CN104496535B - Using silica sand mine tailing and flyash as foamed ceramics of primary raw material and preparation method thereof - Google Patents

Using silica sand mine tailing and flyash as foamed ceramics of primary raw material and preparation method thereof Download PDF

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Publication number
CN104496535B
CN104496535B CN201510000877.5A CN201510000877A CN104496535B CN 104496535 B CN104496535 B CN 104496535B CN 201510000877 A CN201510000877 A CN 201510000877A CN 104496535 B CN104496535 B CN 104496535B
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flyash
mine tailing
silica sand
sand mine
foamed ceramics
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CN104496535A (en
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卢安贤
李卓
刘涛涌
李秀英
罗志伟
胡晓林
刘飘
张骞
宋俊
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Central South University
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Central South University
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Abstract

It is a kind of using silica sand mine tailing and flyash as high porosity foamed ceramics of primary raw material and preparation method thereof, Glass Batch Quality percentage of the present invention is:Silica sand or quartz sand ore tail 25 ~ 45%, flyash 40 ~ 60%, additive 15 ~ 20%, sintering aid 5 ~ 10%, foaming agent 5 ~ 10%, binding agent 2.5 ~ 5% in additive.Each material is weighed by component design, through ball milling, sieving, adding additives, batch is made;Batch is pressed into block base substrate, sintered, cooling, high porosity foamed ceramics is made.The density of foamed ceramics of the present invention is 0.59~0.73g/cm3, the porosity 65.7~69.8%, 4.0~4.7MPa of bending strength, 10.9~12.9MPa of compression strength, acid resistance 98.1~98.3%, alkali resistance 99.1~99.4%, can be used as that there is heat-insulated, insulation, sound insulation, the construction material of fire-proof function.

Description

Using silica sand mine tailing and flyash as foamed ceramics of primary raw material and preparation method thereof
Technical field
The present invention relates to a kind of using silica sand mine tailing and flyash as the high porosity foamed ceramics of primary raw material and its preparation Method, belong to resource, environment, new material multi-crossed disciplines technical field.
Technical background
China is plate glass big producer, and yield ranks first in the world always.Producing the primary raw material of plate glass is Silica sand or quartz sand, the SiO introduced by silica sand or quartz sand2Account for more than the 70% of plate glass weight.With the hair of glass industry Exhibition, the construction in siliceous raw material base also achieve significant progress.In some SiO2Stone has been built up in resourceful area successively Sand or silica sand ore dressing plant, it is mainly produced for the refined SiO of glass industry2Raw material.Because the silica flour of particulate enters meeting after stove Etch refractory material, the life-span of melting furnaces is reduced, influence the uniformity of batch, while can also brought and block checker brick passage etc. no Sharp factor, therefore glass industry is to the granularity requirements of quartz sand or silica sand:Granule content between 0.125 ~ 0.71mm is big In 95%, the quartzy powder content less than 0. 125 mm is less than 5%.This granularity requirements necessarily cause to produce substantial amounts of quartz sand Or silica sand mine tailing.Meanwhile China is many local using quartzite, vein quartz as raw ore, using broken-grinding-screening-deferrization process Produce quartz sand or silica sand raw material.According to statistics, the quartz sand or silica sand that China is produced using quartzite, vein quartz as raw ore are up to 400 Ten thousand tons/year, caused about 1,000,000 tons/year of quartz sand or silica sand mine tailing.In addition to flat glass industry, domestic glass, ceramics, water Mud, refractories industry will also use a large amount of quartz sand or silica sand raw materials.In the process of quartz sand or silica sand raw material, Produce a large amount of mine tailings.These tailings are most of not utilized rationally in addition to the raw material on a small quantity as waterglass and ceramics, both A large amount of soils, increase enterprise maintenance cost are taken, also seriously pollutes air and waters.
