CN101698567B - electrolytic manganese slag microcrystalline glass and preparation method thereof - Google Patents
electrolytic manganese slag microcrystalline glass and preparation method thereof Download PDFInfo
- Publication number
- CN101698567B CN101698567B CN2009101913355A CN200910191335A CN101698567B CN 101698567 B CN101698567 B CN 101698567B CN 2009101913355 A CN2009101913355 A CN 2009101913355A CN 200910191335 A CN200910191335 A CN 200910191335A CN 101698567 B CN101698567 B CN 101698567B
- Authority
- CN
- China
- Prior art keywords
- glass
- electrolytic manganese
- temperature
- crystallization
- manganese slag
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Glass Compositions (AREA)
Abstract
The invention discloses electrolytic manganese slag microcrystalline glass and a preparation method thereof, which relate to microcrystalline glass prepared from industrial wastes and a method thereof. The raw materials of the electrolytic manganese slag microcrystalline glass comprise electrolytic manganese slag, calcium carbonate, quartz sand and magnesium carbonate. The method comprises the following steps: mixing the raw materials evenly; then founding basic glass; molding the basic glass; performing nucleation and crystallization on the basic glass; and annealing and processing the basic glass into a finished product. The electrolytic manganese slag microcrystalline glass has the characteristics of fewer raw material components (only four types), high content of the electrolytic manganese slag (75 to 99.7 percent), simple preparation method, low production energy consumption, environmental protection and the like. The electrolytic manganese slag microcrystalline glass prepared by the method can be widely used as architectural decorative materials.
Description
Technical field
The invention belongs to the sytull technical field, be specifically related to utilize trade waste to prepare sytull and method thereof.
Background technology
China is the world topmost manganese Metal Production state, and year manganese output reaches more than 90% of Gross World Product, and the acquisition major part of its product is that (main effective constituent is MnCO through sulfuric acid chemical combination rhodochrosite
3) obtain the electrolytic solution manganous sulfate after electrolysis realizes.Because MnCO in China's manganese ore ore
3Content is merely 20%, and other mineral constituent form with electrolytic manganese residues in the combination reaction process is discharged in the ore, generally speaking, and the electrolytic manganese residues that 1 ton of electrolytic metal Mn average generation of every production is about 7 tons.Owing to lack the means of effectively utilizing; The electrolytic manganese residues that these water ratio reach about 40% is all stored up in the stockyard; The stacking year by year of deslagging has caused severe contamination to environment; Mainly show as a large amount of ammonia nitrogens of containing in the electrolytic manganese residues, vitriol, heavy metal mn ion etc. near the pollution that atmosphere, water source, soil etc. the slag field cause, become the most important reason of restriction China electrolytic manganese industry development.Therefore, the need to be resolved hurrily difficult problem of electrolytic manganese residues recycling.
For a long time; Because China is not enough to the attention degree of waste pollution environment in the Industrial processes; This inert material recycling of electrolytic manganese residues difficulty is bigger in addition, and the harmlessness disposing of China's electrolytic manganese residues still faces a severe challenge, and its recycling is almost blank.Method about the electrolytic manganese residues recycling still is in the laboratory study stage, mainly comprises: the starting material of 1) producing as ordinary Portland cement.Mainly utilize electrolytic manganese residues to belong to the character of silicate material, or electrolytic manganese residues is regarded as industrial gypsum to be used as cement setting retarder, or to use it for the agent of cement color adaptation.2) electrolytic manganese residues is used to produce extraordinary building cementing material.There are problems such as big such as the starting material intractability, that the performance of material property advantage is not obvious in this mode of utilizing, has limited its recycling.The recycling approach of China's electrolytic manganese residues is few, and research electrolytic manganese residues recycling is very important problem.
