CN103145337A - Method for preparing microcrystalline glass by utilizing blast furnace steel slag - Google Patents
Method for preparing microcrystalline glass by utilizing blast furnace steel slag Download PDFInfo
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- CN103145337A CN103145337A CN2013100804234A CN201310080423A CN103145337A CN 103145337 A CN103145337 A CN 103145337A CN 2013100804234 A CN2013100804234 A CN 2013100804234A CN 201310080423 A CN201310080423 A CN 201310080423A CN 103145337 A CN103145337 A CN 103145337A
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Abstract
The invention relates to a method for preparing a microcrystalline glass by utilizing steel slag. The method comprises the following steps of: firstly, carrying out drying and ball milling on the steel slag and removing iron contained in the steel slag to prepare powder of 100 meshes; then mixing the steel slag powder, quartz sand, sodium nitrate, barium nitrate, zinc oxide and cerium dioxide into a compound material; placing the mixture obtained from the former step into a crucible, and smelting at 1250-1380 DEG C to form a transparent steel slag glass; and finally, crystallizing the transparent steel slag glass to form the steel slag microcrystalline glass containing calcium akermanite as a main crystal phase. The method disclosed by the invention utilizes the blast furnace steel slag as a main raw material and achieves the utilization amount of the steel slag at 96%; and the microcrystalline glass prepared according to the method has the advantages of high structural strength, low water absorption, high crystalline degree and various color. The preparation process disclosed by the invention is simple in operation process and low in cost, can effectively reduce the production cost of the microcrystalline glass, protects the environment and changes the wastes into valuables, is suitable for industrialized large-scale production and has obvious economic benefit and environmental benefit.
Description
Technical field
The present invention relates to a kind of manufacture method of devitrified glass, particularly a kind of method of utilizing blast furnace slag to prepare high strength micro-crystalline glass.
Technical background
Devitrified glass is a kind of new decorative material for building that comprehensive glass and ceramic technology grow up, and is the regeneration product of high-grade lithotome.No matter construction industry and building materials industry, in developed country or developing country, all belong to pillar industry in national economy, the output of China's architectural pottery industry has surpassed west Jian Tao big country Italy, occupies the first in the world.But, because product specification is low, the output value is well below western architecture ceramic industry big countries such as Italy, Spain.Crystallizing glass decoration board is nearly 5 years worldwide emerging "dead" harm top-grade building materials, mainly replaces high-grade natural granite, marble.Only have at present several producers such as the U.S., Russia, Japan, Korea S, Taiwan can produce crystallizing glass sheet material.
China's building materials industry policy that the Ministry of Construction formulates is progressively to eliminate product low and middle-grade times, increase expensive goods, make its proportion bring up to 25% left and right of ultimate production, and the development of new decorative panel for building, improve domestic lithotome market product structure, replace imported, the trade that takes part in international competition, expands export and be decided to be one of development priority of building material industry the Eleventh Five-Year Plan period.Devitrified glass has good physicochemical property and mechanical property, water-intake rate is low, compactness good and acidproof, alkaline-resisting, can effectively resist atomospheric corrosion, there is no radiocontamination, surface detail fineness and smooth finish are better than lithotome, cause increasing concern in building and ornament materials are used, become the preferred material that substitutes lithotome.
Blast furnace slag is the refuse of discharging from blast furnace while smelting the pig iron, and in blast furnace slag, main component is CaO, SiO
2, Al
2o
3.According to the ore grade difference, 1 ton of iron of every refining is discharged 0.3～1 ton of slag, and ore grade is lower, and bed drain purge is larger.China approximately discharges more than 2,000 ten thousand tons at present every year.Slag is thrown the meeting land occupation aside, waste resource, contaminate environment.At present, the blast furnace slag that each steel mill produces mainly is used to prepare cement products.But, because Chinese output of steel is larger, also have at present nearly 30% blast furnace slag to recycle.In addition, blast furnace slag is lower for the preparation of the cement products rate of profit.And, at present about how blast furnace slag being recycled in a large number, the high performance material that the preparation added value is higher is not reported.