Flyash is a kind of pozzolanic materials, is mainly derived from thermal power plant the residue after coal burning.China There are abundant coal resources, the development of power industry, be still based on the thermal power generation of fire coal.It is continuous due to coal unit Increase, power plant's scale constantly expand, and result in the sharp increase of flyash discharge capacity.Some researchs show there is 20 in flyash A variety of heavy metals that environmental and human health impacts are harmful to, the material such as compound, including nervous system injury, life may be caused Manage the defect even heavy metal of cancer.If substantial amounts of flyash is not acted upon, airborne dust can be produced, air is polluted, to human body Health hazard is very big;Being discharged into river course water system can then cause river to silt up, polluted water, human body and biology be damaged.
In the developmental research of the industrial solid waste residue such as quartz sand or silica sand CHARACTERISTICS OF TAILINGS SAND and flyash, Publication No. CN A kind of haydite made using quartz sand mine tailing and sludge and preparation method thereof is disclosed in 103864404A Chinese patent, should Patent mainly makes haydite, the reference amount of quartz sand ore tailings using quartz sand mine tailing, sludge, river bottom mud and adjuvant (Mass percent)20~30%, sintering temperature is up to 1100 ~ 1500 DEG C.In Publication No. CN103396150A Chinese patent A kind of method that foam ceramic self-insulation wall material is prepared using solid waste is disclosed, the patent mainly utilizes chromium slag, Flyash, ceramic polished waste residue, albite, bentonite and additive prepare foam ceramic thermal insulation materials for wall, and it is sintered Process need to be carried out under reducing atmosphere, complex process, and be not directed to the utilization of quartz sand or silica sand mine tailing.In Publication No. CN A kind of light floamed ceramic building board and preparation method thereof is disclosed in 101434475 B Chinese patent, the patent is main Light floamed ceramic building board is prepared using flyash, china clay, expanded material, feldspar and lepidolite stone.It was prepared Journey will carry out iron removaling and 12 ~ 24 hours ripenings in early stage to raw material, also to divide nine sections in the later stage and finished product is carried out at annealing Reason, preparation process cycle are oversize.The patent is also not directed to the utilization of quartz sand or silica sand mine tailing.
The content of the invention
It is an object of the invention to provide a kind of using quartz sand or silica sand tailings and flyash as for building light of primary raw material Foam ceramic material and preparation method thereof.The main composition of the foamed ceramics is:Quartz sand or silica sand ore deposit tail 25 ~ 45%, fine coal Ash 40 ~ 60% and additive 15 ~ 20%.Wherein, the sintering aid 5 ~ 10% in additive, foaming agent 5 ~ 10%, binding agent 2.5 ~ 5%, it is mass percent.Sintering aid is borax(Also referred to as sodium tetraborate), foaming agent is calcium carbonate, and binding agent is waterglass, Waterglass plays foam stabilizer simultaneously.
The present invention solves its technical problem and uses following technical scheme:
1st, a kind of high porosity light floamed ceramic using industrial residue as primary raw material, it is characterized in that the foamed ceramics Main composition(Mass percent, wt%)For:Quartz sand or silica sand ore deposit mine tailing 25 ~ 45%, flyash 40 ~ 60% and additive 15 ~ 20%。
2nd, it is a kind of using industrial residue as primary raw material high porosity light floamed ceramic, it is characterized in that the foamed ceramics institute In additive, sintering aid is that 5 ~ 10%, foaming agent is that 5 ~ 10%, binding agent is 2.5 ~ 5%, is the percentage of gross mass. Wherein, sintering aid is borax(Also referred to as sodium tetraborate), foaming agent is calcium carbonate, and binding agent is waterglass, and waterglass rises simultaneously Foam stabilizer acts on.
3rd, a kind of preparation method using industrial residue as the high porosity light floamed ceramic of primary raw material, including following step Suddenly:
The first step:It is prepared by raw material
Respectively by quartz sand(Silica sand)Ore deposit tail, flyash and additive are put into ball milling in planetary ball mill.After ball milling Quartz sand(Silica sand)Ore deposit tailings, flyash and additive cross 200~300 mesh sieves respectively, standby.
