CN104445944B - A kind of method that dangerous solid waste prepares devitrified glass - Google Patents
A kind of method that dangerous solid waste prepares devitrified glass Download PDFInfo
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
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Abstract
The invention discloses one kind with dangerous solid waste（Referred to as endanger solid）The method that devitrified glass is prepared for raw material, is nucleating agent using heavy metal of the danger in solid, devitrified glass is obtained by dispensing, melting, calendering, forming core, crystallization and annealing.It is an advantage of the invention that by the heavy metal element stable curing in incinerator ash, stainless steel slag, acid-washing stainless steel sludge, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash, avoid pollution, the devitrified glass of high added value is obtained simultaneously, realize solid innoxious higher value application of endangering, with significant environment benefits and economic gains, wide market.
Description
Technical field
It is solid to endanger the invention discloses one kind（Dangerous solid waste）The method that devitrified glass is prepared for raw material, belongs to ring
Protect and resource reutilization field.By the use of heavy metal of the danger in solid as nucleating agent, devitrified glass is prepared using fusion method.The present invention
Advantage be to realize heavy metal element stable curing using devitrified glass, it is to avoid pollution, at the same obtain high added value crystallite glass
Glass.
Background technology
Industrial production generates substantial amounts of solid waste, wherein there are substantial amounts, the various danger containing heavy metal to consolidate, serious prestige
Coerce the healthy and ecological environment security of people.The danger having a large capacity and a wide range mainly has incinerator ash, stainless steel slag, stainless steel admittedly
Pickling sludge, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash etc..
1. incinerator ash
As Consideration of MSW Incineration Technology is promoted in China, the disposal for incineration ash of household rubbish has turned into restriction industry
The major issue of development.One ton of rubbish of burning disposal about produces 20% bottom ash and 4% bag-type dust ash.Due to containing in incinerator ash
There are the various heavy materials such as Cd, Pb, Cu, Zn and Cr that higher concentration easily leaches, be put into《The solid register of country's danger》, numbering is
HW18。
2. stainless steel slag
Stainless steel slag is the accessory substance of stainless steel smelting.According to the rough estimates of China Metal material circulation association, in 2013
State's stainless steel crude steel yield is 20,500,000 tons.Based on 3 tons of stainless steels 1 ton of stainless steel slags of generation are often produced, stainless steel slag yield surpasses
Cross 5,800,000 tons.Containing part aqueous, carcinogenic, teratogenesis Cr VI in stainless steel slag, grave danger is brought to ecological environment.
The leaching concentration of total chromium is 40 mg/L, wherein Cr in company of China stainless steel slag6+Leaching content be 15mg/L, be
3 times of GB5085.3-2007 settings, belong to danger solid.
3. acid-washing stainless steel sludge
In cold-rolling production process, using HNO3With HF mixing, acid is carried out to stainless steel band steel surface at 40-60 DEG C
Wash and be passivated, produce a large amount of pickle liquors containing poisonous and harmful substances such as Cr, Ni, obtain washing containing chromic acid through lime neutralization precipitation
Sludge, Cr6+And Ni2+Leaching concentration be respectively 35mg/L and 50mg/L, respectively the 7 of GB5085.3-2007 settings times and
10 times, belong to danger solid.
4. electroplating sludge
The electroplating sludge that plating is produced contains the heavy metals such as a large amount of copper, nickel, chromium, zinc, and its contents of many kinds of heavy metal ion concentration is remote
Higher than GB5085.3-2007 settings, belong to danger solid.
5. chromium slag
Chromium slag refers to the industrial residue produced during crome metal and chromium salt production.Chinese You20Duo Ge provinces and cities discharge at present
Chromium slag.According to statistics, l tons of sodium dichromates are often produced, 3-3.5 tons of chromium slag is averagely produced.Chromium salt production enterprise of the country is big every year at present
About discharge ten thousand tons of chromium slags of 20-30.Harmful components in chromium slag are mainly soluble sodium chromate, calcium chromate etc., belong to danger solid.
6. lead and zinc smelting dreg
2013, China's lead zinc total output reached 9,780,000 tons, occupies the first in the world for years.It is estimated that often producing
1 ton of lead discharges 0.71 ton of waste residue, and 1 ton of zinc of production discharges 0.96 ton of slag.China's lead and zinc smelting dreg volume of cargo in storage crosses hundred million tons, containing a variety of
Heavy metal, belongs to danger solid.
7. flyash
Flyash is the fine ash that coal combustion is produced, mainly by SiO2、Al2O3、FeO、Fe2O3、CaO、TiO2Deng composition.China
The annual emissions of coal-burning power plant's flyash have become serious environmental problem up to 2.9 hundred million tons.
