CN104445944A - Method for preparing microcrystalline glass from hazardous solid wastes - Google Patents
Method for preparing microcrystalline glass from hazardous solid wastes Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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 a method for preparing microcrystalline glass by taking hazardous solid wastes which are hazardous solids for short. The method is characterized by taking heavy metals in the hazardous solids as nucleating agents, mixing, fusing, rolling, nucleating, crystallizing and annealing to obtain the microcrystalline glass. The method has the advantages that the heavy metal elements in waste incineration ash, stainless steel slag, stainless steel acid pickling sludge, electroplating sludge, chromium slag, lead-zinc smelting slag and coal ash can be stably solidified; the pollution is avoided; meanwhile, high-additional-value microcrystalline glass is prepared; the harmless high-value application of the hazardous solids is realized; and the method has remarkable environmental and economic benefits and wide market prospects.
Description
Technical field
The invention discloses and a kind of prepare the method for devitrified glass with endanger solid (dangerous solid waste) for raw material, belong to environmental protection and resource reutilization field.Heavy metal in utilizing danger solid, as nucleating agent, adopts scorification to prepare devitrified glass.Advantage of the present invention utilizes devitrified glass to realize heavy metal element stable curing, avoids polluting, and obtains the devitrified glass of high added value simultaneously.
Background technology
Industrial production creates a large amount of solid waste, wherein has substantial amounts, consolidates containing the various danger of heavy metal, the healthy and ecological environment security of serious threat people.The danger had a large capacity and a wide range mainly contains incinerator ash, stainless steel slag, acid-washing stainless steel mud, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash etc. admittedly.
1. incinerator ash
Along with Consideration of MSW Incineration Technology is promoted in China, the disposal for incineration ash of household rubbish has become the major issue of restriction industry development.Burning disposal one ton of rubbish about produces 20% bottom ash and 4% bag-type dust ash.Due to various heavy materials such as Cd, Pb, Cu, Zn and Cr of easily leaching containing higher concentration in incinerator ash, be put into " the solid register of country's danger ", be numbered HW18.
2. stainless steel slag
Stainless steel slag is the by product of stainless steel smelting.According to the rough estimates of China Metal material circulation association, within 2013, Chinese stainless steel crude steel output is 2,050 ten thousand tons.Produce 1 ton of stainless steel slag by often producing 3 tons of stainless steels, stainless steel slag output is more than 5,800,000 tons.Sexavalent chrome containing part aqueous, carcinogenic, teratogenesis in stainless steel slag, brings grave danger to ecotope.In company of China stainless steel slag, the leaching concentration of total chromium is 40 mg/L, wherein Cr
6+leaching content be 15mg/L, be 3 times of GB5085.3-2007 prescribed value, belong to danger solid.
3. acid-washing stainless steel mud
In cold-rolling production process, adopt HNO
3with HF mixing, at 40-60 DEG C, pickling and passivation are carried out to stainless steel strip surface, produce a large amount of spent pickle liquor containing hazardous and noxious substances such as Cr, Ni, obtain containing chromic acid contaminate mud through limestone vegetation precipitation, Cr
6+and Ni
2+leaching concentration be respectively 35mg/L and 50mg/L, be respectively 7 times and 10 times of GB5085.3-2007 prescribed value, belong to danger solid.
4. electroplating sludge
The electroplating sludge that plating produces 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, far above GB5085.3-2007 prescribed value, belongs to danger solid.
5. chromium slag
Chromium slag refers to the industrial residue produced in chromium metal and chromium salt production process.The China's chromium of You20Duo Ge provinces and cities discharge at present slag.According to statistics, often produce l ton sodium dichromate 99, average generation chromium slag 3-3.5 ton.Current domestic chromium salt production enterprise approximately discharges 20-30 ten thousand tons of chromium slags every year.Objectionable constituent in chromium slag are solubility Sodium chromate, yellow ultramarine etc. mainly, belongs to danger solid.
6. lead and zinc smelting dreg
2013, the plumbous zinc ultimate production of China reached 9,780,000 tons, occupies the first in the world for years.It is estimated, often produce 1 ton of plumbous discharge, 0.71 ton of waste residue, produce 1 ton of zinc and discharge 0.96 ton of slag.China's lead and zinc smelting dreg volume of cargo in storage crosses hundred million tons, containing various heavy, belongs to danger solid.