Second step:Dispensing, base
By component design, precise quartz sand(Silica sand)Ore deposit tailings, flyash and each raw material of additive, it is stirred It is even, batch is made.Obtained batch is put into stainless steel mould and is pressed into block base substrate.Briquetting pressure is 6 ~ 12MPa.
3rd step:Dry
The base substrate suppressed is put into drying box, is fully dried at a temperature of 100 DEG C, steams the moisture in base substrate Hair, and there is certain intensity.Described intensity refers to ensure that base substrate transports the intensity caused required for sintering furnace.
4th step:Fire
Dried base substrate is entered in sintering furnace with 3 ~ 8 DEG C/minute of heating rate from room temperature to 1050 ~ 1100 DEG C Row sintering, and 1 ~ 3 hour is incubated at a sintering temperature, then cool to room temperature with the furnace, you can be made with quartz sand(Silica sand) Ore deposit tailings is the high porosity light floamed ceramic of primary raw material.
Using silica sand mine tailing and flyash as the high porosity foamed ceramics of primary raw material, it is mainly formed as quartz the present invention Sand or silica sand mine tailing and flyash, total mass percents of two kinds of waste residues is up to 80~85%.Quartz sand or silica sand mine tailing it is main Chemical composition is SiO2, simultaneously containing a small amount of Al2O3、TiO2、Fe2O3、FeO、MgO、CaO、Na2O、K2The compositions such as O.Flyash Main composition includes SiO2、Al2O3、Na2O, contain Fe simultaneously2O3、CaO、MnO、MgO、K2O、TiO2、P2O5Deng composition.Above-mentioned group Cheng Zhong, SiO2、Al2O3Composition plays skeleton function in foamed material, can assign the excellent mechanical performance of foamed material, calorifics Energy and chemical stability.Generally, SiO in material2、Al2O3Content is higher, then its intensity is higher, thermal coefficient of expansion is lower, chemical Stability is better.But SiO in material2、Al2O3Content is higher, then required sintering temperature is also high, therefore, it is necessary to designs properly SiO2、Al2O3Content.CaO in quartz sand or silica sand mine tailing and flyash is generally with CaCO3Form is present, and additional CaCO3Together as the foaming agent of foamed ceramics.In addition, CaO, MgO, Na2O、K2The alkaline-earth metal such as O and alkali metal oxide are Excellent sintering aid, the sintering temperature of foamed ceramics can be substantially reduced.Meanwhile CaO, MgO, Na2O、K2O and SiO2、Al2O3 Chemically react, generation silicate, aluminic acid molten salt bath, and then form glass phase.On the one hand, the formation of silicate, aluminate Can be to Na+、K+Ion and heavy metal ion play " constraint ", during the use of material, these bound alkali metal from Son and heavy metal ion are difficult to discharge, so as to solve alkalization of soils and heavy metal ion pollution problem;On the other hand, glass phase Formation gas wrapping can be lived again, form loose structure, and poisonous and harmful component sealing can be made obtained foamed ceramics Material does not produce secondary pollution.TiO present in waste residue2、Fe2O3、FeO、MnO、P2O5Etc. being that to prepare foamed material not essential Composition, in sintering process, can make its participate in foamed ceramics composition, so as to reduce the relative cost of raw material.
CaO, MgO, the Na introduced due to silica sand mine tailing and flyash2O、K2O deficiencies, therefore, introducing portion borax(Also referred to as Sodium tetraborate)As sintering aid, to reduce the sintering temperature of foamed ceramics.Meanwhile introducing portion calcium carbonate, with silica sand mine tailing With flyash introduce calcium carbonate together, as foaming agent.Waterglass is introduced as binding agent and foam stabilizer, on the one hand assigns bubble The particle adhesion strength of foam ceramic body before sintering, on the other hand can improve the stability of bubble, be advantageous in foamed ceramics The formation of uniform stomata.