The solid disposal of danger and the focus for having become public attention is recycled, minimizing, recycling and innoxious etc. should be followed
Basic principle.The solid disposal of danger and reutilization technology mainly have curing/stabilizing, reduction and detoxication and valuable metal recovery, precipitation solid
Change and reclaim valuable metal, microbial method etc..
1. curing/stabilizing technology
Curing/stabilizing technology is the solid the most frequently used treatment technology of danger.It is most widely used in curing/stabilizing technology to be
Cement solidification method.But in order to realize solid removing toxic substances of endangering, or reduction toxicity, different types of curing agent is commonly incorporated into, these curing agent
Often play a part of stabilizing heavy metal.The existing solid curing/stabilizing technology of danger mainly has cement-based solidified/stabilisation skill
Art, glass solidification/stabilization technology and brickmaking etc..
Cement solidification/stabilization technology is usually used in solidification danger admittedly, and its mechanism of action is that cement matrix is produced with solid waste reaction
Raw gelation, solid waste particle encapsulation, realizes that heavy metal ion solidifies, but the heavy metal ion in cement is deposited under extreme conditions
Leaching risk.Therefore, on March 1st, 2014 comes into effect《The solid Environmental capacity standard of cement kiln synergic processing danger》(GB
30485-2013)、《The solid environmental protection technology specification of cement kiln synergic processing danger》(HJ 662-2013) has been explicitly pointed out：Cement
When kiln cooperative disposal danger is solid, the maximum dosage limit value for entering heavy metal in furnace charge is：Total Cr≤320 mg/kg, sexavalence Cr≤
The mg/kg of 10 mg/kg, total Ni≤640, the mg/kg of beryllium+chromium+10* tin+50* antimony+copper+manganese+barium+nickel+barium≤1150.
Glass solidification/stabilization technology be using glass as curing agent, by itself and danger are solid mixed with certain charge ratio after,
Melted under high temperature (1400-1600 DEG C), then the annealed glass solidified body stablized.Glass solidification technology is due to its heavy metal
Solidification effect is good, and Solid state fermentation amount is big, simple technological process and other advantages, but high energy consumption, equipment high cost, and added value of product is low.
The solid brick-making technology technique of danger is simple, production cost is low, big with the quantity of slag, is widely used in solid disposal of endangering.But, due to
Brick valency is cheap, can not possibly be crushed and be mixed using ball mill during brickmaking, cause heavy metal ion in bulky grain solid waste not
Easily it is reduced in sintering procedure.In addition, the research of nearly 2 years shows, the microstructure of adobe is more loose, and basicity is relative
It is larger, it is easy to be reacted with acid or alkali, the prolonged curing less effective of adobe heavy metal ion.Thus, most brick fields stop over
Only utilize solid waste of heavy metal brickmaking.
2. valuable metal is reclaimed in precipitation solidification
It is that adding reactant will be valuable after danger is dissolved under acid or alkaline conditions admittedly that valuable metal is reclaimed in precipitation solidification
Metal is reduced or precipitation is reclaimed.Wet processing common problem is that secondary pollution is serious, compares and is suitable for heavy metal decrement
Change, it is impossible to solve heavy metal pollution problem.
3. reduction and detoxication and valuable metal recovery technology
The technology be will danger is solid is mixed with reducing agent, after 600 DEG C of -1000 DEG C of heavy metal ion reduction and detoxications of progress rapid cooling or
Water quenching, realizes valuable metal recovery, and waste is used for cement admixture.The technology has secondary pollution, high energy consumption.Abundant Xinghua factory
Tens thousand of tons of chromium slags are disposed using reduction and detoxication technical security and obtain ferrochrome, waste is used for cement.
4. microbial method
Microbial method is, by the metabolic by the heavy metal ion enrichment in solid waste or reduction of microorganism, to realize that danger is solid
Removing toxic substances or metal recovery.Chinese invention patent（CN 104058565 A）It is open a kind of sour using Thiobacillus ferrooxidans processing
The method for washing sludge, adsorbable recovery 34.48%-79.31% Cr and 94.77%-94.89% Ni.Microbial method it is excellent
Point is that energy consumption is low, but there is long processing period, selective absorption and remain the shortcomings of concentration of heavy metal ion is higher.
Above-mentioned danger is disposed admittedly has that residual heavy metal ion concentration is higher, tail liquid emissions amount is larger, difficulty with reuse method
With the problems such as the requiring that be up to state standards.Therefore, it is badly in need of a kind of solid cooperative disposal of danger of exploitation and high-valued recycling new technology, it is real
Existing solid waste is innoxious, high-valued and recycling.Devitrified glass with a variety of solid wastes of cooperative disposal can obtain compact structure, strong
Degree is high, the Inorganic Non-metallic Materials that hardness is big, wearability is good, resistance to acids and bases is good, can be widely applied to metallurgy, building, house ornamentation, state
The field such as anti-.