7. flyash
Flyash is the thin ash that coal combustion produces, primarily of SiO
2, Al
2o
3, FeO, Fe
2o
3, CaO, TiO
2deng composition.The annual emissions of China's coal-burning power plant's flyash reaches 2.9 hundred million tons, has become serious environmental problem.
Danger is solid to be disposed and recycling has become the focus of public attention, should follow minimizing, resource utilization and the fundamental principle such as innoxious.The solid disposal of danger and reutilization technology mainly contain curing/stabilizing, reduction and detoxication and valuable metal recovery, valuable metal, microbial method etc. are reclaimed in precipitation solidification.
1. curing/stabilizing technology
Curing/stabilizing technology is the solid the most frequently used treatment technology of danger.Most widely used in curing/stabilizing technology is cement solidification method.But in order to realize solid removing toxic substances of endangering, or reduce toxicity, often add different types of solidifying agent, these solidifying agent often play the effect of stabilizing heavy metal.The solid curing/stabilizing technology of existing danger mainly contains cement-based solidified/stabilization technology, vitrification/stabilization technology and brickmaking etc.
It is solid that cement solidification/stabilization technology is usually used in solidification danger, and its mechanism of action is that cement matrix and solid waste reacts and produced gelation, solid waste particle encapsulation, realizes heavy metal ion and solidifies, but the heavy metal ion existence leaching risk under extreme conditions in cement.Therefore; " the solid Environmental capacity standard of cement kiln synergic processing danger " (the GB 30485-2013), " the solid environmental protection technology specification of cement kiln synergic processing danger " (HJ 662-2013) that come into effect on March 1st, 2014 explicitly points out: when cement kiln synergic processing danger is solid; entering the maximum dosage limit value of heavy metal in furnace charge is: total Cr≤320 mg/kg; sexavalence Cr≤10 mg/kg; total Ni≤640 mg/kg, beryllium+chromium+10* tin+50* antimony+copper+manganese+barium+nickel+barium≤1150 mg/kg.
Vitrification/stabilization technology take glass as solidifying agent, after itself and danger are mixed with certain ratio of components admittedly, and melting under high temperature (1400-1600 DEG C), then obtain stable glass solidified body through annealing.Vitrification technology due to its heavy metals immobilization effective, Solid state fermentation amount is large, simple technological process and other advantages, but energy consumption is high, equipment cost is high, and added value of product is low.
The solid brick-making technology technique of danger is simple, production cost is low, large by the quantity of slag, be widely used in solid disposal of endangering.But, because brick valency is cheap, ball mill can not be adopted in brickmaking process to pulverize and mixing, cause the heavy metal ion in macrobead solid waste to be not easily reduced in sintering procedure.In addition, the research of nearly 2 years shows, the microtexture of adobe is comparatively loose, and basicity is relatively large, is easy to and acid or alkali reaction, the prolonged curing less effective of adobe heavy metal ion.Thus, most brick field has stopped utilizing solid waste of heavy metal brickmaking.
2. valuable metal is reclaimed in precipitation solidification
It is by after solid for danger dissolving under acid or alkaline conditions that valuable metal is reclaimed in precipitation solidification, adds reactant and valuable metal reduction or precipitation is reclaimed.The ubiquitous problem of wet processing is that secondary pollution is serious, compares and is suitable for heavy metal minimizing, can not solve heavy metal pollution problem.
3. reduction and detoxication and valuable metal recovery technology
This technology mixes solid for danger with reductive agent, and carry out rapid cooling or shrend after 600 DEG C-1000 DEG C heavy metal ion reduction and detoxications, realize valuable metal recovery, waste is for cement admixture.This technology has secondary pollution, and energy consumption is high.Abundant Xinghua factory adopts reduction and detoxication technical security to dispose tens thousand of tons of chromium slags and obtains ferrochrome, and waste is used for cement.
4. microbial method
Microbial method is by the metabolism of microorganism by the heavy metal ion enrichment in solid waste or reduction, realizes the solid removing toxic substances of danger or metal recovery.Chinese invention patent (CN 104058565 A) discloses a kind of method utilizing thiobacillus ferrooxidant process pickling mud, the Ni of Cr and 94.77%-94.89% of adsorbable recovery 34.48%-79.31%.The advantage of microbial method is that energy consumption is low, but there is the shortcomings such as long processing period, selective adsorption and residual concentration of heavy metal ion are higher.
