CN102584189A - Method for manufacturing alkali complex-phase high-temperature resistant powder containing forsterite-silicon nitride-silicon carbide - Google Patents
Method for manufacturing alkali complex-phase high-temperature resistant powder containing forsterite-silicon nitride-silicon carbide Download PDFInfo
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- CN102584189A CN102584189A CN201210034634XA CN201210034634A CN102584189A CN 102584189 A CN102584189 A CN 102584189A CN 201210034634X A CN201210034634X A CN 201210034634XA CN 201210034634 A CN201210034634 A CN 201210034634A CN 102584189 A CN102584189 A CN 102584189A
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- forsterite
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Abstract
The invention relates to a method for manufacturing alkali complex-phase high-temperature resistant powder containing forsterite-silicon nitride-silicon carbide, and belongs to the technical field of high-temperature resistant materials. The method comprises the following steps of: ball-milling and mixing low-grade serpentine powder ore or other magnesium series silicate mineral tailing and the like serving as a raw material and a proper amount of carbon source (coke, carbon block or graphite and the like), pressing the fully mixed powder into a blank, fully drying, putting in a reductive atmosphere furnace, introducing nitrogen serving as a reductive protective gas, reacting at a high temperature, and thus obtaining the alkali complex-phase high-temperature resistant powder containing the forsterite-silicon nitride-silicon carbide. The alkali complex-phase high-temperature resistant powder containing the forsterite-silicon nitride-silicon carbide has excellent high-temperature resistance, alkali slag corrosion resistance and the like, so the powder has a broad application prospect in the fields of refractory material products, high-performance novel complex-phase high-temperature resistant materials and the like. Meanwhile, the new method for preparing the alkali complex-phase high-temperature resistant powder containing the forsterite-silicon nitride-silicon carbide has the characteristics of simple equipment, low cost and low consumption of energy in the preparation process, provides a new technical path for efficient value-added use of the serpentine powder ore, and has the predominant advantages of protecting the environment, saving the energy, reducing emission and the like.
Description
Technical field:
The present invention relates to a kind of alkaline complex phase high-temperature resistant powder and method of manufacture thereof that contains forsterite-silicon nitride-silicon carbide silicon, belong to the high temperature material field.
Background technology:
High temperature material is the necessary base mateiral of high-temperature technology industry, and the technical progress of high temperature material industry is that the basic industry of Chinese national economy has been made important contribution.Along with developing rapidly of modern science and technology, the excellent properties of various high temperature materials has more and more caused countries in the world research workers' very big concern.Forsterite (Mg
2SiO
4) be a kind of the have high creep stability and basic refractory of refractoriness under load, can be used as a kind of heat-insulation and heat-preservation and high-temperature refractory, have the good high-temperature performance; Forsterite refractory with island structure has high creep stability and refractoriness under load and non-aquation; Chemicalstability is good, and fusing point is high, and thermal conductivity is low; Good anti-molten metal or slag corrosion resistance effect are arranged, and the consistency with most of refractory materialss under the high temperature is good.Its goods are widely used in the elevated temperature heat construction equipments such as casting, ladle, continuous casting tundish, various fire resistive material product, nonferrous smelting, glass manufacturing and cement rotary kiln.Peridotites is widely used in steel casting, particularly high mangaenese steel spare and Precise Alloy foundry goods etc. as the alkaline molding material of novel environment-friendly.This material has high thermal, thermal capacity, refractoriness and even hot expansibility slowly, and anti-preferably MOX erosional competency.
Serpentine ore can produce a large amount of broken ores in recovery process, granularity＜2～3cm is commonly referred to as serpentine fine ore or mine tailing, accounts for 1/3～1/2 of exploitation total amount, like the annual exploitation about 2 * 10 of Henan serpentine ore
5T, abandoned fine ore about 1 * 10
5T, the fine ore accumulation has reached more than 200 ten thousand tons over 20 years, not only wastes Mineral resources but also account for productive area and the farmland, causes serious environmental to pollute, and influence is produced.The serpentine fine ore contains abundant MgO, Si0
2, be the higher Mineral resources of a kind of utility value, the serpentine fine ore also can be used as refractory materials and Mg, Ni and Nd etc. have the important mineral source that utilizes value element.
Utilization to serpentine and mine tailing thereof mainly concentrates on extraction siliceous or magnesia composition wherein; Have that to extract composition single and utilization ratio is limited; In addition since the separation of silicon magnesium not exclusively caused to serpentine and comprehensive utilization degree is not high; Make the high-quality raw mineral materials of China can not get adding fully utilizing effect, economic benefit is not good, in addition; Because the production of annual a large amount of serpentine fine ore can not get effectively utilizing, make that the utilization of a large amount of serpentine fine ores is restricted in the recovery process.