Current devitrified glass raw material is main based on raw ore and slag.Chinese invention patent (CN102531394A) is disclosed
One kind is prepared using lithium mine tailing production micro-crystal board material preparation method with lithium mine tailing, calcium stone flour, quartz sand and colouring agent etc. for raw material
Low-expansion devitrified glass.Chinese invention patent (CN101857367A) disclose it is a kind of prepared using iron tailings as raw material it is black
The method of color devitrified glass.Chinese invention patent (CN1868946A) discloses one kind with Ta Nb tailings, yellow phosphorus furnace slag and useless glass
The method that the comprehensive utilization of waste material such as glass prepare devitrified glass for raw material.Chinese invention patent (CN103086602A) discloses one kind
The method for preparing low expansion coefficient micro crystal glass using microwave technology by primary raw material of golden mine tailing.Chinese invention patent
(CN101328021A) one kind is disclosed using flyash, rare metal ore-dressing mine tailing as raw material, prepares CaO-MgO-Al2O3-
SiO2The porous devitrified glass of system.Above-mentioned devitrified glass Patents use raw ore and slag for raw material, are not related to crystallite
Glass heavy metals immobilization effect, does not possess the solid effect of safe disposal danger.
Devitrified glass is prepared admittedly the invention discloses danger, by the use of heavy metal element of the danger in solid as original nucleus, then
Long great achievement micron-sized crystallite containing heavy metal, is uniformly distributed in vitreum.Danger can not only be prepared into acidproof by the present invention admittedly
Caustic corrosion, wear-resisting, safety non-toxic devitrified glass, and heavy metals immobilization is realized, reach the effect for administering heavy metal pollution.
The content of the invention
The invention discloses a kind of method that dangerous solid waste prepares devitrified glass, by Cr, Ni, Mn, Pb, Zn in endangering admittedly,
The heavy metals such as Cu are used as nucleus, CaO, MgO, SiO2And Al2O3Oxide prepares crystallite glass as main component using fusion method
Glass.Danger used by the present invention is incinerator ash, stainless steel slag, acid-washing stainless steel sludge, electroplating sludge, chromium slag, lead zinc smelting admittedly
The one or more in slag, flyash are refined, additive is the one or more in cullet, quartz sand, lime stone.
The present invention is comprised the following steps that：
Dispensing：Incinerator ash, stainless steel slag, acid-washing stainless steel sludge, electroplating sludge, chromium slag, lead and zinc smelting dreg, fine coal
One or more kinds of danger in ash are consolidated, the one or more in cullet, quartz sand and lime stone, by design into
Divide and matched；
Batch mixing：The raw material matched, which be well mixed, obtains compound；
Fusing：Mixed material heating to fusing obtains melt；
Calendering：Melt obtains parent glass, the i.e. glass without forming core through calendering；
Coring：Parent glass obtains coring glass, the i.e. glass containing a large amount of nucleating agents through coring；
Crystallization：Coring glass forms the crystallized glass that crystallite is evenly distributed, i.e. nucleating agent length greatly micron order after crystallization
The glass of crystallite；
Annealing：The annealed stress that eliminates of crystallized glass obtains devitrified glass product.
Structure of Glass Ceramic even compact prepared by the present invention, Leaching of Heavy Metals concentration is low, Cr≤5.0 mg/L, Pb
≤ 5.0 mg/L, Cd≤1.0 mg/L, Ni≤1.0 mg/L, Zn≤5.0 mg/L, Cu≤5.0 mg/L is remote low
In GB5085.3-2007 settings.It is an advantage of the invention that by incinerator ash, stainless steel slag, acid-washing stainless steel sludge, plating
Heavy metal element stable curing in sludge, chromium slag, lead and zinc smelting dreg, flyash, it is to avoid pollution, while obtaining high added value
Devitrified glass, the solid innoxious higher value application of danger is realized, with significant environment benefits and economic gains, wide market.
Brief description of the drawings
Fig. 1 devitrified glass preparation flows.
Fig. 2 devitrified glass microscopic structures.
Embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited solely to following examples.
