CN106630712A - Water-resistant building gypsum powder prepared from copper-containing sludge biological leaching residues and preparation method thereof - Google Patents
Water-resistant building gypsum powder prepared from copper-containing sludge biological leaching residues and preparation method thereof Download PDFInfo
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- CN106630712A CN106630712A CN201611071676.5A CN201611071676A CN106630712A CN 106630712 A CN106630712 A CN 106630712A CN 201611071676 A CN201611071676 A CN 201611071676A CN 106630712 A CN106630712 A CN 106630712A
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- copper
- slag
- resistant building
- water
- contained sludge
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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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than 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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/022—Simultaneous dehydrating of gypsum and slaking of lime
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/036—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the dry process, e.g. dehydrating in a fluidised bed or in a rotary kiln, i.e. to obtain beta-hemihydrate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention relates to a water-resistant building gypsum powder prepared from copper-containing sludge biological leaching residues. The water-resistant building gypsum powder prepared from copper-containing sludge biological leaching residues is mainly prepared by grinding and uniformly mixing the following components in percentage by mass: 85-90% of copper-containing sludge biological leaching mature residue, 0.4-1.5% of activity excitation modifier, 8-14% of thickening time control agent and 0.6-1.5% of water reducing agent. The preparation method comprises the following steps: carrying out low-temperature drying on copper-containing sludge biological leaching residues, crushing and grinding to obtain leaching residue powder; carrying out dry heat treatment on the leaching residue powder at certain temperature to obtain the copper-containing sludge biological leaching mature residues; and uniformly grinding and mixing the copper-containing sludge biological leaching mature residues, activity excitation modifier, thickening time control agent and water reducing agent according to the proportioning requirement to obtain the water-resistant building gypsum powder product. The preparation of the water-resistant building gypsum powder from copper-containing sludge microbiological leaching residues is implemented in the simplest treatment mode, and the obtained product conforms to the related Chinese standard.
Description
Technical field
Invention is related to comprehensive utilization solid waste and prepares building material technical field, more particularly to one kind utilizes Bioleaching
Building gypsum plaster and preparation method that slag is prepared.
Background technology
With the fast development of electronics finishing industry, the thing followed is that the copper-contained sludge of manufacturer's discharge is accumulated year by year
It is tired, heavy metal pollution is easily caused, huge are endangered to environmental and human health impacts, it is the problem that environmental protection must be solved.Such waste water
Sludge is processed because tenor is high, easily migration, is put into National Hazard waste register, be generally acknowledged most intractable sludge in the industry
One of.Copper-contained sludge, because its tenor is higher than the mining grade of current mineral, is a kind of city mineral products for being easier and obtaining
Resource, but its water content is higher, and if directly higher using pyrogenic attack energy consumption, recovery rate of valuable metals is low, easily forms secondary
Pollution, and simple wet-treating is adopted, its residue is extremely difficult to innoxious requirement again.Processed using the method for biological metallurgy and contained
Copper sludge, can not only effectively leach the most of heavy metal in material, and while carrying out harmlessness disposing to sludge, also
Valuable metal can fully be reclaimed.But after sewage sludge harmlessness disposing, a large amount of Bioleaching slag byproducts equally can be also formed, its
Main component is calcium sulfate, and directly landfill can not only occupy a large amount of soils, and easily cause dust pollution, and not meeting environmental protection will
Ask.
Although also disclosing that the recoverying and utilizing method of some sludge in prior art, the product of the product that these techniques are obtained
Matter is poor, and added value is relatively low, and is often only suitable for the relatively simple Treatment of Sludge of component, and for containing mercury, chromium, cadmium, lead and
Metalloid arsenic this " five big killers ", and the sludge of the heavy metal such as nickel, copper, zinc, silver, prior art is often felt simply helpless, it is difficult to
Expect being carried out the rational method of recycling.In addition, hazardous waste copper-contained sludge biological detoxication slag is often containing suitable
The iron of amount, and the material such as a small amount of flocculant and microorganism, it is directly larger using difficulty, and recycle it is relatively costly,
Often it is extremely difficult to corresponding product requirement.
The content of the invention
The technical problem to be solved is the Bioleaching slag money for overcoming existing biological stirring extract technology to obtain
Source approach is single, especially the low problem of inorganic non-metallic component recycling added value therein, there is provided one kind is with most
Simple processing mode realizes the method that copper-contained sludge Microorganism Leaching slag prepares water resistant building gypsum plaster, and the product for obtaining meets
Concerned countries standard.