So new way of the serpentine abandoned mine of reasonable development enormous amount utilization; The high performance that solves the serpentine fine ore utilizes problem to make it become renewable resource; Both helped turning waste into wealth, economized on resources, and be beneficial to again and preserve the ecological environment; Reduce and abandon the valuable soil that occupies usefulness, enlarge the human living space.The comprehensive utilization of serpentine resource is to serve multiple, and when obtaining economic benefit, has also improved ecotope, accelerates the Sustainable development process simultaneously.
Solution serpentine fine ore is put forth effort in this research invention and other magnesium is the utilization again of silicate minerals, and realizing turns waste into wealth alleviates the dp of environmental pollution simultaneously.Adopting carbothermal reduction-nitridation technology to make magnesium is that the silicate minerals mine tailing is converted into the alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon.Preparing method of the present invention has that cost is low, processing condition are easy to realize; Environment is not polluted, be appropriate to the scale of chemical production, adopt it to have good resistance to elevated temperatures, anti-fusion and remarkable advantages such as alkali-resistivity scouring performance and thermal property as the powder raw material of making alkaline complex phase high-temperature resistant material.
Summary of the invention:
Order of the present invention is to recycle these problems for solving the environmental pollution that generation that a large amount of serpentine fine ores that produce of present China and other magnesium is the silicate minerals solid waste causes to realize its high added value and high-performance, and propose a kind of technology simply, cost is lower, energy consumption is lower, contain forsterite-method of manufacture of the alkaline complex phase high-temperature resistant powder of silicon nitride-silicon carbide silicon.
For realizing above-mentioned purpose, technical scheme of the present invention is following:
The present invention is silicate minerals solid waste and carbon source (coke powder with serpentine fine ore or other magnesium; Or other carbon material is like the charcoal piece before and after using and graphite electrode powder, electric calcined anthracite powder, asphalt powder, petroleum coke powder, active black) be main raw material; The two is mixed the back according to a certain ratio add that ball milling 30min～48h is to the two uniform mixing in the ball mill, the mode of ball milling is dry ball milling or wet ball grinding.Wherein ball-milling medium can be selected Ceramic Balls or agate ball etc. for use, and the ball milling liquid that wet ball grinding is selected for use is water or absolute ethyl alcohol etc.Then with the raw material process moulding that mixes; Wherein moulding process can adopt dry-pressing formed, half-dried molded or isostatic pressing; Or adopt dribbling balling machine to be shaped to spheroidal particle the raw material; The base substrate that drying is good (or directly be contained in admixtion in the plumbago crucible or in the reaction vessel of other high temperature resistant and suitable reductibility reaction mediums) places thermal kiln furnace (the coal-fired kiln of Ma Fushi combustion gas kiln or closed) to feed nitrogen to heat and burn till through carbothermal reduction-nitridation; Base substrate burns till through the carbothermal reduction-nitridation in the TR of normal temperature to 1300 ℃～2000 ℃ in the sintering process; Need feed nitrogen simultaneously so that reducing atmosphere to be provided, nitrogen partial pressure remains on 0.01～0.5MPa, and heat-up rate does not have particular requirement; And under final firing temperature, be incubated 30min～90h; Technological processs such as after under reducing atmosphere, naturally cooling to room temperature then, the above-mentioned product that burns till is through naturally cooling, and is broken, levigate can be prepared the said alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon.This contains in the alkaline complex phase high-temperature resistant powder of forsterite-silicon nitride-silicon carbide silicon and contains thing phase Mg
2SiO
4, β-Si
3N
4And β-SiC and a small amount of unreacted coke completely, this complex phase powder has good resistance to elevated temperatures, alkali-resistivity scouring performance etc., so it has broad application prospects in fields such as fire resistive material product and the novel complex phase high-temperature resistant materials of high-performance.
The novel method that this preparation that the present invention relates to contains the alkaline complex phase high-temperature resistant powder of forsterite-silicon nitride-silicon carbide silicon has that equipment is simple, with low cost, preparation process consumed energy is few and is convenient to outstanding advantage such as scale operation, simultaneously also for the efficient increment utilization of serpentine fine ore, realize energy-saving and emission-reduction in the industrial production, protect the Sustainable development of environment that a new technological approaches is provided.