Having now utilizes trade waste to prepare sytull and method; Like application number is " a kind of method of utilizing thermal power plant's liquid sludge-removing furnace to prepare sintering glass ceramics " patent of 200810018384.4, and the component of disclosed sintering glass ceramics and weight percentage thereof are:
Silicon-dioxide (SiO
2) 50～56%
Aluminium sesquioxide (Al
2O
3) 5～15%
Red oxide of iron (Fe
2O
3) 0～9%
Quicklime and Natural manganese dioxide (CaO+MgO) 10～25%
Sodium oxide and potassium oxide (Na
2O+K
2O) 1～10%
Zinc oxide and barium oxide (ZnO+BaO) 1～8%.
Disclosed method is: analyze lime-ash chemical ingredients in thermal power plant's liquid sludge-removing furnace earlier; Again through the charging opening on the furnace wall add scarce chemical ingredients and at least a oxide raw material (is that 98% zinc oxide, purity are that 98% silica powder, purity are that 54% permanent white, purity are 98% soda ash like purity); And then molten slag bath is interior under 1500～1700 ℃ of temperature; Stir fusing more than 20 minutes, give off vitreous slag, through shrend and oven dry by conventional liq deslagging shrend mode; At last by existing fire sytull technology and carry out sintering, crystallization, annealing after, at grinding and polishing, cutting and finished product.The main drawback of this patent is: component is many and complicated; Underuse sytull and form the character that can in a big way, change, make complex manufacturingization, be unfavorable for applying; This invention is to utilize thermal power plant's slag tap to prepare sintering glass ceramics, can not utilize electrolytic manganese residues to prepare sytull.
Summary of the invention
The objective of the invention is to utilize trade waste to prepare the deficiency of sytull and method, a kind of electrolytic manganese slag microcrystalline glass and preparation method thereof is provided, have the starting material source extensively to existing; Be prone to obtain, form and lack, the preparation method is simple; Easy to utilize; Parent glass founds that the process energy consumption is little, and production cost is low, characteristics such as the sytull superior performance of producing.
The technical scheme that realizes the object of the invention is: a kind of feed composition of electrolytic manganese slag microcrystalline glass and mass percent thereof are:
Electrolytic manganese residues: 75～99.7%
Lime carbonate: 0.1～10%
Silica sand: 0.1～10%
Magnesiumcarbonate: 0.1～5%.
A kind of preparation method of electrolytic manganese slag microcrystalline glass is a raw material with electrolytic manganese residues, lime carbonate, silica sand, magnesiumcarbonate, handles through founding parent glass, parent glass moulding, coring and crystallization, anneals at last and is processed as finished product.Concrete method steps is following:
(1) parent glass is founded
With electrolytic manganese residues, lime carbonate, silica sand, magnesiumcarbonate is raw material; Earlier in electrolytic manganese residues: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 75～99.7%: 0.1～10%: 0.1～10%: 0.1～5% ratio; With its mixing and stirring, again raw mix to be put into stove and found, glass melting temperature is 1300～1400 ℃; Melting time is 30～60 minutes, has just founded out electrolytic manganese residues parent glass melt.
(2) parent glass moulding
After the completion of (1) step; The electrolytic manganese residues parent glass melt water of earlier (1) step being founded out carries out quench treatment; After glass particle after will quenching place baking oven to dry, using the aperture again is that the square hole sieve of 0.5 millimeter and 6 millimeters carries out size grading, is that the glass particle of 0.5-6 millimeter is tiled on the refractory materials with particle size range then; Its thickness is 10～30 millimeters, has just prepared the electrolytic manganese residues parent glass.
(3) coring and crystallization are handled
After the completion of (2) step; With (2) the electrolytic manganese residues parent glass that obtains of step together with refractory materials; Place and carry out coring and crystallization processing in the stove; Coring and crystallization process are: earlier with 5 ℃/minute heat-up rate parent glass is warming up to 700～750 ℃ and carries out coring and handle, and under this temperature, kept nucleation time 1～2 hour, be warming up to 1050～1100 ℃ with 5 ℃/minute the heat-up rate glass after with coring again and carry out crystallization and handle; And under this temperature, kept crystallization time 0.5～2 hour, just prepare electrolytic manganese slag microcrystalline glass.
