved limesand brick, the non-sintering rubbish of JC/T422-2007 tailing-bricks relevant criterion.
It is raw material that the present invention adopts the tailings of phosphorous chemical industry enterprise self by-product fully; Low to raw material ardealite quality requirements; The ardealite that sanitary index is qualified can both use, and produces the environmental type autoclaved phosphogypsum brick that is up to state standards, its low cost of manufacture; Preparation method is simple, can fully utilize industrial residue in enormous quantities.Adopt technical scheme of the present invention to make autoclaved phosphogypsum brick; Can fully utilize ardealite on a large scale to greatest extent, substitute traditional loam brick, shale brick, both protect land resources; For building material industry provides environmental protection, energy-saving pollution-free green building material product; Also be the effective measure of comprehensive environmental improvement simultaneously, meet the recycling economy strategy of the construction sustainable development of country, economic benefit and obvious social benefit.
The specific embodiment
Below in conjunction with the specific embodiment the present invention is made further detailed description.But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, allly all belong to scope of the present invention based on the technology that content of the present invention realized.
Autoclaved phosphogypsum brick is prepared from following materials of weight proportions among the cited embodiment of the present invention:
Ardealite 60-80 part, in modifier 3.9-7.8 part, active fusion material 15-30 part; Glued aggregate 1-2 part, exciting agent 0.1-0.2 part, water 10-15 part; In said with modifier be carbide slag or lime mud; Said active fusion material is that zinc is smelted any one or a few in grain slag, the coal-fired slag of fluidized bed furnace, the coal-fired slag of chain grate furnace, and said glued aggregate is building sand, and said exciting agent is saltcake or glauber salt.
The preparation method of autoclaved phosphogypsum brick is following among the cited embodiment of the present invention:
(1), gets the raw materials ready: mass percentage content<5% that ardealite is dried to its free moisture; With in be dried to the mass percentage content of its free moisture<2% back grinding respectively with modifier, active fusion material and become the fine powder of 80 order fineness;
(2), the batching: with ardealite, in and modifier, exciting agent, active fusion material prepare burden by weight proportion;
(3), grind: step (2) gained batching is placed? The cement testing ball mill of 00 * 500mm grinds, and mixes;
(4), stir: in step (3) gained batching, add the building sand of particle diameter<2mm by weight ratio, add entry after stirring in proportion, stir;
(5), brickmaking: add water and stir in the 15min of back, place brickmaking machine to be pressed into adobe step (4) gained batching;
(6), maintenance: with the adobe that makes in pressure is the steam-cured still of 0.4~1.5MPa with saturated vapour maintenance 7h~10h, make finished product.
Embodiment 1
The autoclaved phosphogypsum brick that present embodiment provides is processed by following raw material:
Ardealite 60kg, carbide slag 7.8kg, zinc is smelted grain slag 30kg, the building sand 2kg of particle diameter<2mm, saltcake 0.2kg, water 15kg.
With the raw material of said ratio according to get the raw materials ready, prepare burden, grind, the step of stirring, brickmaking, maintenance is prepared into autoclaved phosphogypsum brick.In the autoclaved phosphogypsum brick that present embodiment makes, choose 5 wantonly, according to the standard of GB/T 2542-2003 " Test methods for wall bricks ", carry out compression test with the TYE-3000 pressure testing machine, its result sees table 1.
Embodiment 2
The autoclaved phosphogypsum brick that present embodiment provides is processed by following raw material:
Ardealite 75kg, carbide slag 3.9kg, the coal-fired slag 20kg of fluidized bed furnace, the building sand 1kg of particle diameter<2mm, saltcake 0.1kg, water 11kg.
With the raw material of said ratio according to get the raw materials ready, prepare burden, grind, the step of stirring, brickmaking, maintenance is prepared into autoclaved phosphogypsum brick.In the autoclaved phosphogypsum brick that present embodiment makes, choose 5 wantonly, according to the standard of GB/T 2542-2003 " Test methods for wall bricks ", carry out compression test with the TYE-3000 pressure testing machine, its result sees table 1.
Embodiment 3
The autoclaved phosphogypsum brick that present embodiment provides is processed by following raw material:
Gypsum 80kg, lime mud 3.9kg, the coal-fired slag 15kg of chain grate furnace, the building sand 1kg of particle diameter<2mm, glauber salt 0.1kg, water 10kg.
With the raw material of said ratio according to get the raw materials ready, prepare burden, grind, the step of stirring, brickmaking, maintenance is prepared into autoclaved phosphogypsum brick.In the autoclaved phosphogypsum brick that present embodiment makes, choose 5 wantonly, according to the standard of GB/T 2542-2003 " Test methods for wall bricks ", carry out compression test with the TYE-3000 pressure testing machine, its result sees table 1.
Table 1 baking-free ardealite brick compression test result
Test Example
Below in conjunction with Comparative Examples effect of the present invention is done further to describe in detail.Test Example and Comparative Examples autoclaved phosphogypsum brick process by following raw material:
Ardealite 70kg, carbide slag 5kg, zinc is smelted grain slag 22.8kg, the building sand 2kg of particle diameter<2mm, saltcake 0.2kg, water 12kg.
Test Example is ground batching in preparation process, and Comparative Examples is not ground, and remaining preparation method is identical, be prepared into finished product after, do resistance to compression and detect for optional at random respectively 3, it the results are shown in Table 2.The result shows to grind can make the compressive strength of autoclaved phosphogypsum brick obviously increase.
Table 2, grinding, do not grind contrast test

