CN101255503A - Method for mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas - Google Patents
Method for mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas Download PDFInfo
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- CN101255503A CN101255503A CNA2008100844353A CN200810084435A CN101255503A CN 101255503 A CN101255503 A CN 101255503A CN A2008100844353 A CNA2008100844353 A CN A2008100844353A CN 200810084435 A CN200810084435 A CN 200810084435A CN 101255503 A CN101255503 A CN 101255503A
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Abstract
The invention discloses a method for mining metallurgical co-producing metal aluminum, silicon, acetylene and coal gas, comprising the following steps: coal refuse and high-silicon alumyte are pretreated and gasifiedly integrated, the purifying gas is used as synthesis gas or for fuel gas-steam generating, calcium chloride is chloridized to prepare aluminum subchloride and smelt with calcium carbide and simple substance silicon; aluminum subchloride is reduced to prepare high-pure aluminum or aluminum powder by gas phase method, high-pure superfin alumina is prepared by hydrolysis on oxyhydrogen flame, high-pure superfine aluminum nitride is prepared by pyrolyzing ammonia; silicon-containing calcium carbide is hydrolyzed to prepare acetylene, ash is dissolved by recycled hydrochloric acid, calcium chloride is recycled, industrial silicon is got by acid cleaning for impurity removing. The method belongs to sustainable development mining metallurgical ecological industrial cycle economics, and has considerable economic benefit and social benefit, compared with traditional industry in energy saving, emission reduction and comprehensive utilization.
Description
Technical field
The invention discloses the method for a kind of mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, belong to coloured light-weight metal metallurfgy technical field, especially relevant with the production method of electrolytic aluminum, aluminum oxide, electric heating process melting aluminum silicon alloy, calcium carbide, industrial silicon, Coal Chemical Industry, the clean generating of coal etc.
Background technology
That industries such as the clean generating of known electrolytic aluminum, electric heating process melting aluminum silicon alloy, industrial silicon, calcium carbide, Coal Chemical Industry, coal belong to is with high investment, high flow rate, high pollution industry, is the big power consumer.
Aluminium is the most representative light metal.The method of known production aluminium, the one, molten salt electrolysis method, the 2nd, carbon reduction electric heating process.Carbon is a product of the reduction-oxidation reactive aluminum oxycarbide Al that is aluminium at high temperature
4O
4C, rather than metallic aluminium or aluminium carbide are very difficult and get metallic aluminium from the oxidation of coal aluminum.The production of traditional industry aluminium is that aluminum oxide-cryolite fused salt electrolytic process power consumption is very big, it is calculated that to show, produces one ton of primary aluminum and exploits aluminum ingot casting from bauxite, and all power consumption is 22800KWh.High-silica diaspore ore is not suitable for producing aluminium oxide by bayer, adopts the acid system environmental pollution serious.And the every product of industrial silicon 1t power consumption is 13000～17000KWh, and the every product of carbide acetylene 1t acetylene power consumption is about 7500KWh.
Newer aluminium metallurgy is the electric heating process aluminium metallurgy, promptly a kind of non-electrolysis aluminium metallurgy, and this method is identical with the electrosmelting method of calcium carbide, ferrosilicon, industrial silicon, all is electric heating process reduction with carbon melting.It is compared with traditional electrolytic process, has flow process simple, and facility investment is few; Production capacity is big, and the capacity usage ratio height is without rectifying installation; To ingredient requirement not high (kaolin, clay promptly can be raw material), do not need advantages such as fluoride salt.But this method can only obtain aluminum silicon alloy.Because carbon must go out metal in the hydrogen reduction that just can capture in the aluminum oxide more than 2000 ℃, with this understanding, the vaporization losses of aluminium is big, and the aluminium content in the gas phase is higher, and normal pressure is finished drilling and done to be difficult to carry out, and output is very little.SiO by contrast
2Just can be about 1700 ℃ by carbon reduction, produce the existing proven technique of polysilicon and silicon carbide, practice points out, more than 1700～1800 ℃ the time, the extraction yield of silicon can reach 80～84% in the furnace charge.Aluminum oxide and silicon-dioxide can make the aluminum silicon alloy of aluminum content 70～80% jointly by carbon reduction.Studies show that Al
2O
3And SiO
2Be to carry out in three steps by the reaction of carbon reduction jointly:
The first step:
Second step:
The 3rd step:
This electric heating method also can be used for producing silicocalcium and calsibar alloy.