(4) annealing and processing
After the completion of (3) step; Electrolytic manganese slag microcrystalline glass with (3) step made with 10 ℃/minute annealing cooling rate, carries out anneal; When temperature is reduced to 250～300 ℃; Naturally cool to room temperature again, just prepared coffee-like electrolytic manganese slag microcrystalline glass, then after cutting, polishing and obtain required electrolytic manganese slag microcrystalline glass finishing material.
After the present invention adopts technique scheme, mainly contain following effect:
1, the starting material component of material of the present invention is few, has only 4 kinds, and raw material is easy to get, and cost is low.In the proportioning raw materials, the electrolytic manganese residues volume is big, can reach 75～99.7%, has realized the target of large, the high added value recycling of electrolytic manganese residues, for electrolytic manganese enterprise solves its trade waste difficult problem new way is provided, and helps environment protection.
2, the temperature that the parent glass melt is founded in the inventive method is lower, and minimum glass melting temperature is 1300 ℃, and energy-saving effect is more outstanding, has reduced production cost.
3, the present invention utilizes starting material self compositing characteristic; Make full use of elements such as the iron that wherein contains, manganese as the sytull nucleating agent, be beneficial to the formation of crystallite in the sytull, need not in raw material, to replenish in addition nucleating agent; This had both simplified production technique, had reduced production cost again.
4, method of the present invention is simple, and is easy and simple to handle, and institute's use equipment is simple, further reduced production cost, is beneficial to and applies.
The electrolytic manganese slag microcrystalline glass that adopts the present invention to prepare can be widely used in making constructure decorative material, is good finishing material.
Embodiment
To combine embodiment that the present invention is further specified below.
Embodiment 1
A kind of component of raw material of electrolytic manganese slag microcrystalline glass and mass percent thereof are:
Electrolytic manganese residues: 75%
Lime carbonate: 10%
Silica sand: 10%
Magnesiumcarbonate: 5%.
A kind of electrolytic manganese slag microcrystalline glass preparing method's concrete steps are following:
(1) parent glass is founded
With electrolytic manganese residues, lime carbonate, silica sand, magnesiumcarbonate is raw material; Earlier in electrolytic manganese residues: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 75%: 10%: 10%: 5% ratio stirs it; To join raw mix puts into stove and founds; Glass melting temperature is 1400 ℃, and melting time is 30 minutes, has just founded out electrolytic manganese residues parent glass melt.
(2) parent glass moulding
After the completion of (1) step; The electrolytic manganese residues parent glass melt water of earlier (1) step being founded out carries out quench treatment; After glass particle after will quenching place baking oven to dry; Using the aperture again is that the square hole sieve of 0.5 millimeter and 6 millimeters carries out size grading, is that the glass particle of 0.5-6 millimeter is tiled on the refractory materials with particle size range then, and its thickness is 10 millimeters.
(3) coring and crystallization are handled
After the completion of (2) step; With (2) the electrolytic manganese residues parent glass that obtains of step together with refractory materials; Place and carry out coring and crystallization processing in the stove, coring and crystallization process are: first heat-up rate with 5 ℃/minute is warming up to 700 ℃ with parent glass and carries out the coring processing, and keeps nucleation time 2 hours; Be warming up to 1100 ℃ with 5 ℃/minute the heat-up rate glass after with coring again and carry out crystallization and handle, and under this temperature, kept crystallization time 0.5 hour.
(4) annealing and processing
After the completion of (3) step; With the annealing cooling rate of (3) electrolytic manganese slag microcrystalline glass that makes of step with 10 ℃/minute; Carry out anneal, when temperature is reduced to 300 ℃, naturally cool to room temperature again; Just prepared coffee-like electrolytic manganese slag microcrystalline glass, then after cutting, polishing and obtain required electrolytic manganese slag microcrystalline glass finishing material.