Claims (3)

1. autoclaved phosphogypsum brick is characterized in that it is to be got by the feedstock production of following weight portion:
Ardealite 60-80 part, in modifier 3.9-7.8 part, active fusion material 15-30 part; Glued aggregate 1-2 part, exciting agent 0.1-0.2 part, water 10-15 part; In said with modifier be carbide slag or lime mud; Said active fusion material is that zinc is smelted any one or a few in grain slag, the coal-fired slag of fluidized bed furnace, the coal-fired slag of chain grate furnace, and said glued aggregate is building sand, and said exciting agent is saltcake or glauber salt.
2. autoclaved phosphogypsum brick according to claim 1 is characterized in that: the building sand that said building sand is particle diameter<2mm.
3. the manufacturing approach of autoclaved phosphogypsum brick according to claim 1 is characterized in that may further comprise the steps:
(1), gets the raw materials ready: mass percentage content<5% that ardealite is dried to its free moisture; With in be dried to the mass percentage content of its free moisture<2% back grinding respectively with modifier, active fusion material and become the fine powder of 80 order fineness;
(2), batching: with ardealite in the step (1), in and modifier, active fusion material and exciting agent by following weight portion batching: ardealite 60-80 part, in and modifier 3.9-7.8 part, active fusion material 15-30 part, exciting agent 0.1-0.2 part;
(3), grind: step (2) gained batching is placed ball mill, grind, mix;
(4), stir: in step (3) gained batching, add glued aggregate 1-2 part and stir; Add water 10-15 part again, stir;
(5), brickmaking: place brickmaking machine to be pressed into adobe step (4) gained batching;
(6), maintenance: with the adobe that makes in pressure is the steam-cured still of 0.4~1.5MPa with saturated vapour maintenance 7-10h, make finished product.
CN2009103057886A 2009-08-19 2009-08-19 Autoclaved phosphogypsum brick and method for preparing same Expired - Fee Related CN101684675B (en)

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CN102643107B (en) * 2012-05-17 2013-12-04 浙江方远建材科技有限公司 Calcination-free desulfurized gypsum-based ceramsite concrete perforated brick
CN104788073A (en) * 2015-04-22 2015-07-22 武汉理工大学 Heat-preservation moisture-adjusting type semi-hydrated gypsum cast-in-situ wall body material
CN106348706B (en) * 2016-08-19 2018-12-28 中盐安徽红四方新型建材科技有限公司 Inhibit the autoclave plaster building block and preparation method of scum
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CN106278104B (en) * 2016-08-19 2019-03-08 中盐安徽红四方新型建材科技有限公司 Autoclaved lime-sand brick and preparation method thereof
CN106316322B (en) * 2016-08-19 2018-07-24 中盐安徽红四方新型建材科技有限公司 Steam pressure α-type gypsum brick and preparation method thereof
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