Aluminum silicon alloy extracts fine aluminium, commonly electrolytic process and lower chloride fork solution.Aluminum silicon alloy is energy-conservation unlike spreading method through refining aluminium again.The principle of aluminum chloride fork solution be because aluminium is easier to generate halogenide at a low price with halogen, and aluminum halide is only at high temperature stable at a low price, just decomposes at low temperatures at a low price.Can at high temperature make the aluminium in the aluminum silicon alloy transform AlCl in view of the above
(gas), fork is separated and is aluminium and aluminum chloride at low temperatures then, to reach the purpose of extracting fine aluminium from aluminum silicon alloy.
The aluminum chloride fork is separated to react and is at a low price
Aluminum chloride fork solution can also be carried out in fused salt at a low price, at this moment is with the same AlCl of aluminum silicon alloy
3React in the fused salt that itself and KCl form, because AlCl is dissolvable in water in the high-temperature fusant and non-volatile, AlCl just decomposites aluminium when melt cools off, and this method makes the volume of equipment greatly reduce.Aluminum chloride fork solution is the industrial a kind of effective means that extracts fine aluminium from aluminum silicon alloy at a low price.
Electrolytic aluminum, electric heating process melting aluminum silicon alloy, the outstanding feature of industries such as industrial silicon, calcium carbide, Coal Chemical Industry, the clean generating of coal is that energy consumption is very big, next is low, " three wastes " seriously polluted, economic growth transition dependence Energy resources consumption of utilization ratio of Mineral resources.The industrial residue main component is generally with SiO
2, CaO, Al
2O
3Exist Deng oxide form, abandon as refuse, and these oxide compounds also are the required important source material of industrial production.How reasonable development industrial residue resource technology is an important problem, and the discharging that fundamentally solves industrial residue is prior problem.
Summary of the invention
The method that the purpose of this invention is to provide a kind of mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, this method have low input, high production, low consumption, fewly discharges, can circulate, coloured light metal circulation metallurgical technology flow process of integrated, a plurality of industry products energy of a plurality of art energy coproduction.
For realizing that purpose of the present invention has adopted following technical scheme:
The method of mining metallurgy with coproduction of metal aluminium of the present invention, silicon, acetylene and coal gas, be to comprise that Mineral resources pre-treatment such as coal gangue, high-silica diaspore ore and gasification form integrated, the chlorination of slag carbon reduction electric heating produces that at a low price aluminum chloride and carbide of calcium melting and elemental silicon melting are integrated, with coal and industrial oxygen respectively with high-silica diaspore ore or coal gangue slag tap pressurized gasification, output with CO and H
2Be main high heating value gas, this purifies coal gas as synthetic gas or fuel gas-steam generating, high-silica diaspore ore, coal gangue carbon containing slag and CaCl
2Fused salt batching, the chlorination of carbon reduction electric heating are produced aluminum chloride gasification product at a low price, absorb AlCl with the circulation of high temperature KCl fused salt and separate with coal gas, and cooling KCl absorption melt AlCl once fork separates and isolates crude aluminum liquid and AlCl
3, adopt low price aluminum chloride fork solution secondary fork to separate and extract fine aluminium and AlCl
3, direct H when AlCl secondary high-temperature gasification
2Superfine aluminium power (or aluminium liquid) and hydrochloric acid are produced in reduction, the H that is purifying
2And O
2Flame on oxydrolysis directly produce high-purity ultra-fine alumina, with the NH that purifies
3Solid/liquid/gas reactions is directly produced high-purity ultra-fine aluminum nitride, and the slag main component that the electric heating process chlorination is discharged is the carbide of calcium melt that contains elemental silicon, produces acetylene through the cooling hydrolysis, and calcium carbide clinker is with reclaiming the dissolving with hydrochloric acid that HCl makes, CaCl
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
High-silica diaspore ore of the present invention and coal and industrial oxygen slag tap pressurized gasification, output are with CO and H
2The condition that is main coal gas is: the batching of raw material high-silica diaspore ore and coal and oxygen, make the C and the Al of reductive agent total amount
2O
3Mol ratio be 3: 1, with SiO
2Mol ratio be 2: 1, with contained H
2The O mol ratio is 1: 1, and C and O act as a fuel
2Mol ratio be 2: 1, be 1500～1900 ℃ of pressure 2.0～3.0MPa, melt oxidation layer temperature with bunker coal and industrial oxygen control slag tap pressurized gasification condition, purify coal gas as synthetic gas or fuel gas-steam generating.