Embodiment 2
A kind of component of raw material of electrolytic manganese slag microcrystalline glass and mass percent thereof are:
Electrolytic manganese residues: 99.7%
Lime carbonate: 0.1%
Silica sand: 0.1%
Magnesiumcarbonate: 0.1%.
A kind of electrolytic manganese slag microcrystalline glass preparing method's concrete steps are following:
(1) parent glass is founded
With embodiment 1, wherein: electrolytic manganese residues: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 99.7%: 0.1%: 0.1: 0.1%, and glass melting temperature is 1300 ℃, melting time is 45 minutes.
(2) parent glass moulding
With embodiment 1, wherein: parent glass tiling thickness is 20 millimeters.
(3) coring and crystallization are handled
With embodiment 1, wherein: the glass nucleation temperature is 750 ℃, and nucleation time is 1 hour, and crystallization temperature is 1050 ℃, and crystallization time is 1 hour.
(4) annealing and processing
With embodiment 1, wherein: annealing temperature is reduced to 250 ℃.
Embodiment 3
A kind of component of raw material of electrolytic manganese slag microcrystalline glass and mass percent thereof are:
Electrolytic manganese residues: 90%
Lime carbonate: 8%
Silica sand: 0.2%
Magnesiumcarbonate: 1.8%.
A kind of electrolytic manganese slag microcrystalline glass preparing method's concrete steps are following:
(1) parent glass is founded
With embodiment 1, wherein: electrolytic manganese residues: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 90%: 8%: 0.2%: 1.8%, and glass melting temperature is 1350 ℃, melting time is 60 minutes.
(2) parent glass moulding
With embodiment 1, wherein: parent glass tiling thickness is 30 millimeters.
(3) coring and crystallization are handled
With embodiment 1, wherein: the glass nucleation temperature is 725 ℃, and nucleation time is 1.5 hours, and crystallization temperature is 1080 ℃, and crystallization time is 2 hours.
(4) annealing and processing
With embodiment 1, wherein: annealing temperature is reduced to 270 ℃.
Test-results
The electrolytic manganese slag microcrystalline glass of preparing with embodiment 2 carries out microscopic diffraction test, microhardness, porosity test, and its result is: the principal crystalline phase of electrolytic manganese slag microcrystalline glass is diopside and lime feldspar, and microhardness is 420MPa, and porosity is 1.3%.
Know from test-results: the high added value sytull that the present invention utilizes electrolytic manganese residues to prepare to satisfy certain performance requriements, invention have reached that the electrolytic manganese residues of dissolving in a large number, simple batching, glass melt glass melting temperature are low, the effect of energy-saving and emission-reduction.
Claims (4)
1. the preparation method of an electrolytic manganese slag microcrystalline glass is characterized in that concrete method steps is following:
(1) parent glass is founded
With electrolytic manganese residues, lime carbonate, silica sand, magnesiumcarbonate is raw material; Earlier in electrolytic manganese residues: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 75～99.7%: 0.1～10%: 0.1～10%: 0.1～5% ratio; With its mixing and stirring; Raw mix is put into stove found, glass melting temperature is 1300～1400 ℃, and melting time is 30～60 minutes;
(2) parent glass moulding
After the completion of (1) step; The electrolytic manganese residues parent glass melt water of earlier (1) step being founded out carries out quench treatment; After glass particle after will quenching place baking oven to dry; Using the aperture to carry out size grading as the square hole sieve of 0.5mm and 6mm again, is that the glass particle of 0.5-6 millimeter is tiled on the horizontal plane of refractory materials with particle size range then, and its thickness is 10～30 millimeters;
(3) coring and crystallization are handled
After the completion of (2) step; With (2) the electrolytic manganese residues parent glass that obtains of step together with refractory materials; Place and carry out coring and crystallization processing in the stove; Coring and crystallization process are: first heat-up rate with 5 ℃/minute is warming up to 700～750 ℃ with parent glass and carries out the coring processing; And under this temperature, kept nucleation time 1～2 hour, be warming up to 1050～1100 ℃ with 5 ℃/minute the heat-up rate glass after with coring again and carry out crystallization and handle, and under this temperature, kept crystallization time 0.5～2 hour;
(4) annealing and processing
After (3) step accomplished, the electrolytic manganese slag microcrystalline glass that (3) step was made carried out anneal with 10 ℃/minute annealing cooling rate; When temperature is reduced to 250～300 ℃; Naturally cool to room temperature again, just prepare coffee-like electrolytic manganese slag microcrystalline glass, after cut, polished finish.
