CN107311455A - A kind of method that utilization arsenic-containing waste residue prepares the curing glass containing arsenic - Google Patents
A kind of method that utilization arsenic-containing waste residue prepares the curing glass containing arsenic Download PDFInfo
- Publication number
- CN107311455A CN107311455A CN201710664986.6A CN201710664986A CN107311455A CN 107311455 A CN107311455 A CN 107311455A CN 201710664986 A CN201710664986 A CN 201710664986A CN 107311455 A CN107311455 A CN 107311455A
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- Prior art keywords
- arsenic
- waste residue
- containing waste
- method described
- curing glass
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Classifications
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/09—Other methods of shaping glass by fusing powdered glass in a shaping mould
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of method that utilization arsenic-containing waste residue prepares the curing glass containing arsenic.By by arsenic-containing waste residue, Copper making waste residue, silica-base material and boric acid according to certain mass than mixing and ball milling, sieving, compound is placed in fireproof die, the solid phase reaction under the conditions of certain temperature, then take out and cool down in the condition of high temperature, the curing glass that uniform color, hardness are high, surface is smooth is obtained, gained curing glass meets the requirement of general industry unorganic glass material.This method is converted into the curing glass of industrial utility value using copper ashes and hazardous waste arsenic-containing waste residue the orientation regulation and control discarded in industry.Not only realize minimizing and the secondary resource of copper ashes, solve copper ashes terminal open circuit and problem of environmental pollution, and the target of arsenic-containing waste residue harmlessness disposing is realized, turn waste into wealth, be that the processing of Copper making industry copper ashes and arsenic pollution opens a Green Sustainable road.
Description
Technical field
The invention belongs to inorganic non-metallic material and environmental project crossing domain, it is related to a kind of prepared using arsenic-containing waste residue and contains
The method of arsenic curing glass.
Background technology
Substantial amounts of arsenic-containing waste residue is produced during mining, smelting and chemical industry etc..The annual arsenic row of the only coloured industry of China
High-volume more than 40,000 tons, the arsenic slag of generation is more than 3,000,000 tons/year.Because the market of arsenic is limited, enterprise is in recycling removal process
Middle shortage economic stimuli, the arsenic-containing waste residue produced at present is mostly disposed in the way of banking up or simply solidifying landfill, is had
Great environmental risk, while also result in the waste of arsenic resource.
Curing/stabilizing technology is mostly used on arsenic Slag treatment, disposal at present, rarely has and relates to the use of the preparation of arsenic slag containing arsenic
The research report of curing glass or license.(bavin founds member etc. to an only correlation patent, and one kind solidification is useless containing arsenic at present
The method of material and the solid arsenic class crystal product of generation and application, number of patent application：201310188317.8), researcher will contain
Arsenic waste residue and iron boron phosphorus system's parent glass and arsenic stabilizer are placed in pressurization (10~12Mpa) in stainless steel mould, warp after drying
0.8-1.2h is at the uniform velocity warming up to 400-500 degrees Celsius of firing, then the natural cooling demoulding obtains solid arsenic class crystal.Although the above method
Solid arsenic class crystal can be obtained, but needs to add iron boron phosphorus system's parent glass and arsenic stabilizer progress dispensing, in addition the curing reaction
Need under pressure (10~12Mpa) solid arsenic class crystal could be obtained, otherwise can be only formed cured block.And the present invention is logical
Curing glass containing arsenic can be fired at ambient pressure by crossing special formulation and ratio.
Up to the present, being prepared under also no normal pressure using arsenic slag and Copper making waste residue, silica-base material and boric acid is had
The relevant report of the practical curing glass containing arsenic of high rigidity.
The content of the invention
Residue resource is utilized it is an object of the invention to provide one kind, solidifying containing arsenic with industrial utility value is prepared
The method of glass, turns waste into wealth, and solves the terminal open circuit of copper ashes and the harmlessness disposing of arsenic-containing waste residue.
To achieve the above object, the invention provides a kind of method that utilization arsenic-containing waste residue prepares the curing glass containing arsenic：Will
Arsenic-containing waste residue, Copper making waste residue, silica-base material and boric acid are according to certain mass percent mixing and ball milling, sieving, by compound
It is placed in fireproof die, the solid phase reaction under the conditions of certain temperature, then takes out and cool down in the condition of high temperature, finally give containing arsenic
Curing glass.
The arsenic-containing waste residue refers to the waste residue that arsenic exists in the form of arsenate (arsenic acid is received, calcium arsenate, ferric arsenate etc.), gives up
As is no more than 30wt% in slag, and Na accounts for 10wt%-30wt%, and Ca is no more than 30wt%, and Fe is no more than 20wt%.