Above-mentioned danger is disposed admittedly to exist with reuse method that residual heavy metal ionic concn is higher, tail liquid emissions amount is comparatively large, be difficult to the problems such as requirement that are up to state standards.Therefore, be badly in need of the exploitation solid cooperative disposal of a kind of danger and high-valued recycling new technology, realize innoxious, the high-valued and recycling of solid waste.Devitrified glass can the multiple solid waste of cooperative disposal, obtains compact structure, intensity is high, hardness is large, wear resistance is good, resistance to acids and bases is good ceramic, can be widely used in the fields such as metallurgy, building, house ornamentation, national defence.
Current devitrified glass raw material is mainly based on raw ore and slag.Chinese invention patent (CN102531394A) discloses one and utilizes lithium mine tailing to produce micro-crystal board material preparation method, with lithium mine tailing, calcium stone flour, quartz sand and tinting material etc. for low-expansion devitrified glass prepared by raw material.It take iron tailings as the method that black glass ceramic prepared by raw material that Chinese invention patent (CN101857367A) discloses a kind of.Chinese invention patent (CN1868946A) disclose a kind of with comprehensive utilization of waste material such as Ta Nb tailings, yellow phosphorus furnace slag and cullet for the method for devitrified glass prepared by raw material.Chinese invention patent (CN103086602A) disclose a kind of with golden mine tailing for main raw material adopts microwave technology to prepare the method for low expansion coefficient micro crystal glass.Chinese invention patent (CN101328021A) disclose a kind of with flyash, rare metal ore-dressing mine tailing for raw material, prepare CaO-MgO-Al
2o
3-SiO
2the porous devitrified glass of system.Above-mentioned devitrified glass Patents all adopts raw ore and slag to be raw material, does not relate to devitrified glass heavy metals immobilization effect, does not possess safe disposal and to endanger solid effect.
The invention discloses danger and admittedly prepare devitrified glass, the heavy metal element in utilizing danger solid, as original nucleus, is then grown up into containing the micron-sized crystallite of heavy metal, is uniformly distributed in vitreum.Danger not only can be prepared into the devitrified glass of acid-alkali-corrosive-resisting, wear-resisting, safety non-toxic by the present invention admittedly, and achieves heavy metals immobilization, reaches the effect of administering heavy metal contamination.
Summary of the invention
The invention discloses a kind of method that dangerous solid waste prepares devitrified glass, by the Cr in solid for danger, the heavy metals such as Ni, Mn, Pb, Zn, Cu as nucleus, CaO, MgO, SiO
2and Al
2o
3oxide compound, as main component, adopts scorification to prepare devitrified glass.The present invention's danger used is one or more in incinerator ash, stainless steel slag, acid-washing stainless steel mud, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash admittedly, and addition material is one or more in cullet, quartz sand, Wingdale.Concrete steps of the present invention are as follows:
Batching: one or more the danger in incinerator ash, stainless steel slag, acid-washing stainless steel mud, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash is solid, one or more in cullet, quartz sand and Wingdale, carry out proportioning by the composition of design;
Batch mixing: the raw material that proportioning is good carries out mixing obtaining compound;
Fusing: mixed material heating obtains melt to fusing;
Calendering: melt obtains parent glass through calendering, does not namely have the glass of forming core;
Coring: parent glass obtains coring glass through coring, the glass namely containing a large amount of nucleating agent;
Crystallization: coring glass forms the crystallized glass that crystallite is evenly distributed after crystallization, namely nucleating agent is grown up for the glass of micron order crystallite;
Annealing: crystallized glass obtains devitrified glass product through stress relieving by annealing.
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, far below GB5085.3-2007 prescribed value.Advantage of the present invention is by the heavy metal element stable curing in incinerator ash, stainless steel slag, acid-washing stainless steel mud, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash, avoid pollution, obtain the devitrified glass of high added value simultaneously, achieve the solid innoxious higher value application of danger, there is significant environment benefits and economic gains, wide market.
Accompanying drawing explanation
Fig. 1 devitrified glass preparation flow.