The foamed ceramics as made from patent of the present invention, principal crystalline phase are anorthite(CaAl2Si2O8), also have in addition a small amount of not next Stone(Mullite, 3Al2O3·2SiO2), corundum(Al2O3)And CaAl2Si2O8Crystal and a certain amount of glass phase.Foamed ceramics it is close Spend for 0.59~0.73g/cm3, the porosity 65.7~69.8%, 4.0~4.7MPa of bending strength, compression strength 10.9~ 12.9MPa, acid resistance 98.1~98.3%, alkali resistance 99.1~99.4%, with waste residue utilization rate is high, technique is simple, equipment is wanted Ask the features such as low, cost is low, product strength is high, density is low, the porosity is big, non-secondary pollution, be particularly suitable for use as have every Paste layer and material inside and outside heat, insulation, sound insulation, the building top layer of fire-proof function, indoor non-bearing wall and building.
Compared with the prior art, the method have the characteristics that:
1)The present invention is big to industrial residue quartz sand or the usage amount of silica sand mine tailing and flyash, reaches as high as 85%, can have Effect utilizes quartz sand industrial residue, reduces by two kinds of waste residues to appropriation of land, alleviates its environmental problem triggered.
2)Foamed ceramics made from the invention, its firing temperature are low(1050~1100℃), firing period is short, energy consumption is low, system Standby technique is simple, and equipment requirement is low.
3)For the porosity of foamed ceramics obtained by the present invention up to more than 65%, bulk density is less than 0.75g/cm3, stomata It is evenly distributed, aperture is moderate, and density is small, and thermal conductivity is low, and intensity is high, has excellent heat-insulation and heat-preservation soundproof effect.
4)Foamed ceramics obtained by the present invention passes through high temperature sintering, and the extensive chemical between composition combines, and noxious material is consolidated Change, therefore the foamed ceramics has fire-proof function, chemical stability is good, and secondary pollution is not produced during use.
Brief description of the drawings
Fig. 1 is the XRD of the foamed ceramics prepared by the embodiment of the present invention 2;
Fig. 2 is the profile of the foamed ceramics prepared by the embodiment of the present invention 1,2.
XRD diffracting spectrums understand that the principal crystalline phase in foamed ceramics prepared by this method is anorthite as shown in Figure 1 (CaAl2Si2O8), also a small amount of mullite in addition(Mullite, 3Al2O3·2SiO2), corundum(Al2O3)And CaAl2Si2O8, it is brilliant Phase and a certain amount of glass phase;As shown in Figure 2, between stomata independently of each other, hole of uniform size of holding one's breath is formed.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention will be further described in detail, but does not limit present invention protection model Enclose.
Embodiment 1:
It is a kind of using industrial residue as high porosity light floamed ceramic of primary raw material and preparation method thereof, foamed ceramics Main composition is quartz sand or silica sand mine tailing 40%, flyash 40% and additive 20%.Wherein borax in additive(Also referred to as four Boratex)For 10%, calcium carbonate 5%, waterglass 5%.
Precise silica sand or quartz sand ore tail, flyash, sintering aid, foaming agent, are put into ball milling in planetary ball mill, Mixing and ball milling material is crossed into 200~300 mesh sieves, it is standby.Binding agent is added in powder after sizing, is well mixed, cooperation is made Material.Obtained batch is put into stainless steel mould and is pressed into block base substrate.Briquetting pressure is 12MPa.The base that will be suppressed Body, which is put into air, spontaneously dries 1 hour or is put into constant temperature drying 0.5 hour in 100 DEG C of drying box.By dried base Body is put into sintering furnace and sintered, and wherein heating rate is 5 DEG C/min, 1080 DEG C of sintering temperature, in maximum temperature heat preservation sintering 2 Hour.
Embodiment 2:
It is a kind of using industrial residue as high porosity light floamed ceramic of primary raw material and preparation method thereof, foamed ceramics Main composition is quartz sand or silica sand mine tailing 30%, flyash 50%, and additive 20%.Wherein borax in additive(Also referred to as four Boratex)For 7.5%, calcium carbonate 10%, waterglass 2.5%.