For solve above-mentioned technical problem, technical scheme proposed by the present invention be a kind of water resistant building gypsum plaster, the water resistant
Building gypsum plaster mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 85%-90%；
Activity excitation modifying agent 0.4%-1.5%；
Adjustable solidification agent 8%-14%；With
Water reducer 0.6%-1.5%.
Above-mentioned water resistant building gypsum plaster, it is preferred that the copper-contained sludge Bioleaching matured slag is particle uniformed powder, its
Essential mineral composition includes the component of following mass fraction：
Anhydrous gypsum 75%-85%；
Iron hydroxide 8%-18%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly includes that the various mixing in aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate (account for 5% left
It is right) and remaining all kinds of heavy metal compounds (accounting for 1% or so)；
Specific surface area >=the 500m of the copper-contained sludge Bioleaching matured slag2/kg。
Above-mentioned water resistant building gypsum plaster, it is preferred that the copper-contained sludge Bioleaching matured slag is biological with copper-contained sludge
Leached mud is to prepare after the thermally treated dehydration of base-material, de- organic matter, and iron, silicon are contained in the copper-contained sludge Bioleaching slag
And aluminium element.Aforementioned copper-contained sludge Bioleaching slag derives from amorphous copper-contained sludge, and main component is gypsum, also containing about
3%～10% iron (form is goethite, Schwertmannite or ferrovanadium etc.), and on a small quantity with the blending of iron hydroxide isocolloid one
Rise, also containing a small amount of insoluble organic principle (including insoluble flocculant and microbial cells etc.), Jing high temperature dehydrations are de- to be had
Machine thing is made can be used as the quality raw materials of water resistant building gypsum plaster of the present invention after powder grog.In addition, copper-contained sludge in the present invention
Containing compositions such as iron, aluminium, silicon, these compositions also contribute to improve the strength character of material Bioleaching slag itself, in preparation also
The addition of other additives can be reduced.
Above-mentioned water resistant building gypsum plaster, it is preferred that the activity excitation modifying agent is potassium sulfate, ferrous sulfate, sulfuric acid
One or more in sodium, alum, aluminum sulfate.Particularly preferred potassium sulfate, the mixture of ferrous sulfate, and matter during the two mixing
Amount is than being 1-10:1.Aforementioned preferred modified exciting agent can accelerate the hydration process of anhydrous gypsum early stage, shorten setting time, and
And hardenite microstructure can be improved, and dihydrate gypsum crystal size is refined, hardenite intensity is significantly improved.
Above-mentioned water resistant building gypsum plaster, it is preferred that the adjustable solidification agent is in lime, cement, flyash, slag micropowder
One or more.Particularly preferred cement, the mixture of lime, and mass ratio during the two mixing is 1-11:1.
Above-mentioned water resistant building gypsum plaster, it is preferred that the water reducer is naphthalene water reducer or polycarboxylate water-reducer.
Used as a total technology design, the present invention also provides a kind of preparation method of above-mentioned water resistant building gypsum plaster, wraps
Include following steps：
(1) grinding flour：It is first that cupric is dirty with copper-contained sludge Bioleaching slag (general aqueous 40%-60%) as base-material
Mud Bioleaching slag carries out low temperature drying, broken, grinding, and leached mud powder is obtained；
(2) calcining curing：The leached mud powder of gained is carried out at a certain temperature dry heat treatment, Muffle is selected in calcining
One kind in stove, rotary kiln, vertical furnace, tunnel cave or annular kiln, generates semi-hydrated gypsum, when temperature is increased to calcining in dehydration early stage
Continue to be dehydrated during temperature, little water is remained in gypsum, condense hardening slowly, main containing containing anhydrous gypsum is finally obtained
Copper sludge organism leaches matured slag；
(3) because copper-contained sludge Bioleaching matured slag hydration activity is poor, we press the dispensing of the water resistant building gypsum plaster
The copper-contained sludge Bioleaching matured slag of the mass fraction, activity excitation modifying agent, adjustable solidification agent and water reducer stone roller is mixed even, is obtained
To water resistant building gypsum plaster product, (product can meet GB/T 9776-2008《Plaster of Paris》In standard require).