Fig. 2 devitrified glass microstructure.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not only confined to following examples.
embodiment 1
Mixed by incinerator ash 60.0wt.% and cullet 40.0wt.%, compound is containing Cr 0.8 wt.%, Pb 1.4 wt.%, Ni 2.0 wt.%, Cd 2.0 wt.%, Zn 5.0 wt.%, Cu 2.1 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 70.0 MPa of devitrified glass, microhardness 6.0GPa, ultimate compression strength 450.0MPa, wear loss 0.040g/cm
2acid fastness (20wt% sulfuric acid) is 96.0%, fastness to alkali (20wt% sodium hydroxide) is 98.0%, Cr leaching concentration is 0.2 mg/L, Pb leaching concentration be 0.07 mg/L, Cd leaching concentration be 0.6 mg/L, Ni leaching concentration be 0.25 mg/L, Zn leaching concentration be 5.0 mg/L, Cu leaching concentration is 3.11 mg/L.
embodiment 2
Mixed by stainless steel slag 50 wt.% and quartz sand 50 wt.%, compound is containing Cr 4.0 wt.%, Pb 0 wt.%, Ni 0.5 wt.%, Cd 0 wt.%, Zn 0.7 wt.%, Cu 1.1 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.The bending strength 150.0MPa of devitrified glass, microhardness 7.8GPa, ultimate compression strength 792.0MPa, wear loss 0.100g/cm
2acid fastness (20wt% sulfuric acid) is 97.1%, fastness to alkali (20wt% sodium hydroxide) is 98.4%, Cr leaching concentration be 5.0 mg/L, Pb leaching concentrations be 0 mg/L, Cd leaching concentration be 0 mg/L, Ni leaching concentration be 0.15 mg/L, Zn leaching concentration be 2.10 mg/L, Cu leaching concentrations is 1.54 mg/L.
embodiment 3
Electroplating sludge 20wt.%, Wingdale 40wt.% and cullet 40wt.% are mixed, compound is containing 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 obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 100.0 MPa of devitrified glass, microhardness 6.5GPa, ultimate compression strength 550.0MPa, wear loss 0.050g/cm
2acid fastness (20wt% sulfuric acid) is 98.2%, fastness to alkali (20wt% sodium hydroxide) is 98.8%, Cr leaching concentration be 0.22 mg/L, Pb leaching concentration be 0.15 mg/L, Cd leaching concentration be 0.11 mg/L, Ni leaching concentration be 0 mg/L, Zn leaching concentration be 5.0 mg/L, Cu leaching concentrations is 5.0 mg/L.
embodiment 4
Mixed by chromium slag 40 wt.% and quartz sand 60 wt.%, compound is containing Cr 2.9 wt.%, Pb 1.5 wt.%, Ni 0.3 wt.%, Cd 0.6 wt.%, Zn 0.4 wt.%, Cu 2.02 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 122.0 MPa of devitrified glass, microhardness 6.8GPa, ultimate compression strength 600.0MPa, wear loss 0.054g/cm
2acid fastness (20wt% sulfuric acid) is 97.4%, fastness to alkali (20wt% sodium hydroxide) is 98.9%, Cr leaching concentration be 0.12 mg/L, Pb leaching concentration be 0.14 mg/L, Cd leaching concentration to be 0.04 mg/L, Ni leaching concentration be 0.14 mg/L, Zn 1.5 mg/L, Cu leaching concentration be 2.01 mg/L.
embodiment 5
Mixed by lead and zinc smelting dreg 55wt.% and quartz sand 45wt.%, compound is containing Cr 1.1 wt.%, Pb 4.0 wt.%, Ni 0.3 wt.%, Cd 0.6 wt.%, Zn 4.2 wt.%, Cu 0 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 110.0 MPa of devitrified glass, microhardness 7.2GPa, ultimate compression strength 760.0MPa, wear loss 0.050g/cm
2acid fastness (20wt% sulfuric acid) is 98.0%, fastness to alkali (20wt% sodium hydroxide) is 99.2%, Cr leaching concentration be 0.14 mg/L, Pb leaching concentration be 5.0 mg/L, Cd leaching concentrations be 0.01 mg/L, Ni leaching concentration to be 0.04 mg/L, Zn leaching concentration be 3.4 mg/L, Cu 0 mg/L.
embodiment 6
Mixed by flyash 45wt.% and cullet 55wt.%, compound is containing Cr 0 wt.%, Pb 1.04 wt.%, Ni 1.0 wt.%, Cd 1.0 wt.%, Zn 0 wt.%, Cu 2.4 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 144.0 MPa of devitrified glass, microhardness 7.3GPa, ultimate compression strength 656.0MPa, wear loss 0.080g/cm
2acid fastness (20wt% sulfuric acid) is 97.2%, fastness to alkali (20wt% sodium hydroxide) is 99.1%, Cr leaching concentration be 0 mg/L, Pb leaching concentration be 1.02 mg/L, Cd leaching concentrations be 1.0 mg/L, Ni leaching concentrations be 1.0 mg/L, Zn leaching concentrations be 0 mg/L, Cu leaching concentration is 2.65 mg/L.