Precise silica sand or quartz sand ore tail, flyash, sintering aid, foaming agent, are put into ball milling in planetary ball mill, Mixing and ball milling material is crossed into 200~300 mesh sieves, it is standby.Binding agent is added in powder after sizing, is well mixed, cooperation is made Material.Obtained batch is put into stainless steel mould and is pressed into block base substrate.Briquetting pressure is 10MPa.The base that will be suppressed Body is put into constant temperature and dried 1 hour in 100 DEG C of drying box.Dried base substrate is put into sintering furnace and sintered, wherein heating up Speed was 8 DEG C/min, 1080 DEG C of sintering temperature, in maximum temperature heat preservation sintering 1 hour.
Embodiment 3:
It is a kind of using industrial residue as high porosity light floamed ceramic of primary raw material and preparation method thereof, foamed ceramics Main composition is quartz sand or silica sand mine tailing 25%, flyash 60%, additive 15%.Wherein borax in additive(Also referred to as tetraboric acid Sodium)For 5%, calcium carbonate 5%, waterglass 5%.
Precise silica sand or quartz sand ore tail, flyash, sintering aid, foaming agent, are put into ball milling in planetary ball mill, Mixing and ball milling material is crossed into 200~300 mesh sieves, it is standby.Binding agent is added in powder after sizing, is well mixed, cooperation is made Material.Obtained batch is put into stainless steel mould and is pressed into block base substrate.Briquetting pressure is 8MPa.The base substrate that will be suppressed Constant temperature is put into dry 1 hour in 100 DEG C of drying box.Dried base substrate is put into sintering furnace and sintered, wherein heating speed Rate was 3 DEG C/min, 1100 DEG C of sintering temperature, in maximum temperature heat preservation sintering 1 hour.
Embodiment 4:
It is a kind of using industrial residue as high porosity light floamed ceramic of primary raw material and preparation method thereof, foamed ceramics Main composition is quartz sand or silica sand mine tailing 45%, flyash 37%, and additive 15%.Wherein borax in additive(Also referred to as four Boratex)For 10%, calcium carbonate 5%, waterglass 3%.
Precise silica sand or quartz sand ore tail, flyash, sintering aid, foaming agent, are put into ball milling in planetary ball mill, Mixing and ball milling material is crossed into 200~300 mesh sieves, it is standby.Binding agent is added in powder after sizing, is well mixed, cooperation is made Material.Obtained batch is put into stainless steel mould and is pressed into block base substrate.Briquetting pressure is 6MPa.The base substrate that will be suppressed It is put into air and spontaneously dries 2 hours.Dried base substrate is put into sintering furnace and sintered, wherein heating rate is 5 DEG C/minute Clock, 1080 DEG C of sintering temperature, in maximum temperature heat preservation sintering 3 hours.
Embodiment 5:
It is a kind of using industrial residue as high porosity light floamed ceramic of primary raw material and preparation method thereof, foamed ceramics Main composition is quartz sand or silica sand mine tailing 25%, flyash 55%, and additive 20%.Wherein borax in additive(Also referred to as four Boratex)For 10%, calcium carbonate 5%, waterglass 5%.
Precise silica sand or quartz sand ore tail, flyash, sintering aid, foaming agent, are put into ball milling in planetary ball mill, Mixing and ball milling material is crossed into 200~300 mesh sieves, it is standby.Binding agent is added in powder after sizing, is well mixed, cooperation is made Material.Obtained batch is put into stainless steel mould and is pressed into block base substrate.Briquetting pressure is 8MPa.The base substrate that will be suppressed It is put into air and spontaneously dries 3 hours.Dried base substrate is put into sintering furnace and sintered, wherein heating rate is 5 DEG C/minute Clock, 1050 DEG C of sintering temperature, in maximum temperature heat preservation sintering 2 hours.
