CN103159493A - Method for preparing high-alumina refractory material by utilizing pyrite tailing as main raw material - Google Patents
Method for preparing high-alumina refractory material by utilizing pyrite tailing as main raw material Download PDFInfo
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- CN103159493A CN103159493A CN2013101322756A CN201310132275A CN103159493A CN 103159493 A CN103159493 A CN 103159493A CN 2013101322756 A CN2013101322756 A CN 2013101322756A CN 201310132275 A CN201310132275 A CN 201310132275A CN 103159493 A CN103159493 A CN 103159493A
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- pyrite tailing
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Abstract
The invention relates to a method for preparing a high-alumina refractory material by utilizing pyrite tailing as a main raw material. According to the method, the high-alumina refractory material comprises the following raw materials by weight percent: 20% to 82% of pyrite tailing and 18% to 80% of alumina clinker, wherein the content of Al2O3 in the batch mixture is guaranteed to be greater than or equal to 48% and the content of Fe2O3 is less than or equal to 3% by weight percent. In addition, an adhesion agent and water which respectively account for 0% to 2% (weight percent) and 5% to 8% (weight percent) of the total weight of the pyrite tailing and the alumina clinker are added. The method comprises the following steps: drying the raw materials; calcining the clinker; burdening, grinding, mixing, staling, molding and drying the raw materials; and then firing at the oxidizing atmosphere of 1300 to 1450 DEG C, thereby obtaining the high-alumina refractory material with mullite, corundum and cristobalite thereof as main crystal phases.
Description
Technical field
The present invention relates to the refractory materials preparation field, is a kind of method for preparing high alumina refractories take pyrite tailing as main raw material.
Background technology
Pyrite tailing is the waste residue of discharging after pyrite beneficiation.Pyrite tailing is dumped in ground or the gully as waste residue for a long time, serious environment pollution.From the angle of Sustainable development, pyrite tailing is also a kind of potential secondary resource, rationally, effectively fully utilizes these waste resources simultaneously, for saving Mineral resources and preserving the ecological environment significant.
China's pyrite tailing slag dump storage is huge.Take Sichuan Province of the whole nation one of six large Pyrite Mine Areas as example, its sulfurous iron ore reserves are the first in the nation, and wherein regional (Yibin, two cities, the Luzhou) sulfurous iron ore in south, river accounts for again 97% of the whole province, and prognostic reserves reach 45.2 hundred million tons, and the mine tailing amount accounts for the 60-70% of raw ore.Estimate that the mine tailing that store up on regional ground, south, present river has reached more than 1,000 ten thousand tons.Because mineral processing circuit, appointed condition and the state of the art of each Pyrite Mine Enterprises differs larger, so the chemical component fluctuation of south, river pyrite tailing is larger.The chemical constitution of south, river pyrite tailing is (weight percent) SiO
230 ~ 52%, Al
2O
325 ~ 40%, CaO 0.2 ~ 2.0%, Fe
2O
30.6 ~ 19%, TiO
20.5 ~ 7.0%, SO
30.5 ~ 4.5%, other impurity composition 1 ~ 5%.The essential mineral composition of this pyrite tailing is kaolinite, also contains the dirts such as a small amount of anatase titanium dioxide, pyrite and calcite.In this mine tailing, thinner part is semisoft clay, and the essential mineral composition is kaolinite, the pyrite that contains anatase octahedrite, organic matter, hydromica etc. and be not selected, and pyrite content is less.Thicker part forms tailings, the canescence particle, and granularity is difficult to aquation generally at 1～5 mm, belongs to flint clay, is embedded with the pyrite that does not split therebetween.