Above-mentioned preparation method, it is preferred that the copper-contained sludge Bioleaching slag is electroplating industry or printed circuit board row
The copper-contained sludge that industry is produced disposes the byproduct for obtaining through biological harmless.The byproduct is constituted similar to by-product gypsum,
Residual total metalses are less than 1%, and toxicity is leached and meets general industry solid waste standard.The biological harmless is disposed
Particularly preferably refer to and first extraction process is carried out to copper-contained sludge using complex microorganism preparations, then washed again, dried
To byproduct.The complex microorganism preparations are preferably acidophilus irony bacterium (Ferroplasma acidiphilum) CCTCC M
2015017th, cold-resistant acidophilus iron-oxidizing bacteria (Acidithiobacillus ferrivorans) CCTCC M 2015009, acidophilus oxygen
Change ferrous iron Thiobacillus (Acidithiobacillus ferrooxidans) CCTCC M 2015007, thermophilic cleek end pylori
(Leptospirillum ferriphilum) CCTCC M 2015010 and Sulfobacillus acidophilus (Sulfobacillus
Acidophilus) CCTCC M2015006 press 2～4: 2～4: 1.5～2.5: 1.0～3: 1.5～2.0 dense quantitative proportion of bacterium
Culture is configured to after blending, the domestication of Jing copper-contained sludges stress conditions is obtained.
Above-mentioned preparation method, it is preferred that the actual temp of the low temperature drying is controlled to 100 DEG C -105 DEG C, it is described broken
The leached mud powder size obtained after broken, grinding is below -200 mesh.
Above-mentioned preparation method, it is preferred that the dry heat treatment is referred at a temperature of non reducing conditions, 150 DEG C -280 DEG C
Calcining.
The technical scheme of the invention described above is based primarily upon following principle：Because copper-contained sludge Bioleaching slag essential mineral into
It is divided into dihydrate gypsum, we consider other mineral compositions, the copper-contained sludge Bioleaching slag is not suitable for being largely used to brickmaking
With production Portland cement, manufacture ceramics, glaze and haydite are also poorly suitable for.In order that copper-contained sludge Bioleaching slag
Recycling is able to, research repeatedly and experiment is We conducted, it has been found that because dihydrate gypsum belongs to air-setting gelling
Material, itself there are problems that water-resistance it is poor, after gypsum is hardened, determine gypsum structure intensity crystal due to right
The suction-operated of water, meeting water causes dissolution of crystals, and adhesion weakens significantly between crystal, promotes material deformation and intensity substantially to drop
It is low.For this purpose, the dihydrate gypsum need through high temperature dehydration process, and carry out activity excitation be modified, the water-resistance of raising itself and
The performances such as compression strength.In addition, because, containing a large amount of ferric hydroxide colloids and a small amount of heavy metal, making in copper-contained sludge Bioleaching slag
The consumptive use of water normal consistence of plaster of Paris increased, but the impact to setting time and intensity is little.From economy, safety, ring
Conformal degree sets out, and the copper-contained sludge Bioleaching residue material after treatment, can be used not only as manufacture of cement adjustable solidification agent, more excellent
Choosing can produce modified building land plaster and its product.Dihydrate gypsum obtains anhydrous gypsum after processed, in the present invention, I
That activity excitation is carried out to anhydrous gypsum is modified main while employing physical method and chemical method.Physical method includes improving
Grinding fineness, calcining heat；Chemical method includes the modified exciting agent of addition, by the crystalline texture for changing anhydrite, increases brilliant
Lattice distort and defect, increasing specific surface area, improve surface property, so as to improve its hydration activity.By biological to copper-contained sludge
The calcining curing of leached mud and chemical modification are processed, and are finally obtained the water resistant building gypsum plaster with recycling value
Product.
In view of copper-contained sludge Bioleaching slag byproduct there is no at present treatment technology, advantages of the present invention to be especially embodied in：
1) present invention is directly with the HW17 classes in National Hazard waste register and the Bioleaching slag of HW22 class hazardous wastes
As raw material, this in the prior art few people refer to and carry out effective recycling, and make full use of in the present invention
Calcium and iron in Bioleaching slag preparing gypsum powder body, on the premise of performance is not reduced, the amount of dissolving ratio than it is existing other
Method is big.
2) present invention directly prepares water resistant building gypsum plaster, simple production process, energy using copper-contained sludge Bioleaching slag
Low, small investment is consumed, prepared land plaster has compression strength height, and (properties of product are more than GB/T 9776-2008《Plaster of Paris》
In standard require), setting time is suitable, water repelling property is excellent, it is economic and environment-friendly the features such as.The present invention is biological using copper-contained sludge
Leached mud prepares water resistant building gypsum plaster, and solid waste is turned waste into wealth, and Bioleaching slag volume is big, not only copper-contained sludge
Treatment and use provide new way, and meet national green, environmental protection, energy-saving strategy, to promoting China's sustainable development war
Somewhat there is important economic worth and realistic meaning.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can be with basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is the process chart of the present invention.