Described Copper making waste residue derives from Copper making melting slow cooling operation, and main component is SiO2Account for 25%-35%,
FeO accounts for 30%-50%, Fe3O4Account for 5%-20%, Cu<2%, CaO account for 3%-20%, and remaining is a small amount of magnesium, aluminum oxide.
The silica-base material is scrap glass or flyash, and main component is SiO2Account for 65%-100%, B2O3Account for 0%-
20%, Na2O accounts for 0%-10%, and remaining is a small amount of alkaline metal oxide.
Described method：Arsenic-containing waste residue, Copper making waste residue, silica-base material and boric acid mass ratio be (10%-30%),
(30%-50%), (20%-50%), (5%-15%).
Described method：The mixing and ball milling crosses grit number for 100-300 mesh.It is preferred that 150 mesh.
Described method：Reaction is carried out in air and/or inert atmosphere, and preferably atmosphere is air.Sintering temperature is
1000-1500 DEG C, preferable temperature is 1200 DEG C.5-20 DEG C of heating rate/min, preferably heating rate are 10 DEG C/min.During insulation
Between be 1-5h, preferably soaking time be 2h.
Described method：The fireproof die material is ceramic-like or corundum class.
Described method：The type of cooling includes air cooling, air-cooled, water cooling or liquid nitrogen cooling.It is preferred that the type of cooling
Cooled down for air.
Compared with the prior art, the beneficial effect that technical scheme is brought：
1st, the uniform color of curing glass containing arsenic obtained by the present invention, hardness is high, with higher industrial utility value.
2nd, the present invention, without being carried out under the conditions of reaction under high pressure, saves energy consumption relative to prior art.
3rd, the primary raw material used in the present invention is industrial residue and dangerous waste containing arsenic, turns waste into wealth, is Copper making industry copper ashes
And the processing of arsenic pollution opens a Green Sustainable road.
Brief description of the drawings
Fig. 1 is the process chart of the inventive method；
The XRD for the curing glass containing arsenic that Fig. 2 is prepared for the present invention；
The pattern for the curing glass containing arsenic that Fig. 3 is prepared for the present invention.
Embodiment
The present invention is described in further details with reference to specific embodiment, specific embodiment described herein is only used
In explaining the present invention, it is not intended to limit the invention.
Embodiment 1
Copper smelting slag, arsenic-containing waste residue, silica-base material and boric acid are used for raw material, wherein arsenic-containing waste residue, copper smelting slag and
The group composition of silica-base material see the table below.By copper smelting slag, arsenic-containing waste residue, silica-base material and boric acid according to mass ratio be 40:20:
31:9 carry out dispensing ball milling 1h, cross 150 mesh and are placed in ceramic crucible, and ceramic crucible is placed in Muffle furnace in air atmosphere
It is fired, it is 10 DEG C/min to 1100 DEG C to keep heating rate, is incubated 1h.After reaction terminates, ceramic crucible is taken out and is placed in
Cooled down in air, obtain curing glass containing arsenic.X-ray diffraction analysis are carried out to the glass material of synthesis, figure is as a result seen；Meanwhile,
Leaching characteristic and intensity test are carried out using U.S.'s TCLP methods and GB_T17671-1999 Test method for strength of hydraulic cement mortar,
As a result it see the table below.
Table 1-1 arsenic-containing waste residue chemical compositions
| Element | As | Na | Si | K | Fe | P | Ca |
| Content (wt%) | 25.9 | 29.2 | 0.035 | 0.02 | 0.45 | 0.19 | 0.72 |
Table 1-2 copper smelting slag chemical compositions
| Element | Fe | Si | Cu | Zn | Mg | As | Ca |
| Content (wt%) | 46.97 | 13.37 | 0.61 | 1.61 | 0.64 | 0.0061 | 0.41 |
Table 1-3 silica-base material cullet chemical compositions
| Element | Fe | Si | Na | B | Al | Zr | Ca |
| Content (wt%) | 0.16 | 34.05 | 2.91 | 4.37 | 1.13 | 0.05 | 0.25 |
The table 1-4 performances of curing glass containing arsenic
Embodiment 2
Copper smelting slag, arsenic-containing waste residue, silica-base material and boric acid are used for raw material, wherein arsenic-containing waste residue, copper smelting slag and
The group composition of silica-base material see the table below.By copper smelting slag, arsenic-containing waste residue, silica-base material and boric acid according to mass ratio be 31:27:
33:9 carry out dispensing ball milling 1h, the raw material for crossing 200 mesh are placed in ceramic crucible, and ceramic crucible is placed in Muffle furnace in sky
It is fired in gas atmosphere, it is 10 DEG C/min to 1150 DEG C to keep heating rate, is incubated 1.5h.After reaction terminates, by ceramic earthenware
Crucible takes out and is placed in water cooling, obtains curing glass containing arsenic.Meanwhile, using U.S.'s TCLP methods and GB_T17671-1999 cement gels
Sand ruggedness test method carries out leaching characteristic and intensity test, as a result see the table below.