embodiment 7
Incinerator ash 20wt.%, flyash 35wt.% and cullet 45wt.% are mixed, compound is containing Cr 1.2 wt.%, Pb 1.14 wt.%, Ni 0.2 wt.%, Cd 0.7 wt.%, Zn 1.2 wt.%, Cu 2.6 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 128.0 MPa of devitrified glass, microhardness 6.2GPa, ultimate compression strength 564.0MPa, wear loss 0.090g/cm
2acid fastness (20wt% sulfuric acid) is 97.2%, fastness to alkali (20wt% sodium hydroxide) is 99.5%, Cr leaching concentration be 0.12 mg/L, Pb leaching concentration be 0.22 mg/L, Cd leaching concentration be 0.42 mg/L, Ni leaching concentration be 0.45 mg/L, Zn leaching concentration be 0.35 mg/L, Cu leaching concentration is 1.55 mg/L.
embodiment 8
Stainless steel slag 35wt.%, acid-washing stainless steel mud 15wt.% and cullet 50wt.% are mixed, compound is containing 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 melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 83.0 MPa of devitrified glass, microhardness 6.6GPa, ultimate compression strength 750.0MPa, wear loss 0.050g/cm
2acid fastness (20wt% sulfuric acid) is 99.5%, fastness to alkali (20wt% sodium hydroxide) is 99.4%, acid resistance 98.7%, alkali resistance 99.2%, Cr leaching concentration is 0.11 mg/L, Pb leaching concentration be 0.12 mg/L, Cd leaching concentration be 0.22 mg/L, Ni leaching concentration be 0.25 mg/L, Zn leaching concentration be 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 mixed, compound is containing Cr 1.3 wt.%, Pb 1.14 wt.%, Ni 0.43 wt.%, Cd 0.31 wt.%, Zn 1.59 wt.%, Cu 2.44 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 147.0 MPa of devitrified glass, microhardness 7.8GPa, ultimate compression strength 532.0MPa, wear loss 0.090g/cm
2acid fastness (20wt% sulfuric acid) is 96.6%, fastness to alkali (20wt% sodium hydroxide) is 98.6%, Cr leaching concentration be 0.13 mg/L, Pb leaching concentration be 0.19 mg/L, Cd leaching concentration be 0.24mg/L, Ni leaching concentration be 0.26 mg/L, Zn leaching concentration be 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 mixed, compound is containing Cr 1.7 wt.%, Pb 2.18 wt.%, Ni 0.51 wt.%, Cd 0.11 wt.%, Zn 1.24 wt.%, Cu 1.24 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 117.0 MPa of devitrified glass, microhardness 7.3GPa, ultimate compression strength 590.0MPa, wear loss 0.065g/cm
2acid fastness (20wt% sulfuric acid) is 99.7%, fastness to alkali (20wt% sodium hydroxide) is 99.8%, Cr leaching concentration be 0.14 mg/L, Pb leaching concentration be 0.12 mg/L, Cd leaching concentration be 0.27mg/L, Ni leaching concentration be 0.28mg/L, Zn leaching concentration be 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 mud 10wt.% and cullet 50wt.% are mixed, 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 melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 93 MPa of devitrified glass, microhardness 7.3GPa, ultimate compression strength 560.0MPa, wear loss 0.080g/cm
2acid fastness (20wt% sulfuric acid) is 98.2%, fastness to alkali (20wt% sodium hydroxide) is 99.3%, Cr leaching concentration be 0.18 mg/L, Pb leaching concentration be 0.45 mg/L, Cd leaching concentration be 0.29mg/L, Ni leaching concentration be 0.42mg/L, Zn leaching concentration be 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 mud 10wt.% and cullet 50wt.% are mixed, 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 melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 90.0 MPa of devitrified glass, microhardness 7.2GPa, ultimate compression strength 560.0MPa, wear loss 0.090g/cm
2acid fastness (20wt% sulfuric acid) is 97.7%, fastness to alkali (20wt% sodium hydroxide) is 99.4%, Cr leaching concentration be 0.07 mg/L, Pb leaching concentration be 0.15 mg/L, Cd leaching concentration be 0.24 mg/L, Ni leaching concentration be 0.41 mg/L, Zn leaching concentration be 0.15 mg/L, Cu leaching concentration is 0.27mg/L.