Specific embodiment
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, instrument and equipment used in the present invention etc. can pass through city
Field is commercially available or can be prepared by existing method.
A kind of water resistant building gypsum plaster, water resistant building gypsum plaster mainly grinds the even preparation that is mixed by the component of following mass fraction
Obtain：
Copper-contained sludge Bioleaching matured slag 85%-90%；
Activity excitation modifying agent 0.4%-1.5%；
Adjustable solidification agent 8%-14%；With
Water reducer 0.6%-1.5%.
Above-mentioned copper-contained sludge Bioleaching matured slag is particle uniformed powder, and its essential mineral composition includes following mass fraction
Component：
Anhydrous gypsum 75%-85%；
Iron hydroxide 8%-18%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly includes the various mixing in aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate and remaining
All kinds of heavy metal compounds；
Specific surface area >=the 500m of copper-contained sludge Bioleaching matured slag2/kg。
Above-mentioned activity excitation modifying agent is the ferrous mixture of technical grade sulfuric acid potassium and technical grade sulfuric acid, and the two mixes
When mass ratio be 1-10:1.
Above-mentioned adjustable solidification agent is (effective for cement (strength grade is equal to or higher than 42.5 Portland cement), lime
Calcium content 75%, according to cement fineness standard detection, screen over-size is mixture 4.8%), and mass ratio during the two mixing is
1-11:1。
Above-mentioned water reducer is naphthalene water reducer.
As shown in figure 1, the preparation method of above-mentioned water resistant building gypsum plaster is comprised the following steps：
(1) grinding flour：It is first that cupric is dirty with copper-contained sludge Bioleaching slag (general aqueous 40%-60%) as base-material
Mud Bioleaching slag carries out low temperature drying (100 DEG C -105 DEG C), broken, grinding, be obtained leached mud powder (granularity -200 mesh with
Under)；
(2) calcining curing：The leached mud powder of gained is carried out at a certain temperature dry heat treatment, dry heat treatment is referred to
Non reducing conditions, 150 DEG C of -280 DEG C of temperature lower calcinations, calcining is from Muffle furnace, rotary kiln, vertical furnace, tunnel cave or annular kiln
One kind, that is, copper-contained sludge Bioleaching matured slag is obtained；
(3) by the dispensing of above-mentioned water resistant building gypsum plaster by copper-contained sludge Bioleaching matured slag, the work of the mass fraction
Property excite modifying agent, adjustable solidification agent and water reducer to grind to be mixed even, obtain water resistant building gypsum plaster product.
Above-mentioned copper-contained sludge Bioleaching slag is that the copper-contained sludge that electroplating industry or printed circuit board industry are produced passes through life
The byproduct that thing method harmlessness disposing is obtained.Biological harmless is disposed and particularly related to first using complex microorganism preparations to cupric
Sludge carries out extraction process, is then washed again, dries and obtain byproduct.Group's composition of complex microorganism preparations is comprising thermophilic
Sour irony bacterium (Ferroplasma acidiphilum) CCTCC M 2015017, cold-resistant acidophilus iron-oxidizing bacteria
(Acidithiobacillus ferrivorans) CCTCC M 2015009, Acidithiobacillus ferrooxidans strain GF
(Acidithiobacillus ferrooxidans) CCTCC M 2015007, thermophilic cleek end pylori
(Leptospirillum ferriphilum) CCTCC M 2015010 and Sulfobacillus acidophilus (Sulfobacillus
acidophilus)CCTCC M 2015006；And aforementioned five kinds of bacterial strains be by 2～4: 2～4: 1.5～2.5: 1.0～3: 1.5～
Culture is configured to after the 2.0 dense quantitative proportion blending of bacterium, the domestication of Jing copper-contained sludges stress conditions is obtained.
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Embodiment 1：
Specific embodiment according to more than, is processed Jiangsu copper-contained sludge Bioleaching slag, and initial material contains
Water rate 48% (in following examples the person of not specializing, percentage represent mass fraction), butt composition：Ca 18.68%, S
18.17%, Mg 0.02%, Na 0.006%, Al 0.22%, Si 0.21%, P 0.17%, K 0.03%, Cr
0.029%, Mn 0.001%, Fe 7.38%, Cr 0.14%, Ni 0.023%, Zn 0.004%, Sb 0.06%.