Table 2-1 arsenic-containing waste residue chemical compositions
| Element | As | Na | Si | Fe | P | Ca |
| Content (wt%) | 22.1 | 7.62 | 0.49 | 1.46 | 0.17 | 21.2 |
Table 2-2 copper smelting slag chemical compositions
| Element | Fe | Si | Cu | Zn | Mg | As | Ca |
| Content (wt%) | 46.97 | 13.37 | 0.61 | 1.61 | 0.64 | 0.0061 | 0.41 |
Table 2-3 silica-base material cullet chemical compositions
| Element | Fe | Si | Na | B | Al | Zr | Ca |
| Content (wt%) | 0.16 | 34.05 | 2.91 | 4.37 | 1.13 | 0.05 | 0.25 |
The table 2-4 performances of curing glass containing arsenic
Embodiment 3
Copper smelting slag, arsenic-containing waste residue, silica-base material and boric acid are used for raw material, wherein arsenic-containing waste residue, copper smelting slag and
The group composition of silica-base material see the table below.By copper smelting slag, arsenic-containing waste residue, silica-base material and boric acid according to mass ratio be 44:18:
28:10 carry out dispensing ball milling 1h, the raw material for crossing 300 mesh are placed in corundum crucible, and corundum crucible is placed in Muffle furnace
It is fired in air atmosphere, it is 10 DEG C/min to 1100 DEG C to keep heating rate, is incubated 1h.After reaction terminates, by ceramic earthenware
Crucible takes out to be placed in liquid nitrogen and cooled down, and obtains curing glass containing arsenic.Meanwhile, using U.S.'s TCLP methods and GB_T17671-1999 cement
The cement mortar strength method of inspection carries out leaching characteristic and intensity test, as a result see the table below.
Table 3-1 arsenic-containing waste residue chemical compositions
| Element | As | Na | Si | K | Fe | P | Ca |
| Content (wt%) | 25.9 | 29.2 | 0.035 | 0.02 | 0.45 | 0.19 | 0.72 |
Table 3-2 copper smelting slag chemical compositions
| Element | Fe | Si | Cu | Zn | S | As | Ca |
| Content (wt%) | 43.31 | 16.14 | 1.77 | 3.64 | 1.32 | 0.0061 | 4.38 |
Table 3-3 silica-base material cullet chemical compositions
| Element | Fe | Si | Na | B | Al | Zr | Ca |
| Content (wt%) | 0.16 | 34.05 | 2.91 | 4.37 | 1.13 | 0.05 | 0.25 |
The table 3-4 performances of curing glass containing arsenic
Claims (9)
1. a kind of method that utilization arsenic-containing waste residue prepares the curing glass containing arsenic, it is characterised in that：Arsenic-containing waste residue, Copper making are given up
Compound is placed in fireproof die by slag, silica-base material and boric acid according to certain mass percent mixing and ball milling, sieving,
The solid phase reaction under the conditions of certain temperature, then takes out in the condition of high temperature and cools down, finally give curing glass containing arsenic.
2. according to the method described in claim 1, it is characterised in that：The arsenic-containing waste residue refers to that arsenic exists in the form of arsenate
Waste residue, As is no more than 30wt% in waste residue, and Na accounts for 10wt%-30wt%, and Ca is no more than 30wt%, and Fe is no more than 20wt%.
3. according to the method described in claim 1, it is characterised in that：Described Copper making waste residue derives from Copper making melting slow cooling
Process, main component is SiO225%-35% is accounted for, FeO accounts for 30%-50%, Fe3O4Account for 5%-20%, Cu<2%, CaO account for 3%-
20%, remaining is a small amount of magnesium, aluminum oxide.
4. according to the method described in claim 1, it is characterised in that：The silica-base material be scrap glass or flyash, mainly
Composition is SiO2Account for 65%-100%, B2O3Account for 0%-20%, Na2O accounts for 0%-10%, and remaining is a small amount of alkaline metal oxide.
5. according to the method described in claim 1, it is characterised in that：Arsenic-containing waste residue, Copper making waste residue, silica-base material and boric acid
Mass ratio is (10%-30%), (30%-50%), (20%-50%), (5%-15%).