At present, about utilizing more ([1] Yang Zhijie of the standby devitrified glass of prepared from steel slag, grey large strong, Li Yu etc. molten steel slag prepares the experimental study [J] of devitrified glass. New Building Materials, 2011, (7): 52-53, 65.[2] Lu Lei, Yao Qiang, Jiang Qin etc. the research [J] of Glass-Ceramics from Steel Slag feed proportioning optimization scheme. glass and enamel, 2005, 33 (6): 28-31, 50.[3] University Of Science and Technology of the Inner Mongol. a kind of hot steel slag directly prepares the method for ferromagnetic glass-ceramics: China, CN201210359035.5[P] .2012-12-19.[4] Peng Feng, Gao Zhanyong, Li Baowei etc. utilize Baogang's converter slag to prepare the experimental study [J] of devitrified glass. University Of Science and Technology of the Inner Mongol's journal, 2010, 29 (3): 232-236.[5] Yang Jiakuan, Xiao Bo, Tang east antelope etc. the preparation of slag base microcrystal glass and microstructure analysis [J]. the Materials Science and Engineering journal, 2003, 21 (1): 34-36.[6] rich of heap of stone. slag is founded devitrified glass technical study [D]. the Central China University of Science and Technology, 2007.[7] Zhang Shengxiao, Yue Qinyan, Yu Hui etc. blast furnace slag prepares the research [J] of devitrified glass. journal of Shandong university (Edition), 2006, 41 (5): 129-133..[8] Liu Baichen. SiO under condition of different temperatures
2-CaO-MgO-Fe
2o
3microcrystalline glass in series crystallization behavior [J]. industry heating, 2009,38 (1): 53-54.[9] magnify bravely, Wang Yuanyuan, the .CaO such as Shi Peiyang are to CaO-MgO-A1
2o
3-SiO
2-Na
2the impact of O microcrystalline glass in series crystallization behavior and performance [C]. the 14 the academic proceeding .2006:378-381.[10 of whole nation steel-making] woods is skilful, Yang Zhihong, Xie Hongjia etc. utilize copper ashes to prepare the research [J] of devitrified glass. the silicate circular, 2012, 31 (5): 1204-1207, 1211.[11] Zhang Wei, Yang Shumin, the circumferential tinkling of pieces of jade etc. direct sintering prepares the research [J] of high slag microcrystallite glass. Xinjiang University's journal (natural science edition), 2010, 27 (2): 209-213.), but main existing problems are that the steel slag utilization rate is lower than 80%, utilization ratio is low, and glass smelting temperature higher (being greater than 1400 ℃), simultaneously, after crystallization, crystalline phase is impure, principal crystalline phase is with rankinite, wollastonite, diopside is main.And not take the report that calcio-akermanite is unique principal crystalline phase.Yang Shumin etc. be take 95% blast furnace slag and 5% potassium felspar sand and are prepared devitrified glass as raw material, and principal crystalline phase is gehlenite, the prepared devitrified glass color of the document is single, can not fill a prescription and prepare transparent or semitransparent devitrified glass by adjustment, and crystalline phase is the poor gehlenite crystalline phase of mechanical property ([1] Yang Shumin, Zhang Wei, the circumferential tinkling of pieces of jade etc. heat treating regime is to high slag microcrystallite glass performance impact [J]. Chongqing University of Technology's journal: natural science, 2011, (10): 34-39.[2] Lu Hongxia, Zhang Wei, Li Lijian etc. utilize the metallurgy high furnace slag to prepare the research [J] of devitrified glass. Zhengzhou University's journal (engineering version), 2007, 28 (3): 98-100.[3] Liu Hongyu, Sun Yuanyuan, appoint and wait forward. the impact [J] of sintering temperature on high slag microcrystallite glass building materials performance. brick and tile, 2010, (4): 58-61.[4] Yu Pingli, horse is fastened lock. the application [J] of Yicheng, Shanxi blast furnace slag in devitrified glass. and Huaqiao University's journal (natural science edition), 2008, 29 (1): 17-21.).