embodiment 13
Stainless steel slag 25wt.%, electroplating sludge 10wt.%, acid-washing stainless steel mud 5wt.%, flyash 10wt.% and cullet 50wt.% are mixed, compound is containing Cr 1.4 wt.%, Pb 2.16 wt.%, Ni 0.11 wt.%, Cd 0.14 wt.%, Zn 1.27wt.%, Cu 1.21 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 134.0 MPa of devitrified glass, microhardness 6.79GPa, ultimate compression strength 676.0MPa, wear loss 0.045g/cm
2acid fastness (20wt% sulfuric acid) is 97.7%, fastness to alkali (20wt% sodium hydroxide) is 98.8%, Cr leaching concentration be 0.085 mg/L, Pb leaching concentration be 0.025 mg/L, Cd leaching concentration be 0.27 mg/L, Ni leaching concentration be 0.19 mg/L, Zn leaching concentration be 0.12 mg/L, Cu leaching concentration is 0.97mg/L.
embodiment 14
Incinerator ash 25wt.%, electroplating sludge 5wt.%, acid-washing stainless steel mud 10wt.%, flyash 10wt.% and cullet 50wt.% are mixed, compound is containing Cr 1.78 wt.%, Pb 0.16 wt.%, Ni 0.41 wt.%, Cd 1.14 wt.%, Zn 1.17wt.%, Cu 1.75 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 146 MPa of devitrified glass, microhardness 6.9GPa, ultimate compression strength 650.0MPa, wear loss 0.090g/cm
2acid fastness (20wt% sulfuric acid) is 96.8%, fastness to alkali (20wt% sodium hydroxide) is 98.9%, Cr leaching concentration be 0.25 mg/L, Pb leaching concentration be 0.15 mg/L, Cd leaching concentration be 0.57 mg/L, Ni leaching concentration be 0.12 mg/L, Zn leaching concentration be 0.17 mg/L, Cu leaching concentration is 0.57mg/L.
embodiment 15
Incinerator ash 15 wt.%, chromium slag 10 wt.%, electroplating sludge 15 wt.%, lead and zinc smelting dreg 10 wt.%, flyash 10 wt.% and cullet 40 wt.% are mixed, compound is containing Cr 1.24 wt.%, Pb 0.24 wt.%, Ni 0.44 wt.%, Cd 1.12 wt.%, Zn 0.12wt.%, Cu 1.25 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 98 MPa of devitrified glass, microhardness 6.7GPa, ultimate compression strength 756.0MPa, wear loss 0.070g/cm
2acid fastness (20wt% sulfuric acid) is 96.8%, fastness to alkali (20wt% sodium hydroxide) is 98.8%, Cr leaching concentration be 0.15 mg/L, Pb leaching concentration be 0.12 mg/L, Cd leaching concentration be 0.18 mg/L, Ni leaching concentration be 0.17 mg/L, Zn leaching concentration be 0.12 mg/L, Cu leaching concentration is 0.54mg/L.
embodiment 16
Incinerator ash 15wt.%, stainless steel slag 10wt.%, acid-washing stainless steel mud 5wt.%, electroplating sludge 10wt.%, lead and zinc smelting dreg 10wt.%, flyash 10wt.% and cullet 40wt.% are mixed, compound is containing Cr 1.23 wt.%, Pb 0.12 wt.%, Ni 0.14 wt.%, Cd 1.75 wt.%, Zn 0.18wt.%, Cu 1.26 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.The bending strength 134MPa of devitrified glass, microhardness 7.76GPa, ultimate compression strength 453.0MPa, wear loss 0.060g/cm
2acid fastness (20wt% sulfuric acid) is 96.3%, fastness to alkali (20wt% sodium hydroxide) is 98.6%, Cr leaching concentration be 0.079 mg/L, Pb leaching concentration be 0.42 mg/L, Cd leaching concentration be 0.24 mg/L, Ni leaching concentration be 0.15 mg/L, Zn leaching concentration be 0.17 mg/L, Cu leaching concentration is 0.27mg/L.