First with copper-contained sludge Bioleaching slag as base-material, first copper-contained sludge Bioleaching slag is carried out into low temperature drying (100
DEG C -105 DEG C), broken, grinding, leached mud powder is obtained (granularity is below -200 mesh)；Then the leached mud powder of gained is existed
Dry heat treatment is carried out under calcining heat, dry heat treatment is referred in non reducing conditions, 250 DEG C of temperature lower calcinations, copper-contained sludge is obtained
Bioleaching matured slag；Copper-contained sludge Bioleaching matured slag, activity excitation modifying agent, adjustable solidification agent and water reducer are ground according to the following ratio
It is mixed even, obtains water resistant building gypsum plaster product.
Water resistant building gypsum plaster obtained in the present embodiment mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 88.6%；
Activity excitation modifying agent (including potassium sulfate 1.1% and ferrous sulfate 0.2%) 1.3%；
Adjustable solidification agent (including cement 12% and lime 2%) 14%；
Naphthalene water reducer 1.1%.
Above-mentioned copper-contained sludge Bioleaching matured slag is particle uniformed powder, and its essential mineral composition includes following mass fraction
Component：
Anhydrous gypsum 82.98%；
Iron hydroxide 14.10%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly includes the various mixing (accounting for 2%) in aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate
And all kinds of heavy metal compounds (surplus) of remaining；
Specific surface area >=the 500m of copper-contained sludge Bioleaching matured slag2/kg。
After testing, water resistant building gypsum plaster meets national standard obtained in the present embodiment 1《Plaster of Paris》GB/T 9776-
Requirement in 2008, according to《Solid waste Leaching leaching method sulfonitric method》Copper in (HJ T299-2007) leachate
Concentration be 0.03mg/L, other heavy metal concentrations are far below《Hazardous waste judging standard leaching characteristic identification》
(GB5085.3-2007) desired minimum limit value..
Embodiment 2：
Specific embodiment according to more than, the copper-contained sludge Bioleaching slag to the discharge of Hunan printed circuit board enterprise
Processed, initial material moisture content 57%, butt composition：Ca 23.41%, S 24.67%, Mg 0.12%, Na
0.016%, Al 0.14%, Si 0.54%, P 0.13%, K 0.001%, Cd 0.002%, Mn 0.001%, Fe
5.42%, Cr 0.01%, Ni 0.001%, Zn 0.03%, Sb 0.001%.
First with copper-contained sludge Bioleaching slag as base-material, first copper-contained sludge Bioleaching slag is carried out into low temperature drying (105
DEG C), broken, grinding, leached mud powder is obtained (granularity is below -200 mesh)；Then by the leached mud powder of gained in calcining temperature
Dry heat treatment is carried out under degree, dry heat treatment is referred in non reducing conditions, 280 DEG C of temperature lower calcinations, the biological leaching of copper-contained sludge is obtained
Go out matured slag；Copper-contained sludge Bioleaching matured slag, activity excitation modifying agent, adjustable solidification agent and water reducer are ground according to the following ratio is mixed
It is even, obtain water resistant building gypsum plaster product.
Water resistant building gypsum plaster obtained in the present embodiment mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 85.3%；
Activity excitation modifying agent (including potassium sulfate 0.9% and ferrous sulfate 0.1%) 1.0%；
Adjustable solidification agent (including cement 11.2% and lime 1.6%) 12.8%；
Naphthalene water reducer 0.9%.
Above-mentioned copper-contained sludge Bioleaching matured slag is particle uniformed powder, and its essential mineral composition includes following mass fraction
Component：
Anhydrous gypsum 78.5%；
Iron hydroxide 8.9%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly include aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate in various mixing (accounting for 5%) with
And all kinds of heavy metal compounds (surplus) of remaining；
Specific surface area >=the 500m of copper-contained sludge Bioleaching matured slag2/kg。
After testing, water resistant building gypsum plaster meets national standard obtained in the present embodiment 2《Plaster of Paris》GB/T 9776-
Requirement in 2008, according to《Solid waste Leaching leaching method sulfonitric method》Copper in (HJ T299-2007) leachate
Concentration be 0.05mg/L, other heavy metal concentrations are far below《Hazardous waste judging standard leaching characteristic identification》
(GB5085.3-2007) desired minimum limit value.