The external research to the blast furnace slag devitrified glass is more ([1] Das, Kaberi also; Raha, Sanjay; Chakraborty; Dibyendu.Effect of nucleating agents on the crystallization and microstructural characteristics of blast furnace slag derived glassceramics[J] .Transactions of the Indian Ceramic Society; 2012; 71 (3): 137-142.[2] Wang, Yici; Zhang, Jianliang; Jiang; Qi.Crystallization behavior during preparation of glass-ceramics from BF slag of Baotou iron and steel company[J] .Advanced Materials Research; 2012; 581-582 (Pt.2): 836-841.[3] Wang, Yici; Jiang, Qi; Luo; Guoping.Mutual influence of special components in Baotou steel blast furnace slag on the crystallization behavior of glass[J] .Journal of Metallurgy; 2012,954021.[4] Zhao, Yan; Chen, Dengfu; Bi, Yanyan.Preparation of low cost glass-ceramics from molten blast furnace slag[J] .Ceramics International, 2012,38 (3): 2495-2500.[5] Mihailova, I.K.; Djambazki, P.R.; Mehandjiev; D.The effect of the composition on the crystallization behavior of sintered glass-ceramics from blast furnace slag[J] .Bulgarian Chemical Communications; 2011; 43 (2): 293-300.[6] Francis; A.A.Conversion of blast furnace slag into new glass-ceramic material[J] .Journal of the European; 2004; 24 (9): 2819-2824.[7] Francis, Adel A.; Shoeib, Madiha A.Development of a new composite product from blast furnace slag[J] .Materials Science Forum, 2003,426-432 (Pt.3): 2071-2076.[8] Wang, Zhong-jie; Ni, Wen; Li; Ke-qing.Crystallization characteristics of iron-rich glass ceramics prepared from nickel slag and blast furnace slag[J] .International Journal of Minerals; Metallurgy and Materials; 2011; 18 (4): 455-459.[9] ElBatal, Fatma H.; Azooz, Moenis A.; Hamdy; Yousry M.Production and characterization of glasses and glass-ceramics from Egyptian iron slag waste[J] .Transactions of the Indian Ceramic Society; 2010; 69 (1): 29-36.[10] Lu, Hongxia; Hou, Tiecui; Zhang; Wei.Use of Angang slag for the production of glass-ceramic materials [J] .Key Engineering Materials; 2008; 368-372 (2): 1426-1428.[11] Ovecoglu; at950 ° of Cand1100 ° of C[J of M.L.Microstructural characterization and physical properties of a slag-based glass-ceramic crystallized] .Journal of the European Ceramic Society; 1998; 18 (2): 161-168.[12] Saucedo, E.M.; Perera, Y.M.; Robles, D.Plasma assisted novel production process of glass-ceramic spheres in the quaternary system CaO-SiO
2-Al
2o
3-MgO[J] .Ceramics International, 2012,38 (4): 3161-3165.), but the system adopted mostly is calcium magnesium system on silicon, exists equally steel slag utilization low, and glass melting temperature is high, the crystalline phase poor-performing that forms, the shortcoming such as the devitrified glass color of preparation is single, and transmittance is lower.
In sum, devitrified glass is a kind of new decorative material for building that comprehensive glass and ceramic technology grow up, and is the regeneration product of high-grade lithotome.Bibliographical information is mostly around utilizing the standby devitrified glass of all kinds of prepared from steel slags and performance study thereof at present, about high volume, utilize blast furnace slag for main raw material, prepare multiple color transparent glass goods, and then crystallization prepares multiple color, the technique of the high strength micro-crystalline glass that crystalline phase is single and performance correlative study be report not.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of method of utilizing blast furnace slag to prepare devitrified glass is provided.The crystallizing glass sheet material structural strength made according to preparation method of the present invention is high, color variety is many, and water-intake rate is low, crystallization degree is high, the single purity of crystalline phase is high, can be extensively as high-grade building and ornament materials.
For achieving the above object, the technical solution used in the present invention is:
The first step, slag is dried and ball-milling processing
At first, blast furnace slag is put into to the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, be warming up to 120 ℃, and, with the rotational speed of 20～30 turn/min, after being incubated 2～4h, be cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 80～96% blast furnace slag powder, 0～8% quartz sand, 0～6% SODIUMNITRATE, 1～5% nitrate of baryta, 0～2% zinc oxide and 3～6% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1250～1380 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1250～1380 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 550～650 ℃ after insulation 3h, with the rate of cooling of 0.5～1 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, according to after size cutting, put into continuous tunnel furnace, burn till according to following calcining system: with the heat-up rate of 5～8 ℃/min, after room temperature is warming up to 750～800 ℃, be incubated 30～60min; Then, after being warming up to 860～920 ℃ with the heat-up rate of 10～20 ℃/min, after being incubated 120～300min, with the cooling rate of 1～2 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
Should sieve during rotary dryer charging used in the present invention and remove granularity and be greater than the above particle of 10mm.