embodiment 17
Incinerator ash 10wt.%, chromium slag 10wt.%, stainless steel slag 10wt.%, acid-washing stainless steel mud 10wt.%, electroplating sludge 10wt.%, lead and zinc smelting dreg 5wt.%, flyash 5wt.% and cullet 40wt.% are mixed, compound is containing Cr 1.43 wt.%, Pb 0.42 wt.%, Ni 0.84 wt.%, Cd 1.42 wt.%, Zn 0.11wt.%, Cu 1.24 wt.%.Mixed material heating is obtained melt to 1550 DEG C of fusings, parent glass is obtained through calendering, then be heated to 750 DEG C of coring and obtain coring glass, be warmed up to the crystallized glass that 950 DEG C of crystallization formation crystallites are evenly distributed subsequently, last stress relieving by annealing obtains devitrified glass product.Bending strength 128.0 MPa of devitrified glass, microhardness 6.9GPa, ultimate compression strength 680.0MPa, wear loss 0.070g/cm
2acid fastness (20wt% sulfuric acid) is 98.2%, fastness to alkali (20wt% sodium hydroxide) is 99.3%, Cr leaching concentration be 0.019 mg/L, Pb leaching concentration be 0.22 mg/L, Cd leaching concentration be 0.14 mg/L, Ni leaching concentration be 0.17 mg/L, Zn leaching concentration be 0.12 mg/L, Cu leaching concentration is 0.41mg/L.
Claims (9)
1. a dangerous solid waste prepares devitrified glass, it is characterized in that: the raw material of devitrified glass is that one or more the danger in incinerator ash, stainless steel slag, acid-washing stainless steel mud, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash is solid, and one or more in cullet, quartz sand and Wingdale.
2. the dangerous solid waste of one according to claim 1 prepares devitrified glass, it is characterized in that: in described devitrified glass raw material, the solid addition of danger is 20.0 wt.%-60.0 wt.%, and surplus is one or both in cullet, quartz sand and Wingdale.
3. the dangerous solid waste of one according to claim 1 prepares devitrified glass, it is characterized in that: be 0wt.%-4.0 wt.%, Pb be 0wt.%-4.0 wt.%, Ni be 0 wt.%-2.0 wt. %, Cd be 0 wt.%-2.0 wt.%, Zn be 0wt.%-5.0 wt.%, Cu containing Cr in described devitrified glass raw material be 0wt.%-5.0 wt.%.
4. the dangerous solid waste of one according to claim 1 prepares devitrified glass, it is characterized in that: in obtained devitrified glass, Leaching of Heavy Metals concentration is: 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.
5. the dangerous solid waste of one according to claim 1 prepares devitrified glass, it is characterized in that: bending strength 70.0MPa-150.0 MPa of prepared devitrified glass, microhardness 6.0GPa-7.8GPa, ultimate compression strength 450.0MPa-792.0MPa, wear loss 0.040g/cm
2-0.100g/cm
2, acid fastness (20wt% sulfuric acid)>=96.0%, fastness to alkali (20wt% sodium hydroxide)>=98.0%.
6. dangerous solid waste prepares a method for devitrified glass, it is characterized in that, said method comprising the steps of:
1) batch mixing: the raw material that proportioning is good carries out mixing obtaining compound;
2) melt: mixed material heating obtains melt to fusing;
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: crystallized glass obtains devitrified glass product through stress relieving by annealing.
7. dangerous solid waste according to claim 6 prepares devitrified glass, it is characterized in that, the raw material that proportioning described in step 1) is good one or more the danger that to be the raw material of devitrified glass be in incinerator ash, stainless steel slag, acid-washing stainless steel mud, electroplating sludge, chromium slag, lead and zinc smelting dreg, flyash is solid, and one or more in cullet, quartz sand and Wingdale.
8. dangerous solid waste according to claim 7 prepares devitrified glass, it is characterized in that, be 0wt.%-4.0 wt.%, Pb be 0wt.%-4.0 wt.%, Ni be 0 wt.%-2.0 wt. %, Cd be 0 wt.%-2.0 wt.%, Zn be 0wt.%-5.0 wt.%, Cu be 0wt.%-5.0 wt.% in described devitrified glass raw material containing Cr.
9. dangerous solid waste according to claim 6 prepares devitrified glass, it is characterized in that, in the devitrified glass obtained by step 6), Leaching of Heavy Metals concentration is: 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.
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| 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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| WO2016095180A1 (en) | 2016-06-23 |
| CN104445944B (en) | 2017-07-18 |
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