Embodiment 1
Incinerator ash 60.0wt.% and cullet 40.0wt.% are well mixed, compound wt.%, Pb containing Cr 0.8
1.4 wt.%、Ni 2.0 wt.%、Cd 2.0 wt.%、Zn 5.0 wt.%、Cu 2.1 wt.%.By mixed material heating to 1550 DEG C
Fusing obtains melt, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring glass, be then warming up to 950
The crystallized glass that DEG C crystallization formation crystallite is evenly distributed, last stress relieving by annealing obtains devitrified glass product.Devitrified glass
Bending strength 70.0 MPa, microhardness 6.0GPa, compression strength 450.0MPa, abrasion loss 0.040g/cm2, acid resistance
（20wt% sulfuric acid）For 96.0%, fastness to alkali（20wt% NaOH）It is that 0.2 mg/L, Pb is leached for 98.0%, Cr leaching concentrations
Concentration is that 0.07 mg/L, Cd leaching concentration is that 0.6 mg/L, Ni leaching concentration is that 0.25 mg/L, Zn leaching concentration is 5.0
Mg/L, Cu leaching concentration are 3.11 mg/L.
Embodiment 2
The wt.% of stainless steel slag 50 and the wt.% of quartz sand 50 are well mixed, compound wt.%, Pb 0 containing Cr 4.0
wt.%、Ni 0.5 wt.%、Cd 0 wt.%、Zn 0.7 wt.%、Cu 1.1 wt.%.Mixed material heating is melted to 1550 DEG C
To melt, parent glass is obtained through calendering, 750 DEG C of coring is then heated to and obtains coring glass, be then warming up to 950 DEG C of crystallization
The crystallized glass that crystallite is evenly distributed is formed, last stress relieving by annealing obtains devitrified glass product.The bending resistance of devitrified glass is strong
Spend 150.0MPa, microhardness 7.8GPa, compression strength 792.0MPa, abrasion loss 0.100g/cm2, acid resistance（20wt% sulphur
Acid）For 97.1%, fastness to alkali（20wt% NaOH）It is that 5.0 mg/L, Pb leaching concentrations are 0 for 98.4%, Cr leaching concentrations
Mg/L, Cd leaching concentration are that 0 mg/L, Ni leaching concentration is that 0.15 mg/L, Zn leaching concentration is that 2.10 mg/L, Cu leachings are dense
Spend for 1.54 mg/L.
Embodiment 3
Electroplating sludge 20wt.%, lime stone 40wt.% and cullet 40wt.% are well mixed, compound contains Cr 2.4
wt.%、Pb 1.4 wt.%、Ni 0 wt.%、Cd 1.2 wt.%、Zn 3.5 wt.%、Cu 5.0 wt.%.Mixed material heating is arrived
1550 DEG C of fusings obtain melt, obtain parent glass through calendering, are then heated to 750 DEG C of coring and obtain coring glass, then rise
The crystallized glass that temperature is evenly distributed to 950 DEG C of crystallization formation crystallites, last stress relieving by annealing obtains devitrified glass product.Crystallite
Bending strength 100.0 MPa, microhardness 6.5GPa, compression strength 550.0MPa, abrasion loss 0.050g/cm of glass2, it is resistance to
Acidity（20wt% sulfuric acid）For 98.2%, fastness to alkali（20wt% NaOH）It is 0.22 mg/L, Pb for 98.8%, Cr leaching concentrations
Leaching concentration is that 0.15 mg/L, Cd leaching concentration is that 0.11 mg/L, Ni leaching concentration is 0 mg/L, Zn leaching concentration
It is 5.0 mg/L for 5.0 mg/L, Cu leaching concentrations.
Embodiment 4
The wt.% of chromium slag 40 and the wt.% of quartz sand 60 are well mixed, compound containing 1.5 wt.% of wt.%, Pb of Cr 2.9,
Ni 0.3 wt.%、Cd 0.6 wt.%、Zn 0.4 wt.%、Cu 2.02 wt.%.Mixed material heating is obtained to 1550 DEG C of fusings
Melt, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring glass, be then warming up to 950 DEG C of crystallization shapes
The crystallized glass being evenly distributed into crystallite, last stress relieving by annealing obtains devitrified glass product.The bending strength of devitrified glass
122.0 MPa, microhardness 6.8GPa, compression strength 600.0MPa, abrasion loss 0.054g/cm2, acid resistance（20wt% sulphur
Acid）For 97.4%, fastness to alkali（20wt% NaOH）It is that 0.12 mg/L, Pb leaching concentration is for 98.9%, Cr leaching concentrations
0.14 mg/L, Cd leaching concentration be 0.04 mg/L, Ni leaching concentration be 0.14 mg/L, Zn 1.5 mg/L, Cu leach
Concentration is 2.01 mg/L.