In the present invention in the balls grinding machine grinding medium be pebbles or Ceramic Balls, the grinding medium diameter is less than 20mm, it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
In the present invention, quartz sand used is industrial quartz sand, and granularity is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm.
SODIUMNITRATE used in the present invention, nitrate of baryta, zinc oxide, cerium dioxides etc. are industrial raw material.
In the present invention, slag glass, when entering continuous tunnel furnace, answers uniform spreading 2mm thick under glass bottom, and granularity is greater than 300 purpose aluminum oxide powders.
The present invention utilizes blast furnace slag for main raw material, adopts smelting process to prepare high strength micro-crystalline glass sheet material.Wherein, the steel slag utilization amount is up to 96%.In addition, in formula, the glass colour capable of regulating of preparing by adding strong oxidizer to make, its visible-range iuuminting rate is high, has increased range of application and the result of use of devitrified glass.In addition, in preparation process, to pulverizing the scum that raw material carries out after deironing, can also be recovered utilization, further improve the utilization ratio of slag, not only turn waste into wealth, and protected environment, make slag obtain recycling fully.The Structure of Glass Ceramic intensity made according to preparation method of the present invention is high, water-intake rate is low, crystallization degree is high, color variety is many, can be extensively as high-grade building and ornament materials.Preparation technology's operating process of the present invention is simple, with low cost, can effectively reduce the production cost of devitrified glass, and protection of the environment, turn waste into wealth, and is suitable for large-scale industrialization production, has obvious economic benefit and environmental benefit.
The accompanying drawing explanation
Fig. 1 is the light transmittance curve figure of the Glass-Ceramics from Steel Slag of embodiment 1 preparation, and wherein X-coordinate is lambda1-wavelength, and ordinate zou is transmittance.
Fig. 2 is the differential calorimetric analysis graphic representation of the Glass-Ceramics from Steel Slag of embodiment 1 preparation, and wherein X-coordinate is specimen temperature, the thermal change that ordinate zou is sample and changes in weight, 10 ℃/min of temperature rise rate.
Fig. 3 is the diffracting spectrum that the Glass-Ceramics from Steel Slag of embodiment 1 preparation detects at X-ray diffractometer, wherein X-coordinate be diffraction angle 2 θ/(°), ordinate zou is diffracted intensity.
The thermal expansion graphic representation of the transparent slag glass of Fig. 4 embodiment 1 preparation, wherein X-coordinate is specimen temperature, the elongation that ordinate zou is sample.
The thermal expansion graphic representation of the Glass-Ceramics from Steel Slag of Fig. 5 embodiment 1 preparation, wherein X-coordinate is specimen temperature, the elongation that ordinate zou is sample.
Embodiment
The first step, slag is dried and ball-milling processing
At first, the blast furnace slag that granularity is less than to 10mm is put into the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, is warming up to 120 ℃, and, with the rotational speed of 20 turn/min, after insulation 4h, is cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 85% blast furnace slag powder, 3% quartz sand, 3% SODIUMNITRATE, 5% nitrate of baryta, 1% zinc oxide and 3% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed; Wherein the granularity of quartz sand is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1250 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1350 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 600 ℃ after insulation 3h, with the rate of cooling of 1 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, after the size cutting, the thicker granularity of uniform spreading 2mm is put into continuous tunnel furnace after being greater than 300 purpose aluminum oxide powders under glass bottom, according to following calcining system, burn till: with the heat-up rate of 5 ℃/min after room temperature is warming up to 750 ℃, insulation 60min; Then, after being warming up to 900 ℃ with the heat-up rate of 10 ℃/min, after insulation 120min, with the cooling rate of 2 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
The present embodiment grinding in ball grinder medium is pebbles or Ceramic Balls, and the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
Formed Glass-Ceramics from Steel Slag smooth surface, adopting the apparent density of drainage determination test is 2.61gcm
-3; Adopt the folding strength of universal testing machine determination test to reach 36MPa.
Referring to accompanying drawing 1, be the light transmittance curve figure of prepared Glass-Ceramics from Steel Slag, wherein X-coordinate is lambda1-wavelength, ordinate zou is transmittance.By picture, can be found out, prepared slag glass approaches 40% in visible-range iuuminting rate, and color is reddish-brown.