Specific embodiment:
Below in conjunction with embodiment technical scheme of the present invention is further specified:
Embodiment 1
To adopt serpentine fine ore and coke to carry out carbothermal reduction-nitridation insulation 6h as carbon source at 1550 ℃, preparing a kind of alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon is example.
Serpentine fine ore add-on is 84.4wt%, wherein SiO
2Percentage composition is 46.3wt%, and median size is 0.074mm; The coke powder add-on is 15.6wt%, and wherein the C percentage composition is 90.0wt%, and median size is less than 0.150mm.
At first with various raw materials according to the above-mentioned ratio mixer of packing into, dry ball milling 48h, the raw material thorough mixing is even, and granularity is less than 0.150mm, the aperture sieve screen over-size is less than 2.0wt%.The material that ball mill mixing is good adds in the mixer and mixes after the adding suitable quantity of water, is configured as spheroidal particle to material with nodulizer then.Sample after the moulding is seasoning 24h at room temperature, makes water ratio≤1.0% of sample.The sample that drying is good places plumbago crucible to pack retort furnace into through the high pure nitrogen carbothermal reduction-nitridation, and nitrogen partial pressure remains on 0.2MPa, and flow control is at 1.5L/min, and firing temperature is set at 1550 ℃ and be incubated 6 hours.Technological processs such as the above-mentioned product that burns till passes through naturally cooling, and is broken, levigate can be prepared the said alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon.
Present embodiment is said to contain that main thing phase composite is Mg in the alkaline complex phase high-temperature resistant powder of forsterite-silicon nitride-silicon carbide silicon
2SiO
4, contain β-Si simultaneously
3N
4And β-SiC and a small amount of unreacted coke completely.
Embodiment 2
Use serpentine fine ore and coke to carry out carbothermal reduction-nitridation and be incubated 6h preparing a kind of alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon and being example at 1600 ℃ to adopt as carbon source.
Use serpentine fine ore add-on to be 72.9wt%, wherein SiO
2Percentage composition is 46.3wt%, and median size is 0.074mm; The coke powder add-on is 27.1wt%, and wherein the C percentage composition is 90.0wt%, and median size is less than 0.150mm.
At first with various raw materials according to the above-mentioned ratio mixer of packing into, water is cooked ball milling liquid wet ball grinding 8h, and the raw material thorough mixing is even, granularity is less than 0.150mm, the aperture sieve screen over-size is less than 2.0wt%.The material that ball mill mixing is good adds in the mixer and mixes after the adding suitable quantity of water, is configured as spheroidal particle to material with nodulizer then.Sample after the moulding is seasoning 12h at room temperature, then in dry kiln in 100 ℃ of dry 12h, make water ratio≤1.0% of sample.The sample that drying is good places plumbago crucible to pack retort furnace into through the high pure nitrogen carbothermal reduction-nitridation, and nitrogen partial pressure remains on 0.3MPa, and flow control is at 1.5L/min, and firing temperature is set at 1600 ℃ and be incubated 6 hours.Technological processs such as the above-mentioned product that burns till passes through naturally cooling, and is broken, levigate can be prepared the said alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon.
Present embodiment is said to contain that main thing phase composite is Mg in the alkaline complex phase high-temperature resistant powder of forsterite-silicon nitride-silicon carbide silicon
2SiO
4And β-Si
3N
4, contain β-SiC and a small amount of unreacted coke completely simultaneously.
Embodiment 3
To adopt serpentine fine ore and graphite to carry out carbothermal reduction-nitridation and be incubated 3h that to prepare a kind of alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon be example at 1600 ℃ as carbon source.
Serpentine fine ore add-on is 78.3wt%, wherein SiO
2Percentage composition is 46.3wt%, and median size is less than 0.074mm; The graphite add-on is 21.7wt%, and wherein the C percentage composition is 99.9wt%, and median size is less than 0.150mm.
At first with various raw materials according to the above-mentioned ratio mixer of packing into, be ball milling liquid wet ball grinding 8h with absolute ethyl alcohol, the raw material thorough mixing is even, and granularity is less than 0.150mm, the aperture sieve screen over-size is less than 2.0wt%.The material that ball mill mixing is good adds in the mixer and mixes after the adding suitable quantity of water, is configured as spheroidal particle to material with nodulizer then.Sample after the moulding is seasoning 12h at room temperature, then in dry kiln in 100 ℃ of dry 12h, make water ratio≤1.0% of sample.The sample that drying is good places plumbago crucible to pack retort furnace into through the high pure nitrogen carbothermal reduction-nitridation, and nitrogen partial pressure remains on the 0.05MPa flow control at 1.5L/min, and firing temperature is set at 1600 ℃ and be incubated 3 hours.Technological processs such as the above-mentioned product that burns till passes through naturally cooling, and is broken, levigate can be prepared the said alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon.