6. according to the method described in claim 1, it is characterised in that：The mixing and ball milling crosses grit number for 100-300 mesh.
7. according to the method described in claim 1, it is characterised in that：Reaction is carried out in air and/or inert atmosphere, sintering temperature
Spend for 1000-1500 DEG C, 5-20 DEG C of heating rate/min, soaking time is 1-5h.
8. according to the method described in claim 1, it is characterised in that：The fireproof die material is ceramic-like or corundum class.
9. according to the method described in claim 1, it is characterised in that：The type of cooling include air cooling, air-cooled, water cooling or
Liquid nitrogen is cooled down.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107913893A (en) * | 2017-11-13 | 2018-04-17 | 中南大学 | A kind of method using biomass solid waste residue containing arsenate |
| CN108620409A (en) * | 2018-03-14 | 2018-10-09 | 中南大学 | A method of fixing arsenic-containing waste using high-temperature liquid furnace slag |
| CN109621278A (en) * | 2019-01-14 | 2019-04-16 | 昆明理工大学 | One kind gypsum tailings containing arsenic cooperates with cured method with copper ashes |
| CN112718793A (en) * | 2020-12-15 | 2021-04-30 | 紫金矿业集团股份有限公司 | Method for directly vitrifying arsenic-fixing material containing arsenite |
| WO2022137259A1 (en) * | 2020-12-23 | 2022-06-30 | Council Of Scientific And Industrial Research | A method for safe disposal of arsenic rich sludge obtained from treatment of contaminated groundwater and its utilization in developing heat protective glass |
| CN115650588A (en) * | 2022-05-24 | 2023-01-31 | 长江师范学院 | Method for preparing microcrystalline glass by solidifying arsenic-alkali slag through ammonium leaching steel slag |
| CN116197209A (en) * | 2023-01-17 | 2023-06-02 | 广西凯玺有色金属有限公司 | Cleaning treatment method for calcium arsenate glass solidification and application thereof |
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| CN102965517A (en) * | 2012-12-03 | 2013-03-13 | 中南大学 | Treatment method for vitrifying arsenic-alkali residue |
| CN103212569A (en) * | 2013-05-08 | 2013-07-24 | 锡矿山闪星锑业有限责任公司 | Innocent treatment method for arsenic containing mixed salt |
| WO2016205925A1 (en) * | 2015-06-23 | 2016-12-29 | Dundee Sustainable Technologies Inc. | A method and composition for sequestration of arsenic |
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2017
- 2017-08-07 CN CN201710664986.6A patent/CN107311455A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102965517A (en) * | 2012-12-03 | 2013-03-13 | 中南大学 | Treatment method for vitrifying arsenic-alkali residue |
| CN103212569A (en) * | 2013-05-08 | 2013-07-24 | 锡矿山闪星锑业有限责任公司 | Innocent treatment method for arsenic containing mixed salt |
| WO2016205925A1 (en) * | 2015-06-23 | 2016-12-29 | Dundee Sustainable Technologies Inc. | A method and composition for sequestration of arsenic |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107913893A (en) * | 2017-11-13 | 2018-04-17 | 中南大学 | A kind of method using biomass solid waste residue containing arsenate |
| CN108620409A (en) * | 2018-03-14 | 2018-10-09 | 中南大学 | A method of fixing arsenic-containing waste using high-temperature liquid furnace slag |
| CN109621278A (en) * | 2019-01-14 | 2019-04-16 | 昆明理工大学 | One kind gypsum tailings containing arsenic cooperates with cured method with copper ashes |
| CN112718793A (en) * | 2020-12-15 | 2021-04-30 | 紫金矿业集团股份有限公司 | Method for directly vitrifying arsenic-fixing material containing arsenite |
| CN112718793B (en) * | 2020-12-15 | 2022-03-11 | 紫金矿业集团股份有限公司 | Method for directly vitrifying arsenic-fixing material containing arsenite |
| WO2022137259A1 (en) * | 2020-12-23 | 2022-06-30 | Council Of Scientific And Industrial Research | A method for safe disposal of arsenic rich sludge obtained from treatment of contaminated groundwater and its utilization in developing heat protective glass |
| CN115650588A (en) * | 2022-05-24 | 2023-01-31 | 长江师范学院 | Method for preparing microcrystalline glass by solidifying arsenic-alkali slag through ammonium leaching steel slag |
| CN116197209A (en) * | 2023-01-17 | 2023-06-02 | 广西凯玺有色金属有限公司 | Cleaning treatment method for calcium arsenate glass solidification and application thereof |
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