Referring to accompanying drawing 2, be the differential calorimetric analysis graphic representation of prepared Glass-Ceramics from Steel Slag, wherein X-coordinate is specimen temperature, the thermal change that ordinate zou is sample and changes in weight.By picture, can be found out, sample is warming up to 1200 ℃ of processes from room temperature with 10 ℃/min of temperature rise rate, mass loss 0.28%; Simultaneously, sample has obvious crystallization exothermic peak under 746.8 ℃ and 856.5 ℃.
Referring to accompanying drawing 3, the diffracting spectrum that prepared Glass-Ceramics from Steel Slag detects at X-ray diffractometer, wherein X-coordinate be diffraction angle 2 θ/(°), ordinate zou is diffracted intensity, by picture, can be found out, prepared Glass-Ceramics from Steel Slag is with calcio-akermanite (Ca
2mgSi
2o
7) be the devitrified glass of unique crystalline phase.
Referring to accompanying drawing 4, be the thermal expansion graphic representation of prepared transparent slag glass, wherein X-coordinate is specimen temperature, and the elongation that ordinate zou is sample can be found out by picture, and the linear expansivity of prepared slag glass material is 102 * 10
-7/ ℃, transition temperature is 633.9 ℃, texturing temperature is 712 ℃.
Referring to accompanying drawing 5, be the thermal expansion graphic representation of prepared Glass-Ceramics from Steel Slag, wherein X-coordinate is specimen temperature, the elongation that ordinate zou is sample.By picture, can be found out, after crystallization, the linear expansivity of prepared Glass-Ceramics from Steel Slag material is 91 * 10
-7/ ℃.
The first step, slag is dried and ball-milling processing
At first, the blast furnace slag that granularity is less than to 10mm is put into the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, is warming up to 120 ℃, and, with the rotational speed of 22 turn/min, after insulation 3h, is cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 80% blast furnace slag powder, 8% quartz sand, 1% SODIUMNITRATE, 4% nitrate of baryta, 1% zinc oxide and 6% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed; Wherein the granularity of quartz sand is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1250 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1250 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 550 ℃ after insulation 3h, with the rate of cooling of 0.5 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, after the size cutting, the thicker granularity of uniform spreading 2mm is put into continuous tunnel furnace after being greater than 300 purpose aluminum oxide powders under glass bottom, according to following calcining system, burn till: with the heat-up rate of 5 ℃/min after room temperature is warming up to 800 ℃, insulation 60min; Then, after being warming up to 860 ℃ with the heat-up rate of 20 ℃/min, after insulation 120min, with the cooling rate of 1 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
The present embodiment grinding in ball grinder medium is pebbles or Ceramic Balls, and the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
Formed Glass-Ceramics from Steel Slag smooth surface, color is reddish brown, adopting the apparent density of drainage determination test is 2.53gcm
-3; Adopt the folding strength of universal testing machine determination test to reach 34MPa.
Embodiment 3,
The first step, slag is dried and ball-milling processing
At first, the blast furnace slag that granularity is less than to 10mm is put into the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, is warming up to 120 ℃, and, with the rotational speed of 25 turn/min, after insulation 2h, is cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 83% blast furnace slag powder, 4% quartz sand, 6% SODIUMNITRATE, 2% nitrate of baryta, 2% zinc oxide and 3% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed; Wherein the granularity of quartz sand is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1260 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1260 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper grinding tool that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 600 ℃ after insulation 3h, with the rate of cooling of 1 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, after the size cutting, the thicker granularity of uniform spreading 2mm is put into continuous tunnel furnace after being greater than 300 purpose aluminum oxide powders under glass bottom, according to following calcining system, burn till: with the heat-up rate of 6 ℃/min after room temperature is warming up to 780 ℃, insulation 50min; Then, after being warming up to 900 ℃ with the heat-up rate of 15 ℃/min, after insulation 200min, with the cooling rate of 1.5 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
The present embodiment grinding in ball grinder medium is pebbles or Ceramic Balls, and the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
Formed Glass-Ceramics from Steel Slag smooth surface, color is reddish brown, adopting the apparent density of drainage determination test is 2.64gcm
-3; Adopt the folding strength of universal testing machine determination test to reach 37MPa.