From the chemical constitution of south, above river pyrite tailing as seen, its topmost chemical composition is Al
2O
3And SiO
2Al
2O
3-SiO
2Binary phase diagram is the basic phasor in aluminosillicate refractory, is also the basis of this system refractory materials.Exist inner link between the chemical constitution of aluminosillicate refractory, phase composite and capabilities of refractory materials.A1 in clay
2O
3When content is 20%～50%, can be according to its refractoriness of following formula proximate calculation t:
t=（360＋A1
2O
3－R）/0.228 （1-1）
In formula: A1
2O
3--the A1 in clay
2O
3And SiO
2When total amount is scaled 100%, the A1 of institute
2O
3The massfraction that accounts for;
The massfraction of R--other impurity.
Take the mean value of aforementioned pyrite tailing chemical constitution as basis, the refractoriness that calculates pyrite tailing according to (1-1) formula is 1690 ℃.Actual analysis has been tested a pyrite tailing sample in addition, and its chemical constitution (weight percent) is: SiO
238.41%, A1
2O
332.40%, CaO 3.02%, TiO
24.01%, MgO 0.76%, Fe
2O
31.91%, Na
2O: 0.16%, K
2O 0.35%, SO
30.92%, loss on ignition 14.30%, surplus are other trace ingredientss.The refractoriness that calculates this pyrite tailing as basis is 1703 ℃.Therefore, in theory, can use pyrite tailing to prepare pure aluminium silicate system refractory materials.Generally can be by Al in pure aluminium silicate system refractory materials
2O
3Content is divided into semi-silica refractory material (Al with refractory materials
2O
315～30%), fireclay refractory (Al
2O
330～48%), high alumina refractories (Al
2O
348%) three classes.
The chemical constitution that the data of should be noted that provides is (weight percent) SiO
230 ~ 52%, Al
2O
325 ~ 40%, CaO 0.2 ~ 2.0%, Fe
2O
30.6 ~ 19%, TiO
20.5 ~ 7.0%, SO
30.5 ~ 4.5%, Fe in the pyrite tailing of other impurity composition 1 ~ 5%
2O
3Too high part is not suitable for preparing refractory materials, because the high Fe in raw material
2O
3Content can have a strong impact on the use propertieies such as refractoriness of refractory materials.But actual the investigation shows Fe in the pyrite tailing chemical constitution
2O
3The part that content is high is all only to adopt gravity separation method to carry out to the sulfurous iron ore raw ore mine tailing that ore dressing produces, and wherein contains quite a lot of pyrite of not selecting, and this mine tailing is for producing in decades and storing up the tailing that gets off.Some enterprise carries out ore dressing again to this mine tailing at present, has both reclaimed sulphur, produces economic benefit, makes again the Fe in pyrite tailing
2O
3Content descends greatly.Along with the renewal of technique of preparing, now a lot of enterprises all adopt heavily floating connection to select technique to carry out the pyrite beneficiation operation, make pyrite remaining in mine tailing drop to very low level, have namely reduced Fe
2O
3Content is for the pyrite tailing comprehensive utilization provides certain condition.
The main raw material that the present invention prepares high alumina refractories is pyrite tailing and bauxitic clay.In order to guarantee that prepared refractory materials has good performance, requires Fe in fire resistive material product
2O
3≤ 3%.From present pyrite beneficiation state of the art, this requirement can reach fully.Can reach this requirement by ore dressing again for storing up for a long time the tailing that gets off.Therefore it is feasible preparing high alumina refractories take pyrite tailing as raw material.
From the document that retrieves, the relevant report that has some to prepare various refractory materialss take mine tailing as main raw material, but have no the correlation technique for preparing high alumina refractories take pyrite tailing as raw material.
Summary of the invention
The objective of the invention is to prepare well behaved high alumina refractories take pyrite tailing, bauxitic clay as main raw material, pyrite tailing is fully utilized, can solve the environmental pollution that pyrite tailing brings, can create economic worth again.
Use pyrite tailing of the present invention prepares the method for high alumina refractories, and following processing step is arranged:
(1) raw material is prepared: pyrite tailing is dried at 80-120 ℃ of temperature.
(2) calcining bauxite clinker: bauxitic clay 1400 ~ 1500 ℃ of temperature lower calcinations 2～3 hours, is sintered into bauxite clinker.