Embodiment 5
Lead and zinc smelting dreg 55wt.% and quartz sand 45wt.% are well mixed, compound wt.%, Pb 4.0 containing Cr 1.1
wt.%、Ni 0.3 wt.%、Cd 0.6 wt.%、Zn 4.2 wt.%、Cu 0 wt.%.Mixed material heating is melted to 1550 DEG C
To melt, parent glass is obtained through calendering, 750 DEG C of coring is then heated to and obtains coring glass, be then warming up to 950 DEG C of crystallization
The crystallized glass that crystallite is evenly distributed is formed, last stress relieving by annealing obtains devitrified glass product.The bending resistance of devitrified glass is strong
Spend 110.0 MPa, microhardness 7.2GPa, compression strength 760.0MPa, abrasion loss 0.050g/cm2, acid resistance（20wt% sulphur
Acid）For 98.0%, fastness to alkali（20wt% NaOH）It is that 0.14 mg/L, Pb leaching concentration is for 99.2%, Cr leaching concentrations
5.0 mg/L, Cd leaching concentrations are that 0.01 mg/L, Ni leaching concentration is that 0.04 mg/L, Zn leaching concentration is 3.4 mg/
L、Cu 0 mg/L。
Embodiment 6
Flyash 45wt.% and cullet 55wt.% are well mixed, compound containing 1.04 wt.% of wt.%, Pb of Cr 0,
Ni 1.0 wt.%、Cd 1.0 wt.%、Zn 0 wt.%、Cu 2.4 wt.%.Mixed material heating is melted to 1550 DEG C
Body, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring glass, be then warming up to 950 DEG C of crystallization and formed
The crystallized glass that crystallite is evenly distributed, last stress relieving by annealing obtains devitrified glass product.The bending strength of devitrified glass
144.0 MPa, microhardness 7.3GPa, compression strength 656.0MPa, abrasion loss 0.080g/cm2, acid resistance（20wt% sulphur
Acid）For 97.2%, fastness to alkali（20wt% NaOH）It is that 0 mg/L, Pb leaching concentration is 1.02 for 99.1%, Cr leaching concentrations
Mg/L, Cd leaching concentration are that 1.0 mg/L, Ni leaching concentrations are that 1.0 mg/L, Zn leaching concentrations are that 0 mg/L, Cu is leached
Concentration is 2.65 mg/L.
Embodiment 7
Incinerator ash 20wt.%, flyash 35wt.% and cullet 45wt.% are well mixed, compound contains Cr 1.2
wt.%、Pb 1.14 wt.%、Ni 0.2 wt.%、Cd 0.7 wt.%、Zn 1.2 wt.%、Cu 2.6 wt.%.By compound plus
Heat obtains melt to 1550 DEG C of fusings, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring glass, with
The crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed is warming up to afterwards, and last stress relieving by annealing obtains devitrified glass product.
Bending strength 128.0 MPa, microhardness 6.2GPa, compression strength 564.0MPa, abrasion loss 0.090g/ of devitrified glass
cm2, acid resistance（20wt% sulfuric acid）For 97.2%, fastness to alkali（20wt% NaOH）It is 0.12 for 99.5%, Cr leaching concentrations
Mg/L, Pb leaching concentration are that 0.22 mg/L, Cd leaching concentration is that 0.42 mg/L, Ni leaching concentration is 0.45 mg/L, Zn
Leaching concentration is that 0.35 mg/L, Cu leaching concentration is 1.55 mg/L.
Embodiment 8
Stainless steel slag 35wt.%, acid-washing stainless steel sludge 15wt.% and cullet 50wt.% are well mixed, compound contains
Cr 1.9 wt.%、Pb 1.25 wt.%、Ni 0.47 wt.%、Cd 0.11 wt.%、Zn 1.51 wt.%、Cu 2.02 wt.%。
Mixed material heating is obtained into melt to 1550 DEG C of fusings, parent glass is obtained through calendering, is then heated to 750 DEG C of coring and obtains core
Change glass, be then warming up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed, last stress relieving by annealing obtains crystallite
Glass product.Bending strength 83.0 MPa, microhardness 6.6GPa, compression strength 750.0MPa, abrasion loss of devitrified glass
0.050g/cm2, acid resistance（20wt% sulfuric acid）For 99.5%, fastness to alkali（20wt% NaOH）For 99.4%, acid resistance
98.7%, alkali resistance 99.2%, Cr leaching concentrations are that 0.11 mg/L, Pb leaching concentration is that 0.12 mg/L, Cd leaching concentration is
0.22 mg/L, Ni leaching concentration is that 0.25 mg/L, Zn leaching concentration is that 0.05 mg/L, Cu leaching concentration is 1.15
mg/L。
Embodiment 9
Electroplating sludge 25wt.%, chromium slag 25wt.% and quartz sand 50wt.% are well mixed, compound contains Cr 1.3
wt.%、Pb 1.14 wt.%、Ni 0.43 wt.%、Cd 0.31 wt.%、Zn 1.59 wt.%、Cu 2.44 wt.%.Will mixing
Material is heated to 1550 DEG C of fusings and obtains melt, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring glass
Glass, is then warming up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed, and last stress relieving by annealing obtains devitrified glass
Product.Bending strength 147.0 MPa, microhardness 7.8GPa, compression strength 532.0MPa, abrasion loss of devitrified glass
0.090g/cm2, acid resistance（20wt% sulfuric acid）For 96.6%, fastness to alkali（20wt% NaOH）It is for 98.6%, Cr leaching concentrations
0.13 mg/L, Pb leaching concentration is that 0.19 mg/L, Cd leaching concentration is that 0.24mg/L, Ni leaching concentration are 0.26 mg/
L, Zn leaching concentration are that 0.15 mg/L, Cu leaching concentration is 1.62 mg/L.