Embodiment 4,
The first step, slag is dried and ball-milling processing
At first, the blast furnace slag that granularity is less than to 10mm is put into the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, is warming up to 120 ℃, and, with the rotational speed of 27 turn/min, after insulation 3h, is cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 88% blast furnace slag powder, 3% quartz sand, 3% SODIUMNITRATE, 2% nitrate of baryta and 4% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed; Wherein the granularity of quartz sand is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1250 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1350 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 650 ℃ after insulation 3h, with the rate of cooling of 1 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, after the size cutting, the thicker granularity of uniform spreading 2mm is put into continuous tunnel furnace after being greater than 300 purpose aluminum oxide powders under glass bottom, according to following calcining system, burn till: with the heat-up rate of 7 ℃/min after room temperature is warming up to 750 ℃, insulation 40min; Then, after being warming up to 900 ℃ with the heat-up rate of 20 ℃/min, after insulation 260min, with the cooling rate of 2 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
The present embodiment grinding in ball grinder medium is pebbles or Ceramic Balls, and the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
Formed Glass-Ceramics from Steel Slag smooth surface, color is reddish brown, adopting the apparent density of drainage determination test is 2.66gcm
-3; Adopt the folding strength of universal testing machine determination test to reach 35MPa.
The first step, slag is dried and ball-milling processing
At first, the blast furnace slag that granularity is less than to 10mm is put into the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, is warming up to 120 ℃, and, with the rotational speed of 30 turn/min, after insulation 4h, is cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 90% blast furnace slag powder, 1% quartz sand, 2% SODIUMNITRATE, 4% nitrate of baryta and 3% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed; Wherein the granularity of quartz sand is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1300 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1380 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 650 ℃ after insulation 3h, with the rate of cooling of 1 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, after the size cutting, the thicker granularity of uniform spreading 2mm is put into continuous tunnel furnace after being greater than 300 purpose aluminum oxide powders under glass bottom, according to following calcining system, burn till: with the heat-up rate of 7 ℃/min after room temperature is warming up to 800 ℃, insulation 60min; Then, after being warming up to 910 ℃ with the heat-up rate of 20 ℃/min, after insulation 300min, with the cooling rate of 2 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
The present embodiment grinding in ball grinder medium is pebbles or Ceramic Balls, and the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
Formed Glass-Ceramics from Steel Slag smooth surface, color is reddish brown, adopting the apparent density of drainage determination test is 2.68gcm
-3; Adopt the folding strength of universal testing machine determination test to reach 39MPa.
Embodiment 6,
The first step, slag is dried and ball-milling processing
At first, the blast furnace slag that granularity is less than to 10mm is put into the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, is warming up to 120 ℃, and, with the rotational speed of 28 turn/min, after insulation 3.5h, is cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent, by 96% blast furnace slag powder, 1% nitrate of baryta and 3% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed; Wherein the granularity of quartz sand is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1380 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1380 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 650 ℃ after insulation 3h, with the rate of cooling of 0.5 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, after the size cutting, the thicker granularity of uniform spreading 2mm is put into continuous tunnel furnace after being greater than 300 purpose aluminum oxide powders under glass bottom, according to following calcining system, burn till: with the heat-up rate of 8 ℃/min after room temperature is warming up to 800 ℃, insulation 30min; Then, after being warming up to 920 ℃ with the heat-up rate of 20 ℃/min, after insulation 300min, with the cooling rate of 2 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
The present embodiment grinding in ball grinder medium is pebbles or Ceramic Balls, and the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
Formed Glass-Ceramics from Steel Slag smooth surface, color is faint yellow, adopting the apparent density of drainage determination test is 2.69gcm
-3; Adopt the folding strength of universal testing machine determination test to reach 39MPa.