2. according to the preparation method of the described electrolytic manganese slag microcrystalline glass of claim 1, it is characterized in that concrete method steps is following:
Electrolytic manganese residues in (1) step: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 75%: 10%: 10%: 5%, and glass melting temperature is 1400 ℃, melting time is 30 minutes;
Glass coating thickness in (2) step is 10 millimeters;
Glass nucleation temperature in (3) step is 700 ℃, and nucleation time is 2 hours, and crystallization temperature is 1100 ℃, and crystallization time is 0.5 hour;
The temperature of the sytull in (4) step is reduced to 300 ℃.
3. according to the preparation method of the described electrolytic manganese slag microcrystalline glass of claim 1, it is characterized in that concrete method steps is following:
Electrolytic manganese residues in (1) step: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 99.7%: 0.1%: 0.1%: 0.1%, and glass melting temperature is 1300 ℃, melting time is 45 minutes;
Glass coating thickness in (2) step is 20 millimeters;
Glass nucleation temperature in (3) step is 750 ℃, and nucleation time is 1 hour, and crystallization temperature is 1050 ℃, and crystallization time is 1 hour;
The temperature of the sytull in (4) step is reduced to 250 ℃.
4. according to the preparation method of the described electrolytic manganese slag microcrystalline glass of claim 1, it is characterized in that concrete method steps is following:
Electrolytic manganese residues in (1) step: lime carbonate: silica sand: the mass percent of magnesiumcarbonate is 90%: 8%: 0.2%: 1.8%, and glass melting temperature is 1350 ℃, melting time is 60 minutes;
Glass coating thickness in (2) step is 30 millimeters;
Glass nucleation temperature in (3) step is 725 ℃, and nucleation time is 1.5 hours, and crystallization temperature is 1080 ℃, and crystallization time is 2 hours;
The temperature of the sytull in (4) step is reduced to 270 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101913355A CN101698567B (en) | 2009-11-05 | 2009-11-05 | electrolytic manganese slag microcrystalline glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101913355A CN101698567B (en) | 2009-11-05 | 2009-11-05 | electrolytic manganese slag microcrystalline glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101698567A CN101698567A (en) | 2010-04-28 |
| CN101698567B true CN101698567B (en) | 2012-02-22 |
Family
ID=42147027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101913355A Expired - Fee Related CN101698567B (en) | 2009-11-05 | 2009-11-05 | electrolytic manganese slag microcrystalline glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101698567B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102992623A (en) * | 2012-11-29 | 2013-03-27 | 江苏宜达光电科技有限公司 | Water-quenching preparation method for microcrystalline glass |
| CN105601108B (en) * | 2015-12-30 | 2018-05-22 | 三川德青科技有限公司 | A kind of compound tailing slag microcrystalline glass and preparation method thereof |
| CN106145686B (en) * | 2016-06-30 | 2019-07-23 | 湖南科技大学 | A kind of complicated utilization Pb-Zn tailings, devitrified glass of electrolytic manganese waste residue and preparation method thereof |
| CN108059347B (en) * | 2018-01-30 | 2020-08-04 | 铜仁学院 | Microcrystalline glass prepared from electrolytic manganese residues and preparation method thereof |
| CN108264233B (en) * | 2018-02-05 | 2021-05-14 | 北京工业大学 | Method for comprehensively utilizing electrolytic manganese slag and preparing microcrystalline glass |
| CN110981202A (en) * | 2019-12-24 | 2020-04-10 | 北方民族大学 | Microcrystalline glass and preparation method thereof |