The performance of foamed ceramics is shown in Table 1 made from each embodiment.
The performance of foamed ceramics made from 1 each embodiment of table

Claims (2)

1. a kind of made pottery with silica sand mine tailing and flyash, or quartz sand mine tailing and flyash for the high porosity foam of primary raw material Porcelain, it is characterized in that the mass percent composition of foamed ceramics is:Quartz sand mine tailing or silica sand mine tailing 25 ~ 45%, flyash 40 ~ 60% And additive 15 ~ 20%, the mass percent that each material of described additive accounts for gross mass are:Sintering aid 5 ~ 10%, foaming Agent 5 ~ 10%, binding agent 2.5 ~ 5%, wherein, sintering aid is borax, and foaming agent is calcium carbonate, and binding agent is waterglass.
2. one kind is as claimed in claim 1 with silica sand mine tailing and flyash, or quartz sand mine tailing and flyash are primary raw material High porosity foamed ceramics preparation method, it is characterised in that comprise the following steps:
The first step:It is prepared by raw material
Precise silica sand mine tailing or quartz sand mine tailing, flyash, sintering aid, foaming agent, are put into ball milling in planetary ball mill, Mixing and ball milling material is crossed into 200~300 mesh sieves, it is standby;
Second step:Dispensing, base
Binding agent is added in powder after sizing, is well mixed, batch is made, obtained batch is put into stainless steel mold Block base substrate is pressed into tool, briquetting pressure is 6 ~ 12MPa;
3rd step:Dry
The base substrate suppressed is put into air and spontaneously dries 1 ~ 6 hour or be put into constant temperature dry 0.5 in 100 DEG C of drying box ~1 hour, make the moisture evaporation in base substrate, and assign base substrate and transport the intensity caused required for sintering furnace;
4th step:Fire
By dried base substrate in sintering furnace with 3 ~ 8 DEG C/minute of heating rate from room temperature to 1050 ~ 1100 DEG C, carry out Sintering, and 1 ~ 3 hour is incubated at a sintering temperature, then cool to room temperature with the furnace, that is, be made with silica sand mine tailing and flyash, or Quartz sand mine tailing and flyash are the high intensity of primary raw material, high porosity foamed ceramics.
CN201510000877.5A 2015-01-04 2015-01-04 Using silica sand mine tailing and flyash as foamed ceramics of primary raw material and preparation method thereof Expired - Fee Related CN104496535B (en)

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CN105461346A (en) * 2015-11-23 2016-04-06 攀钢集团攀枝花钢铁研究院有限公司 Method for preparing porous material by use of blast furnace slag titanium-extracting tailings
CN106242595A (en) * 2016-07-27 2016-12-21 昆明理工大学 A kind of refractory material and preparation method thereof
CN107115768B (en) * 2017-04-25 2021-02-12 华北电力大学 Preparation method of flue gas dehydration ceramic membrane with fly ash as main raw material
CN107684688A (en) * 2017-09-05 2018-02-13 常州大学 A kind of high-temperature detoxification method of chromium slag
CN108911726B (en) * 2018-08-28 2021-05-11 中南大学 Coal gangue-desulfurized gypsum-calcium carbonate system water-permeable ceramic tile and preparation method thereof
CN110683832B (en) * 2019-10-28 2020-11-06 北京科技大学 Foamed ceramic prepared from waste incineration fly ash and preparation method thereof
CN111320489A (en) * 2020-03-04 2020-06-23 中南大学 Solid waste based high-strength foamed ceramic and preparation method thereof

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CN101698594A (en) * 2009-11-18 2010-04-28 九江学院 Quartz porous ceramic material and preparation technology thereof
CN102731138A (en) * 2012-07-17 2012-10-17 湖南亿泰环保科技股份有限公司 Fly ash based high-strength and high-porosity foamed ceramic and preparation method thereof
CN102826868A (en) * 2012-08-27 2012-12-19 中南大学 Foaming agent for tailing sintering perforated brick and application thereof
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