(3) batching: will prepare burden by the ready pyrite tailing of step (1) and the bauxite clinker that is sintered into by step (2), its ingredients by weight per-cent is: pyrite tailing: 20 ~ 82%, and bauxite clinker: 18 ~ 80%; Guarantee simultaneously in admixtion Al by weight percentage
2O
3〉=48%, Fe
2O
3≤ 3%.
(4) grinding: will be placed in by the material that step (3) weigh batching obtains ball mill levigate to crossing 80 mesh sieves.
(5) mix: add accounting for this material gross weight 0～2%(weight percent in the material that obtains through step (4)) binding agent and 5～8%(weight percent) water, and mix.Described binding agent is methylcellulose gum or carboxymethyl cellulose.
(6) old: the compound that mixes is old more than 24 hours, to increase its plasticity-.
(7) moulding: the material after old is placed in mould by brick pressing machine compression moulding, makes green compact.
(8) drying: green compact being dried to water ratio at 80 ~ 150 ℃ of temperature is 1 ~ 2%.
(9) burn till: will slowly be warming up to 1390 ℃ ~ 1450 ℃ in High Temperature Furnaces Heating Apparatus by the adobe of step (8) preparation, and burn till be incubated 5 ~ 10 hours under oxidizing atmosphere after, and slowly cool to normal temperature.
Not select on a small quantity sulfurous iron ore owing to containing in pyrite tailing, have sulphur emissions when high temperature burns till out, in order preventing the pollution of the environment, will to improve the ore-dressing technique technology on the one hand, reduce the sulphur content in mine tailing; Should carry out flue gas desulfurization on the other hand in pyrite tailing clinker burning and refractory materials sintering process process.
High alumina refractories goods by the preparation of above-mentioned proportion scheme and processing step are orange, and surfacing, color and luster are even, and principal crystalline phase is mullite and corundum and a small amount of cristobalite.The salient features of product is: 1750 ℃ ~ 1900 ℃ of product refractoriness, and the 0.2MPa refractoriness under load: 1420 ~ 1590 ℃, compressive strength: 48 ~ 60MPa, density: 2.00 ~ 2.61g/cm
3, apparent porosity: 9.48 ~ 15.51%, reheat linear change :-0.4 ~ 0.2% (1500 ℃, 2h).
Principal feature of the present invention and advantage are:
(1) using industrial residue---pyrite tailing has reduced product cost, and can realize turning waste into wealth as one of main raw material preparation high alumina refractories, effectively alleviates the environmental hazard because pyrite tailing is stacked for a long time and oxidation brings.
(2) owing to containing a small amount of Fe in pyrite tailing
2O
3, FeO, CaO, do not need to add in addition mineralizer.
Embodiment
Below in conjunction with specific examples, the present invention is further set forth, but do not limit the present invention.
Embodiment 1
The pyrite tailing that uses is taken from the flotation cell of the small-sized heavy floating choosing of south, river certain enterprise of area, and its chemical component weight per-cent is: SiO
238.41%, A1
2O
332.40%, CaO 3.02%, TiO
24.01%, MgO 0.76%, Fe
2O
31.91%, Na
2O: 0.16%, K
2O 0.35%, SO
30.92%, loss on ignition 14.30%, surplus are that other trace form.Bauxitic clay chemical composition weight percent used is: Al
2O
3: 74.0%, CaO:0.8%, Fe
2O
3: 2.7%, be the second-rank first class bauxitic clay.Use this pyrite tailing and bauxitic clay to prepare the processing step of high alumina refractories as follows:
(1) pyrite tailing was dried 4 hours at 80-120 ℃ of temperature.
(2) bauxitic clay was prepared bauxite clinker in 2.5 hours at 1410 ± 10 ℃ of temperature lower calcinations.
(3) will be by weight percentage by step (1) and (2) ready material: pyrite tailing 40%, bauxite clinker 60% carry out weigh batching and are placed on and were milled to 80 mesh sieves in ball mill.