Embodiment 3：
Specific embodiment according to more than, the copper-contained sludge Bioleaching slag to the discharge of Hunan printed circuit board enterprise
Processed, the component of initial material is with above-described embodiment 2.
First with copper-contained sludge Bioleaching slag as base-material, first copper-contained sludge Bioleaching slag is carried out into low temperature drying (105
DEG C), broken, grinding, leached mud powder is obtained (granularity is below -200 mesh)；Then by the leached mud powder of gained in calcining temperature
Dry heat treatment is carried out under degree, dry heat treatment is referred in non reducing conditions, 250 DEG C of temperature lower calcinations, the biological leaching of copper-contained sludge is obtained
Go out matured slag；Copper-contained sludge Bioleaching matured slag, activity excitation modifying agent, adjustable solidification agent and water reducer stone roller is mixed according to the following ratio even
About 10～15 minutes, obtain water resistant building gypsum plaster product.Suitable quantity of water is added to use by being stirred when using.
Water resistant building gypsum plaster obtained in the present embodiment mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 87.5%；
Activity excitation modifying agent (potassium sulfate) 1.0%；
Adjustable solidification agent (including cement 9.5% and lime 1.1%) 10.6%；
Naphthalene water reducer 0.9%.
Above-mentioned copper-contained sludge Bioleaching matured slag is particle uniformed powder, and its essential mineral composition includes following mass fraction
Component：
Anhydrous gypsum 82%；
Iron hydroxide 9%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly include aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate in various mixing (accounting for 7%) with
And all kinds of heavy metal compounds (surplus) of remaining；
Specific surface area >=the 500m of copper-contained sludge Bioleaching matured slag2/kg。
After testing, water resistant building gypsum plaster meets national standard obtained in the present embodiment 3《Plaster of Paris》GB/T 9776-
Requirement in 2008 according to《Solid waste Leaching leaching method sulfonitric method》Copper in (HJ T299-2007) leachate
Concentration be 0.048mg/L, other heavy metal concentrations are far below《Hazardous waste judging standard leaching characteristic identification》
(GB5085.3-2007) desired minimum limit value.
Embodiment 4：
Specific embodiment according to more than, is processed Shenzhen copper-contained sludge Bioleaching slag, and initial material contains
Water rate 60%, butt composition：Ca 17.6%, S 25.39%, Mg 0.04%, Na 0.036%, Al 0.02%, Si
0.57%, P 0.04%, K 0.01%, Cd 0.001%, Mn 0.003%, Fe 8.62%, Cr 0.07%, Ni
0.011%, Zn 0.003%, Sb 0.001%.
First with copper-contained sludge Bioleaching slag as base-material, first copper-contained sludge Bioleaching slag is carried out into low temperature drying (105
DEG C), broken, grinding, leached mud powder is obtained (granularity is below -200 mesh)；Then by the leached mud powder of gained in calcining temperature
Dry heat treatment is carried out under degree, dry heat treatment is referred in non reducing conditions, 250 DEG C of temperature lower calcinations, the biological leaching of copper-contained sludge is obtained
Go out matured slag；Copper-contained sludge Bioleaching matured slag, activity excitation modifying agent, adjustable solidification agent and water reducer are ground according to the following ratio is mixed
It is even, obtain water resistant building gypsum plaster product.
Water resistant building gypsum plaster obtained in the present embodiment mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 85.2%；
Activity excitation modifying agent (including potassium sulfate 0.9% and ferrous sulfate 0.6%) 1.5%；
Adjustable solidification agent (including cement 9.3% and lime 2.7%) 12%；With
Naphthalene water reducer 1.3%.
Above-mentioned copper-contained sludge Bioleaching matured slag is particle uniformed powder, and its essential mineral composition includes following mass fraction
Component：
Anhydrous gypsum 78.68%；
Iron hydroxide 16.47%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly includes the various mixing in aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate and remaining
All kinds of heavy metal compounds, account for 4%；
Specific surface area >=the 500m of copper-contained sludge Bioleaching matured slag2/kg。
After testing, water resistant building gypsum plaster meets national standard obtained in the present embodiment 4《Plaster of Paris》GB/T 9776-
Requirement in 2008, according to《Solid waste Leaching leaching method sulfonitric method》Copper in (HJ T299-2007) leachate
Concentration be 0.037mg/L, other heavy metal concentrations are far below《Hazardous waste judging standard leaching characteristic identification》
(GB5085.3-2007) desired minimum limit value.