| CN112239326A (en) * | 2020-11-03 | 2021-01-19 | 安阳金方冶金有限公司 | Method for preparing anti-reflection glass by utilizing liquid refined manganese slag |
| CN114409261B (en) * | 2021-12-30 | 2023-09-19 | 武汉理工大学 | Textured glass ceramic plate with manganese alloy smelting high-temperature slag as main raw material and preparation method thereof |
-
2009
- 2009-11-05 CN CN2009101913355A patent/CN101698567B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101698567A (en) | 2010-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101698567B (en) | electrolytic manganese slag microcrystalline glass and preparation method thereof | |
| CN101851063B (en) | Technology for preparing microcrystal glass by utilizing blast furnace water granulated slag and coal ash | |
| CN101759368B (en) | Green glass-ceramic plate made from lead-zinc smelting slag and manufacturing method thereof | |
| CN101182120B (en) | Method for manufacturing glass-ceramics | |
| CN103553341A (en) | Fluoride-free granite slag microcrystalline glass and production method thereof | |
| CN108503224B (en) | Microcrystalline glass using coal gangue and rice hull ash as main raw materials and preparation method thereof | |
| CN102795772A (en) | Method for preparing microcrystalline glass from kaolin-type coal gangue or fly ash and carbide slag | |
| CN109052969A (en) | A method of devitrified glass is produced using andradite type red mud | |
| CN106116161B (en) | A method of preparing devitrified glass using yellow phosphorus furnace slag and chromium slag | |
| CN103232164B (en) | Coffee microcrystal glass plate and production method thereof | |
| CN1329328C (en) | Method for preparing micro crystal glass plate for building using waste glass | |
| CN104108882A (en) | Float microcrystalline glass and preparation method thereof | |
| CN101774762B (en) | Black microlite manufactured by using lead and zinc smelting dreg and manufacturing method thereof | |
| CN110950539A (en) | Microcrystalline glass using coal cinder as main raw material and preparation method thereof | |
| CN108358455B (en) | Method for preparing microcrystalline glass by using lead-zinc tailings and quartz tailings | |
| CN101314521B (en) | Method for producing sintered crystallizing glass with slag tapping boiler of heat-engine plant | |
| CN110066114B (en) | Method for preparing transparent glass ceramic with adjustable color by utilizing silicomanganese slag | |
| CN108083644B (en) | A method of devitrified glass is prepared using molten blast furnace slag | |
| CN1209306C (en) | Method for making composite type nucleated glass from flyash used in building | |
| CN106316118A (en) | Brown decorative glass made mainly from liquid blast furnace slag and production method thereof | |
| CN102875025A (en) | Black glass ceramics and preparation method thereof | |
| CN103332860B (en) | Method for manufacturing glass ceramic plate used for architectural decoration by utilizing coal gangue | |
| CN102503528A (en) | Preparation method of red mud iron reduction furnace slag light foamed ceramic and iron reduction furnace | |
| CN102241502B (en) | Artificial jade based on gangue and manufacturing method thereof | |
| CN101767932B (en) | Method for utilizing waste gypsum slag to manufacture green microcrystalline glass plate material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Hunan Dongfang Mining Co., Ltd. Assignor: Chongqing University Contract record no.: 2012990000499 Denomination of invention: Electrolytic manganese slag microcrystalline glass and preparation method thereof Granted publication date: 20120222 License type: Exclusive License Open date: 20100428 Record date: 20120713 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120222 Termination date: 20121105 |