The present invention utilizes blast furnace slag for main raw material, adopts smelting process to prepare high strength micro-crystalline glass sheet material.Wherein the steel slag utilization amount is up to 96%.In addition, in formula, high by the glass transmittance that adds strong oxidizer to make to prepare, color can be adjusted, and has increased range of application and the result of use of devitrified glass.In addition, in preparation process, to pulverizing the scum that raw material carries out after deironing, can also be recovered utilization, further improve the utilization ratio of slag, not only turn waste into wealth, and protected environment, make slag obtain recycling fully.The Structure of Glass Ceramic intensity made according to preparation method of the present invention is high, water-intake rate is low, crystallization degree is high, many present invention of color variety preparation technology operating process is simple; with low cost; can effectively reduce the production cost of devitrified glass; protection of the environment; turn waste into wealth; be suitable for large-scale industrialization production, there is obvious economic benefit and environmental benefit.Prepared devitrified glass can be used as the high-grade construction decoration material of the public people's livelihood facilities such as the underwater engineering such as airport, railway station, subway and hotel, restaurant, bank, market, arenas, conference and exhibition center, exhibition center, villa, business office, home decoration, household electrical appliances, furniture, Leisure Culture, hospital, Library.
Claims (6)
1. a method of utilizing blast furnace slag to prepare devitrified glass is characterized in that:
The first step, slag is dried and ball-milling processing
At first, blast furnace slag is put into to the rotary furnace drying stove, with the heat-up rate of 3 ℃/min, from room temperature, be warming up to 120 ℃, and, with the rotational speed of 20～30 turn/min, after being incubated 2～4h, be cooled to room temperature;
Then, the blast furnace slag of oven dry is put into to ball mill and be milled to 100 order powder;
Finally, the powder after ball milling is poured in deironing apparatus and carried out deironing, both must prepare devitrified glass blast furnace slag powder after deironing;
Second step, transparent slag glass preparation
At first, according to mass percent by 80～96% blast furnace slag powder, 0～8% quartz sand, 0～6% SODIUMNITRATE, 1～5% nitrate of baryta, 0～2% zinc oxide and 3～6% cerium dioxide are put into mixer and are formed admixtion, then, to the distilled water that adds Glass Batch Quality 5% in mixer, open mixer admixtion is mixed;
Secondly, half of mixed admixtion added in the corundum crucible that is warming up to 1200 ℃, be warming up to 1250～1380 ℃ through 10 minutes, and will remain half mixed admixtion after being incubated 20 minutes and add again in corundum crucible, be warming up to 1250～1380 ℃ through 10 minutes, after insulation 60min, adopt stirring rod to glass liquid stirring 1min, after being incubated 60min again, after again adopting stirring rod to glass liquid stirring 1min, after being incubated 30min again, glass metal is cast in to moulding in the copper mould that is warming up to 350 ℃;
Finally, the sample after moulding is sent in the retort furnace of 550～650 ℃ after insulation 3h, with the rate of cooling of 0.5～1 ℃/minute, sample is cooled to room temperature and obtains transparent slag glass;
The 3rd step, the preparation of Glass-Ceramics from Steel Slag
At first, by the slag glass prepared, according to after size cutting, put into continuous tunnel furnace, burn till according to following calcining system: with the heat-up rate of 5～8 ℃/min, after room temperature is warming up to 750～800 ℃, be incubated 30～60min; Then, after being warming up to 860～920 ℃ with the heat-up rate of 10～20 ℃/min, after being incubated 120～300min, with the cooling rate of 1～2 ℃/min, be cooled to below 50 ℃ to obtain Glass-Ceramics from Steel Slag.
2. the method for utilizing blast furnace slag to prepare devitrified glass according to claim 1, it is characterized in that: the granularity of described blast furnace slag is less than 10mm.
3. the method for utilizing blast furnace slag to prepare devitrified glass according to claim 1, it is characterized in that: described grinding in ball grinder medium is pebbles or Ceramic Balls, the grinding medium diameter is less than 20mm, and it is 2:1 with the mass ratio that adds pan feeding that when filling with substance is controlled grinding medium.
4. the method for utilizing blast furnace slag to prepare devitrified glass according to claim 1, it is characterized in that: described quartz sand is industrial quartz sand, and granularity is greater than 50 orders, and in quartz sand, the content of ferric oxide is less than 15ppm.
5. the method for utilizing blast furnace slag to prepare devitrified glass according to claim 1 is characterized in that: described SODIUMNITRATE, and nitrate of baryta, zinc oxide, cerium dioxide is industrial raw material.
6. the method for utilizing blast furnace slag to prepare devitrified glass according to claim 1, it is characterized in that: described slag glass, when entering continuous tunnel furnace, answers the thick granularity of uniform spreading 2mm to be greater than 300 purpose aluminum oxide powders under glass bottom.
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Application publication date: 20130612 |