Embodiment 5：
Specific embodiment according to more than, at the copper-contained sludge Bioleaching slag of Fujian plating industrial district
Reason, initial material moisture content 58%, heavy metal component weight is 0.8%, the burn tinctuer 20.36% under 900 DEG C of hot conditions, three
Sulfur oxide 39.92%, silica 2.37%, alchlor 0.91%, di-iron trioxide 10.54%, calcium oxide 26.04%,
Magnesia 0.25%.
First with copper-contained sludge Bioleaching slag as base-material, by copper-contained sludge Bioleaching slag carry out low temperature drying (105 DEG C),
Broken, grinding, is obtained leached mud powder (granularity is below -200 mesh)；Then by the leached mud powder of gained at calcination temperatures
Dry heat treatment is carried out, dry heat treatment is referred in non reducing conditions, 200 DEG C of temperature lower calcinations, copper-contained sludge Bioleaching is obtained ripe
Slag；Copper-contained sludge Bioleaching matured slag, activity excitation modifying agent, adjustable solidification agent and water reducer stone roller is mixed according to the following ratio even, is obtained
To water resistant building gypsum plaster product.
Water resistant building gypsum plaster obtained in the present embodiment mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 85%；
Activity excitation modifying agent (including potassium sulfate 0.8% and ferrous sulfate 0.5%) 1.3%；
Adjustable solidification agent (including cement 12% and lime 1.1%) 13.1%；With
Naphthalene water reducer 0.6%.
Above-mentioned copper-contained sludge Bioleaching matured slag is particle uniformed powder, and its essential mineral composition includes following mass fraction
Component：
Gypsum 75.2%；
Iron hydroxide 11.9%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly includes the various mixing in aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate and remaining
All kinds of heavy metal compounds；
Specific surface area >=the 500m of copper-contained sludge Bioleaching matured slag2/kg。
After testing, water resistant building gypsum plaster meets national standard obtained in the present embodiment 5《Plaster of Paris》GB/T 9776-
Requirement in 2008, according to《Solid waste Leaching leaching method sulfonitric method》Copper in (HJ T299-2007) leachate
Concentration be 0.01mg/L, other heavy metal concentrations are far below《Hazardous waste judging standard leaching characteristic identification》
(GB5085.3-2007) desired minimum limit value.
In addition, water-resistant building gypsum plaster prepared by above-mentioned five embodiments is according to national standard《Plaster of Paris》
Technical requirement and method of testing in GB/T9776-2008, respectively to fineness (0.2mm square hole screens are tailed over), the presetting period,
Final setting time, 2h rupture strengths, 2h compression strength etc. are tested.Additionally, fracture specimens are placed in the container for filling water, point
The weight of gypsum samples Jin Pao not be determined after 2h, 4h, 24h, the water absorption rate of 2h, 4h, 24h gypsum samples is calculated respectively, be tested
As a result it is as shown in table 1 below.
Table 1：Water resistant building gypsum plaster performance test with copper-contained sludge Bioleaching slag as base material
| Project | Standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| 0.2mm square hole screens are tailed over (%) | ≤10 | 2.8 | 3.1 | 3.5 | 1.8 | 3.6 |
| Presetting period (minute) | ≥3 | 6.2 | 7.8 | 9.3 | 8.6 | 9.1 |
| Final setting time (minute) | ≤30 | 24.2 | 26.9 | 27.4 | 22.8 | 28.6 |
| 2h rupture strengths (MPa) | ≥1.6 | 3.8 | 3.1 | 2.4 | 2.9 | 3.5 |
| 2h compression strength (MPa) | ≥3.0 | 8.4 | 5.8 | 3.9 | 7.1 | 6.7 |
| 2h water absorption rates (%) | ≤5 | 1.17 | 1.2 | 0.93 | 0.61 | 0.79 |
| 4h water absorption rates (%) | ≤5 | 1.48 | 1.43 | 1.12 | 0.99 | 1.2 |
| 24h water absorption rates (%) | ≤5 | 2.25 | 2.40 | 1.91 | 1.84 | 2.0 |
Jing is tested, and as a result shows that water-resistant building gypsum plaster items are obtained using Bioleaching slag in the embodiment of the present invention
Performance indications meet or exceed the requirement of concerned countries standard.
Claims (10)
1. a kind of water resistant building gypsum plaster that prepared by utilization copper-contained sludge Bioleaching slag, it is characterised in that the water resistant building
Land plaster mainly grinds even the preparing that be mixed by the component of following mass fraction：
Copper-contained sludge Bioleaching matured slag 85%-90%；
Activity excitation modifying agent 0.4%-1.5%；
Adjustable solidification agent 8%-14%；With
Water reducer 0.6%-1.5%.