Present embodiment is said to contain that main thing phase composite is Mg in the alkaline complex phase high-temperature resistant powder of forsterite-silicon nitride-silicon carbide silicon
2SiO
4And β-Si
3N
4, contain β-SiC and a small amount of unreacted coke completely simultaneously.
Claims (4)
1. method of manufacture with the alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon; It is characterized in that: the present invention is that silicate minerals mine tailing etc. and coke powder (perhaps other surrogates such as Graphite Powder 99 or carbon black etc.) are main raw material with low-grade serpentine fine ore or other magnesium; With its abundant by a certain percentage mixing; Then through dry-pressing formed (perhaps half-dried molded or isostatic pressing) after drying; (perhaps directly admixtion being contained in plumbago crucible (the reaction to fire container that perhaps is fit to the reductibility reaction medium)); Loading of kiln also feeds nitrogen and does protection gas and nitrogenizing reaction gas and carry out the carbothermal reduction-nitridation reaction, and the final reaction resultant is prepared the alkaline complex phase high-temperature resistant powder that contains forsterite-silicon nitride-silicon carbide silicon through cooling, fragmentation, pulverizing, technological process such as levigate.
2. method of manufacture according to claim 1; It is characterized in that: said serpentine fine ore is the low-grade fine ore of mining; Perhaps other magnesium after industry is purified be the silicate solid waste as; Talcum mine tailing, forsterite mine tailing or boron mud mine tailing etc. require the particle size range 0.047mm～1.50mm of serpentine fine ore.
3. method of manufacture according to claim 1 is characterized in that: require carbon content per-cent greater than 90% in said coke powder or the surrogate, require particle diameter less than 1.50mm, add-on is 20.0～80.0% (mass percents).
4. method of manufacture according to claim 1; It is characterized in that: said carbothermic reduction process adopts carbothermal reduction-nitridation technology; Temperature of reaction requires at 1300 ℃～2000 ℃; Temperature retention time of nitrogenization requires at 30min～6h, and heat-up rate does not have specific limited in the reaction process, and nitrogen atmosphere dividing potential drop scope is at 0.01～0.5MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324790A (en) * | 2017-06-01 | 2017-11-07 | 内蒙古工业大学 | Forsterite-silicon carbide composite ceramic materials and its synthetic method |
| CN109534805A (en) * | 2018-10-16 | 2019-03-29 | 无锡顺佳特种陶瓷有限公司 | Lithium battery powder sintering forsterite-corundum sagger and preparation method thereof |
| CN115485398A (en) * | 2020-10-16 | 2022-12-16 | 朝日化学工业株式会社 | Composition for preventing oxidation of steel and method for preventing oxidation of steel |
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| CN101560603A (en) * | 2009-05-21 | 2009-10-21 | 北京华夏建龙矿业科技有限公司 | Method for preparing magnesium metal and by-product by vacuum carbothermic reduction with serpentine minerals |
| CN101654374A (en) * | 2009-09-18 | 2010-02-24 | 中国地质大学（北京） | Stemming fire-proof material for blast furnace containing coal gangue and white olivine and preparation method thereof |
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2012
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560603A (en) * | 2009-05-21 | 2009-10-21 | 北京华夏建龙矿业科技有限公司 | Method for preparing magnesium metal and by-product by vacuum carbothermic reduction with serpentine minerals |
| CN101654374A (en) * | 2009-09-18 | 2010-02-24 | 中国地质大学（北京） | Stemming fire-proof material for blast furnace containing coal gangue and white olivine and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324790A (en) * | 2017-06-01 | 2017-11-07 | 内蒙古工业大学 | Forsterite-silicon carbide composite ceramic materials and its synthetic method |
| CN107324790B (en) * | 2017-06-01 | 2020-04-10 | 内蒙古工业大学 | Forsterite-silicon carbide composite ceramic material and synthesis method thereof |
| CN109534805A (en) * | 2018-10-16 | 2019-03-29 | 无锡顺佳特种陶瓷有限公司 | Lithium battery powder sintering forsterite-corundum sagger and preparation method thereof |
| CN115485398A (en) * | 2020-10-16 | 2022-12-16 | 朝日化学工业株式会社 | Composition for preventing oxidation of steel and method for preventing oxidation of steel |
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Application publication date: 20120718 |