Embodiment 10
Lead and zinc smelting dreg 40wt.%, flyash 10wt.% and cullet 50wt.% are well mixed, compound contains Cr 1.7
wt.%、Pb 2.18 wt.%、Ni 0.51 wt.%、Cd 0.11 wt.%、Zn 1.24 wt.%、Cu 1.24 wt.%.Will mixing
Material is heated to 1550 DEG C of fusings and obtains melt, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring glass
Glass, is then warming up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed, and last stress relieving by annealing obtains devitrified glass
Product.Bending strength 117.0 MPa, microhardness 7.3GPa, compression strength 590.0MPa, abrasion loss of devitrified glass
0.065g/cm2, acid resistance（20wt% sulfuric acid）For 99.7%, fastness to alkali（20wt% NaOH）For 99.8%, Cr leaching concentrations
It is that 0.12 mg/L, Cd leaching concentration is that 0.27mg/L, Ni leaching concentration are for 0.14 mg/L, Pb leaching concentration
0.28mg/L, Zn leaching concentration are that 0.14 mg/L, Cu leaching concentration is 1.25 mg/L.
Embodiment 11
Lead and zinc smelting dreg 30wt.%, flyash 10wt.%, acid-washing stainless steel sludge 10wt.% and cullet 50wt.% are mixed
Close uniform, compound is containing Cr 1.75 wt.%, Pb 2.01 wt.%, Ni 0.14 wt.%, Cd 0.24 wt.%, Zn
1.22wt.%、Cu 1.29 wt.%.Mixed material heating is obtained into melt to 1550 DEG C of fusings, parent glass is obtained through calendering, so
After be heated to 750 DEG C of coring and obtain coring glass, be then warming up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed,
Last stress relieving by annealing obtains devitrified glass product.Bending strength 93 MPa, microhardness 7.3GPa, resistance to compression of devitrified glass
Intensity 560.0MPa, abrasion loss 0.080g/cm2, acid resistance（20wt% sulfuric acid）For 98.2%, fastness to alkali（20wt% hydroxides
Sodium）It is that 0.18 mg/L, Pb leaching concentration is that 0.45 mg/L, Cd leaching concentration is 0.29mg/ for 99.3%, Cr leaching concentrations
L, Ni leaching concentration are that 0.42mg/L, Zn leaching concentration are that 0.25 mg/L, Cu leaching concentration is 0.25 mg/L.
Embodiment 12
Stainless steel slag 25wt.%, electroplating sludge 15wt.%, acid-washing stainless steel sludge 10wt.% and cullet 50wt.% are mixed
Close uniform, compound is containing Cr 1.35 wt.%, Pb 2.75 wt.%, Ni 0.45 wt.%, Cd 0.86 wt.%, Zn
1.75wt.%、Cu 1.29 wt.%.Mixed material heating is obtained into melt to 1550 DEG C of fusings, parent glass is obtained through calendering, so
After be heated to 750 DEG C of coring and obtain coring glass, be then warming up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed,
Last stress relieving by annealing obtains devitrified glass product.Bending strength 90.0 MPa, the microhardness 7.2GPa of devitrified glass, resist
Compressive Strength 560.0MPa, abrasion loss 0.090g/cm2, acid resistance（20wt% sulfuric acid）For 97.7%, fastness to alkali（20wt% hydroxides
Sodium）It is that 0.07 mg/L, Pb leaching concentration is that 0.15 mg/L, Cd leaching concentration is 0.24 for 99.4%, Cr leaching concentrations
Mg/L, Ni leaching concentration are that 0.41 mg/L, Zn leaching concentration is that 0.15 mg/L, Cu leaching concentration is 0.27mg/L.