(4) add in by the material of step (3) preparation account for this material gross weight 8%(weight percent) water, mixing and stirring, old 24 hours.
(5) material after old is placed in the mould brick pressing machine and is pressed into green compact, forming pressure is 140MPa.
(6) be 1 ~ 2% with brick bat drying to water ratio at 80 ~ 150 ℃ of temperature.
(7) dried green compact are placed in kiln and slowly are warming up to 1420 ± 5 ℃, insulation was burnt till after 6 hours under oxidizing atmosphere, slowly cooled to normal temperature and was product of the present invention.
Prepared product is orange, and surfacing, color and luster are even.The salient features of product is as follows: 1780 ℃ of refractoriness, and the 0.2MPa refractoriness under load: 1490 ℃, compressive strength: 53MPa, density: 2.21g/cm
3, apparent porosity: 10.51%, reheat linear change: 0.09%(1500 ℃, 2h).X ray powder crystal diffraction phase analysis shows that the main crystalline phase of this product is mullite, corundum and a small amount of cristobalite.
Embodiment 2
The pyrite tailing that uses is taken from the flotation cell of the small-sized heavy floating choosing of south, river certain enterprise of area, and its chemical component weight per-cent is: SiO
238.41%, A1
2O
332.40%, CaO 3.02%, TiO
24.01%, MgO 0.76%, Fe
2O
31.91%, Na
2O: 0.16%, K
2O 0.35%, SO
30.92%, loss on ignition 14.30%, surplus are that other trace form.Bauxitic clay chemical composition weight percent used is: Al
2O
3: 74.0%, CaO:0.8%, Fe
2O
3: 2.7%, be the second-rank first class bauxitic clay.Use this pyrite tailing and bauxitic clay to prepare the processing step of high alumina refractories as follows:
(1) pyrite tailing was dried 4 hours at 80-120 ℃ of temperature.
(2) bauxitic clay was prepared bauxite clinker in 2.5 hours at 1410 ± 10 ℃ of temperature lower calcinations.
(3) will be by weight percentage by step (1) and (2) ready material: pyrite tailing 60%, bauxite clinker 40% carry out weigh batching and are placed on and were milled to 80 mesh sieves in ball mill.
(4) add in by the material of step (3) preparation account for this material gross weight 8%(weight percent) water, mixing and stirring, old 24 hours.
(5) material after old is placed in the mould brick pressing machine and is pressed into green compact, forming pressure is 140MPa.
(6) be 1 ~ 2% with brick bat drying to water ratio at 80 ~ 150 ℃ of temperature.
(7) dried green compact slowly are warming up to 1420 ± 5 ℃ in kiln, insulation was burnt till after 6 hours under oxidizing atmosphere, slowly cooled to normal temperature and was product of the present invention.
Prepared product is orange, and surfacing, color and luster are even.The salient features of product is as follows: 1760 ℃ of refractoriness, and the 0.2MPa refractoriness under load: 1420 ℃, refractory brick compressive strength: 49MPa, density: 2.01g/cm
3, apparent porosity: 14.51%, reheat linear change: 0.15%% (1500 ℃, 2h).X ray powder crystal diffraction phase analysis shows that the main crystalline phase of this product is mullite, corundum and a small amount of cristobalite.