2. water resistant building gypsum plaster according to claim 1, it is characterised in that the copper-contained sludge Bioleaching matured slag is
Particle uniformed powder, its essential mineral composition includes the component of following mass fraction：
Anhydrous gypsum 75%-85%；
Iron hydroxide 8%-18%；
Remaining is secondary mineralogical composition；
Secondary mineralogical composition mainly includes the various mixing in aluminum sulfate, magnesium sulfate, sodium metasilicate, magnesium silicate；
Specific surface area >=the 500m of the copper-contained sludge Bioleaching matured slag2/kg。
3. water resistant building gypsum plaster according to claim 1, it is characterised in that the copper-contained sludge Bioleaching matured slag is
Prepare after with copper-contained sludge Bioleaching slag as the thermally treated dehydration of base-material, de- organic matter, the biological leaching of the copper-contained sludge
Contain iron, silicon and aluminium element in slagging tap.
4. the water resistant building gypsum plaster according to any one of claim 1-3, it is characterised in that the activity excitation is modified
Agent is one or more in potassium sulfate, ferrous sulfate, sodium sulphate, alum, aluminum sulfate.
5. the water resistant building gypsum plaster according to any one of claim 1-3, it is characterised in that the adjustable solidification agent is stone
One or more in ash, cement, flyash, slag micropowder.
6. the water resistant building gypsum plaster according to any one of claim 1-3, it is characterised in that the water reducer is naphthalene system
Water reducer or polycarboxylate water-reducer.
7. a kind of preparation method of the water resistant building gypsum plaster as any one of claim 1-6, comprises the following steps：
(1) grinding flour：With copper-contained sludge Bioleaching slag as base-material, first copper-contained sludge Bioleaching slag is carried out into low temperature and done
Dry, broken, grinding, is obtained leached mud powder；
(2) calcining curing：The leached mud powder of gained is carried out at a certain temperature dry heat treatment, the biological leaching of copper-contained sludge is obtained
Go out matured slag；
(3) the copper-contained sludge Bioleaching matured slag of the mass fraction, activity are swashed by the dispensing of the water resistant building gypsum plaster
Send out modifying agent, adjustable solidification agent and water reducer and grind and be mixed even, obtain water resistant building gypsum plaster product.
8. preparation method according to claim 7, it is characterised in that the copper-contained sludge Bioleaching slag is electroplating industry
Or the copper-contained sludge that printed circuit board industry is produced disposes the byproduct for obtaining through biological harmless；The bioanalysis is harmless
Change disposal to refer to and first carry out extraction process to copper-contained sludge using complex microorganism preparations, then washed again, dry and obtain
Byproduct；The complex microorganism preparations are acidophilus irony bacterium (Ferroplasma acidiphilum) CCTCC M
2015017th, cold-resistant acidophilus iron-oxidizing bacteria (Acidithiobacillus ferrivorans) CCTCC M 2015009, acidophilus oxygen
Change ferrous iron Thiobacillus (Acidithiobacillus ferrooxidans) CCTCC M 2015007, thermophilic cleek end pylori
(Leptospirillum ferriphilum) CCTCC M 2015010 and Sulfobacillus acidophilus (Sulfobacillus
Acidophilus) CCTCC M 2015006 press 2～4: 2～4: 1.5～2.5: 1.0～3: 1.5～2.0 dense quantitative proportion of bacterium
Culture is configured to after blending, the domestication of Jing copper-contained sludges stress conditions is obtained.
9. preparation method according to claim 7, it is characterised in that the actual temp of the low temperature drying is controlled to 100
DEG C -105 DEG C, the leached mud powder size obtained after the broken, grinding is below -200 mesh.
10. preparation method according to claim 7, it is characterised in that the dry heat treatment is referred in 150 DEG C of -280 DEG C of bars
Calcine under part.
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Inventor after: Zhao Shaoan Inventor after: Zhou Wenbo Inventor after: Yang Qiwei Inventor after: Zhou Hongbo Inventor after: Chen Junhui Inventor after: Qin Ronggang Inventor before: Zhao Shaoan Inventor before: Zhou Wenbo Inventor before: Yang Qiwei Inventor before: Zhou Hongbo Inventor before: Chen Junhui Inventor before: Qin Ronggang |