Embodiment 13
By stainless steel slag 25wt.%, electroplating sludge 10wt.%, acid-washing stainless steel sludge 5wt.%, flyash 10wt.% and useless
Glass 50wt.% is well mixed, and compound is containing 2.16 0.11 wt.%, the Cd 0.14 of wt.%, Ni of wt.%, Pb of Cr 1.4
wt.%、Zn 1.27wt.%、Cu 1.21 wt.%.Mixed material heating is obtained into melt to 1550 DEG C of fusings, basis is obtained through calendering
Glass, is then heated to 750 DEG C of coring and obtains coring glass, is then warming up to the crystalline substance that 950 DEG C of crystallization formation crystallites are evenly distributed
Change glass, last stress relieving by annealing obtains devitrified glass product.The MPa of bending strength 134.0 of devitrified glass, microhardness
6.79GPa, compression strength 676.0MPa, abrasion loss 0.045g/cm2, acid resistance（20wt% sulfuric acid）For 97.7%, fastness to alkali
（20wt% NaOH）It is that 0.085 mg/L, Pb leaching concentration is that 0.025 mg/L, Cd is leached for 98.8%, Cr leaching concentrations
Concentration is that 0.27 mg/L, Ni leaching concentration is that 0.19 mg/L, Zn leaching concentration is that 0.12 mg/L, Cu leaching concentration is
0.97mg/L。
Embodiment 14
By incinerator ash 25wt.%, electroplating sludge 5wt.%, acid-washing stainless steel sludge 10wt.%, flyash 10wt.% and
Cullet 50wt.% is well mixed, and compound is containing 0.16 0.41 wt.%, the Cd 1.14 of wt.%, Ni of wt.%, Pb of Cr 1.78
wt.%、Zn 1.17wt.%、Cu 1.75 wt.%.Mixed material heating is obtained into melt to 1550 DEG C of fusings, basis is obtained through calendering
Glass, is then heated to 750 DEG C of coring and obtains coring glass, is then warming up to the crystalline substance that 950 DEG C of crystallization formation crystallites are evenly distributed
Change glass, last stress relieving by annealing obtains devitrified glass product.The MPa of bending strength 146 of devitrified glass, microhardness
6.9GPa, compression strength 650.0MPa, abrasion loss 0.090g/cm2, acid resistance（20wt% sulfuric acid）For 96.8%, fastness to alkali
（20wt% NaOH）It is that 0.25 mg/L, Pb leaching concentration is that 0.15 mg/L, Cd leachings are dense for 98.9%, Cr leaching concentrations
Degree is that 0.57 mg/L, Ni leaching concentration is that 0.12 mg/L, Zn leaching concentration is that 0.17 mg/L, Cu leaching concentration is
0.57mg/L。
Embodiment 15
By the wt.% of incinerator ash 15, the wt.% of chromium slag 10, the wt.% of electroplating sludge 15, the wt.% of lead and zinc smelting dreg 10, powder
The wt.% of the coal ash 10 and wt.% of cullet 40 is well mixed, and compound is containing 0.24 wt.%, the Ni 0.44 of wt.%, Pb of Cr 1.24
wt.%、Cd 1.12 wt.%、Zn 0.12wt.%、Cu 1.25 wt.%.Mixed material heating is obtained into melt to 1550 DEG C of fusings,
Parent glass is obtained through calendering, 750 DEG C of coring is then heated to and obtains coring glass, be then warming up to 950 DEG C of crystallization and form micro-
The crystallized glass that crystalline substance is evenly distributed, last stress relieving by annealing obtains devitrified glass product.The bending strength 98 of devitrified glass
MPa, microhardness 6.7GPa, compression strength 756.0MPa, abrasion loss 0.070g/cm2, acid resistance（20wt% sulfuric acid）For
96.8%, fastness to alkali（20wt% NaOH）It is that 0.15 mg/L, Pb leaching concentration is 0.12 for 98.8%, Cr leaching concentrations
Mg/L, Cd leaching concentration are that 0.18 mg/L, Ni leaching concentration is that 0.17 mg/L, Zn leaching concentration is 0.12 mg/L, Cu
Leaching concentration is 0.54mg/L.
Embodiment 16
By incinerator ash 15wt.%, stainless steel slag 10wt.%, acid-washing stainless steel sludge 5wt.%, electroplating sludge 10wt.%,
Lead and zinc smelting dreg 10wt.%, flyash 10wt.% and cullet 40wt.% are well mixed, compound wt.%, Pb containing Cr 1.23
0.12 wt.%、Ni 0.14 wt.%、Cd 1.75 wt.%、Zn 0.18wt.%、Cu 1.26 wt.%.Mixed material heating is arrived
1550 DEG C of fusings obtain melt, obtain parent glass through calendering, are then heated to 750 DEG C of coring and obtain coring glass, then rise
The crystallized glass that temperature is evenly distributed to 950 DEG C of crystallization formation crystallites, last stress relieving by annealing obtains devitrified glass product.Crystallite
The bending strength 134MPa of glass, microhardness 7.76GPa, compression strength 453.0MPa, abrasion loss 0.060g/cm2, it is acidproof
Degree（20wt% sulfuric acid）For 96.3%, fastness to alkali（20wt% NaOH）It is 0.079 mg/L, Pb for 98.6%, Cr leaching concentrations
Leaching concentration is that 0.42 mg/L, Cd leaching concentration is that 0.24 mg/L, Ni leaching concentration is that 0.15 mg/L, Zn leachings are dense
Degree is that 0.17 mg/L, Cu leaching concentration is 0.27mg/L.