Claims (4)
1. method for preparing high alumina refractories take pyrite tailing as main raw material is characterized in that having following processing step:
(1) pyrite tailing is dried at 80-120 ℃ of temperature;
(2) with bauxitic clay 1400 ~ 1500 ℃ of temperature lower calcinations 2～3 hours, be sintered into bauxite clinker;
(3) will prepare burden by the ready pyrite tailing of step (1) and the bauxite clinker that is sintered into by step (2), its ingredients by weight per-cent is: pyrite tailing: 20 ~ 82%, and bauxite clinker: 18 ~ 80%; Guarantee simultaneously Al in admixtion
2O
3Contain by weight percentage greater than 48%, Fe
2O
3≤ 3%;
(4) will be placed in by the material that step (3) weigh batching obtains levigate 80 mesh sieves of extremely crossing of ball mill;
(5) add in the material that obtains through step (4) account for this material gross weight 0～2%(weight percent) binding agent and 5～8%(weight percent) water, and mix;
The admixtion that (6) will be obtained by step (5) is through old, moulding, and drying is made green compact;
(7) will slowly be warming up to 1390 ℃ ~ 1420 ℃ in High Temperature Furnaces Heating Apparatus by the green compact of step (6) preparation, burn till be incubated 5 ~ 10 hours under oxidizing atmosphere after, slowly cool to normal temperature.
2. a kind of method for preparing high alumina refractories take pyrite tailing as main raw material according to claim 1, is characterized in that said binding agent is methylcellulose gum or carboxymethyl cellulose.
3. a kind of method for preparing high alumina refractories take pyrite tailing as main raw material according to claim 1, the main crystalline phase that it is characterized in that prepared refractory materials is mullite and corundum and cristobalite.
4. a kind of method for preparing high alumina refractories take pyrite tailing as main raw material according to claim 1, is characterized in that prepared refractory products is orange, and color and luster is even, surfacing; 1750 ℃ ~ 1900 ℃ of product refractoriness, the 0.2MPa refractoriness under load: 1420 ~ 1590 ℃, compressive strength: 48 ~ 60MPa, density: 2.00 ~ 2.61g/cm
3, apparent porosity: 9.48 ~ 15.51%, reheat linear change :-0.4 ~ 0.2% (1500 ℃, 2h).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033784A (en) * | 2017-12-08 | 2018-05-15 | 安徽雷萨重工机械有限公司 | A kind of recoverying and utilizing method for troilite slag |
| CN109053146A (en) * | 2018-10-18 | 2018-12-21 | 陕西理工大学 | V-ti magnetite tailing prepares the method without glaze stair |
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| JPH06234574A (en) * | 1993-02-08 | 1994-08-23 | Ngk Insulators Ltd | Monolithic refractory for burner nozzle |
| CN1096503A (en) * | 1993-06-19 | 1994-12-21 | 包钢耐火材料厂 | Compact high-alumina refractory brick |
| CN101054308A (en) * | 2007-05-31 | 2007-10-17 | 郑州祥通耐火陶瓷有限公司 | Gas permeable brick for producing carbon baking furnace flame path wall by gold tailings and iron tailings |
| CN101618971A (en) * | 2009-07-31 | 2010-01-06 | 西安墙体材料研究设计院 | Municipal sludge expanded ceramsite and preparation method thereof |
-
2013
- 2013-04-17 CN CN2013101322756A patent/CN103159493A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06234574A (en) * | 1993-02-08 | 1994-08-23 | Ngk Insulators Ltd | Monolithic refractory for burner nozzle |
| CN1096503A (en) * | 1993-06-19 | 1994-12-21 | 包钢耐火材料厂 | Compact high-alumina refractory brick |
| CN101054308A (en) * | 2007-05-31 | 2007-10-17 | 郑州祥通耐火陶瓷有限公司 | Gas permeable brick for producing carbon baking furnace flame path wall by gold tailings and iron tailings |
| CN101618971A (en) * | 2009-07-31 | 2010-01-06 | 西安墙体材料研究设计院 | Municipal sludge expanded ceramsite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《矿物岩石》 20011231 高德政 等 "叙永硫铁矿尾矿(高岭石粘土)的成分特征与利用研究" 第5-9页 1-4 第21卷, 第2期 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033784A (en) * | 2017-12-08 | 2018-05-15 | 安徽雷萨重工机械有限公司 | A kind of recoverying and utilizing method for troilite slag |
| CN109053146A (en) * | 2018-10-18 | 2018-12-21 | 陕西理工大学 | V-ti magnetite tailing prepares the method without glaze stair |
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Application publication date: 20130619 |