Embodiment 17
By incinerator ash 10wt.%, chromium slag 10wt.%, stainless steel slag 10wt.%, acid-washing stainless steel sludge 10wt.%, electricity
Plate sludge 10wt.%, lead and zinc smelting dreg 5wt.%, flyash 5wt.% and cullet 40wt.% well mixed, compound contains Cr
1.43 wt.%、Pb 0.42 wt.%、Ni 0.84 wt.%、Cd 1.42 wt.%、Zn 0.11wt.%、Cu 1.24 wt.%.Will
Mixed material heating obtains melt to 1550 DEG C of fusings, obtains parent glass through calendering, is then heated to 750 DEG C of coring and obtains coring
Glass, is then warming up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed, and last stress relieving by annealing obtains crystallite glass
Glass product.Bending strength 128.0 MPa, microhardness 6.9GPa, compression strength 680.0MPa, abrasion loss of devitrified glass
0.070g/cm2, acid resistance（20wt% sulfuric acid）For 98.2%, fastness to alkali（20wt% NaOH）It is for 99.3%, Cr leaching concentrations
0.019 mg/L, Pb leaching concentration is that 0.22 mg/L, Cd leaching concentration is that 0.14 mg/L, Ni leaching concentration is 0.17
Mg/L, Zn leaching concentration are that 0.12 mg/L, Cu leaching concentration is 0.41mg/L.
Claims (2)
1. devitrified glass prepared by a kind of dangerous solid waste, it is characterised in that：The raw material of devitrified glass is incinerator ash, stainless steel
Slag, acid-washing stainless steel sludge, electroplating sludge, chromium slag, lead and zinc smelting dreg, 7 kinds of flyash danger are solid, and cullet, quartz sand and
Lime stone；
To be endangered in the preparation process of the devitrified glass it is solid in heavy metal Cr, Ni, Mn, Pb, Zn, Cu be nucleus；
Leaching of Heavy Metals concentration is in obtained devitrified glass：Cr≤5.0mg/L、Pb≤5.0mg/L、Cd≤1.0mg/L、Ni
≤1.0mg/L、Zn≤5.0mg/L、Cu≤5.0mg/L；
Containing Cr it is that 2.9wt.%-4.0wt.%, Pb are that 0.12wt.%-4.0wt.%, Ni are in described devitrified glass raw material
0.11wt.%-2.0wt.%, Cd are that 0.11wt.%-2.0wt.%, Zn are that 0.4wt.%-5.0wt.%, Cu are 1.1wt.%-
5.0wt.%；
Solid addition of being endangered in described devitrified glass raw material is 20.0wt.%-60.0wt.%, surplus be cullet, quartz sand and
Lime stone；
The bending strength 70.0MPa-150.0MPa of prepared devitrified glass, microhardness 6.0GPa-7.8GPa, compression strength
450.0MPa-792.0MPa, abrasion loss 0.040g/cm2-0.100g/cm2, the devitrified glass described in 20wt.% sulfuric acid solutions
Acid resistance >=96.0%, fastness to alkali >=98.0% of devitrified glass described in 20wt.% sodium hydroxide solutions.
2. devitrified glass prepared by a kind of dangerous solid waste according to claim 1, it is characterised in that：The devitrified glass
Preparation method comprises the following steps：
1) batch mixing：The raw material matched, which be well mixed, obtains compound；
2) melt：Mixed material heating to fusing obtains melt；
3) roll：Melt obtains parent glass through calendering；
4) coring：Parent glass obtains coring glass through coring；
5) crystallization：Coring glass forms the crystallized glass that crystallite is evenly distributed after crystallization；
6) anneal：The annealed stress that eliminates of crystallized glass obtains devitrified glass product.
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| CN201410783923.9A CN104445944B (en) | 2014-12-16 | 2014-12-16 | A kind of method that dangerous solid waste prepares devitrified glass |
| PCT/CN2014/094283 WO2016095180A1 (en) | 2014-12-16 | 2014-12-19 | Microcrystalline glass prepared from hazardous solid wastes, and preparation method therefor |
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| CN101759368B (en) * | 2010-03-18 | 2011-08-03 | 凤县三联建材有限责任公司 | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof |
| CN102211874B (en) * | 2011-05-10 | 2013-06-05 | 北京科技大学 | Microcrystalline glass and preparation method thereof |
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