High-silica diaspore ore of the present invention and coal and industrial oxygen slag tap pressurized gasification, output CO and H
2Be main coal gas, raw material comprises bauxite such as kaolin, clay, diaspore, boehmite, gibbsite, kyanite, andaluzite, sillimanite, coal gangue and contains Al
2O
3, SiO
2, CaO is the waste of main metal oxide.
CaCl of the present invention
2Fused salt and high-silica diaspore ore pre-treatment carbon containing slag directly mix, and the condition that low price aluminum chloride is produced in the chlorination of carbon reduction electric heating is: CaCl
2The charge ratio of fused salt and high-silica diaspore ore carbon containing slag is as the criterion with the atomic molar ratio of Cl and Al at 1: 1, reductive agent C and CaCl
2Mol ratio is 2: 1, with Al
4O
4The mol ratio of C is 3: 1, with SiO
2Mol ratio be 2: 1,1600～2000 ℃ of melting bed temperature are controlled in electric heating process heating, chlorination gasification in upper strata is that main conversion zone temperature keeps more than 1600 ℃, middle lower floor elemental silicon generates and CaC
2Melting section temperature keeps 1800 ℃～2000 ℃.
Carbon reduction electric heating process chlorination output of the present invention is the mixed gas of primary product with AlCl and CO, KCl high-temperature molten salt absorption AlCl with recycle separates with coal gas, purify coal gas as synthetic gas or fuel gas-steam generating, cooling KCl absorbs melt, low price aluminum chloride once fork is separated, and the KCl fused salt is isolated crude aluminum liquid and AlCl
3The condensation solid.
Employing of the present invention is aluminum chloride fork solution at a low price, AlCl
3Purify being warming up to crude aluminum liquid reaction more than 800 ℃ with removing dust under the high temperature more than 800 ℃ through distillation, be converted into purified AlCl gas again, the secondary fork is separated and is produced fine aluminium and AlCl under cryogenic vacuum degree 1KPa condition then
3
The divergent solution of employing of the present invention is direct H when AlCl secondary high-temperature gasification
2Superfine aluminium power or aluminium liquid are produced in reduction, reclaim HCl gas and produce the hydrochloric acid recycle.
The divergent solution of employing of the present invention is when AlCl secondary high-temperature gasification, with the NH that purifies
3Solid/liquid/gas reactions is directly produced high-purity ultra-fine aluminum nitride, and the gas-phase reaction condition is: gaseous state AlCl and NH
3The mole proportioning be 1: 1.05～1.15,1000～1300 ℃ of control reaction temperature.
The divergent solution of employing of the present invention is when AlCl secondary high-temperature gasification, at the H of purification
2And O
2Flame on the AlCl oxydrolysis directly produce high-purity ultra-fine alumina, the gas-phase reaction condition is: gaseous state AlCl and H
2The mole proportioning be 1: 0.50～0.55, with O
2The mole proportioning be 1: 1.5～1.65,900～1250 ℃ of control reaction temperature.
Carbon reduction electric heating process of the present invention chlorination is produced in the low price aluminum chloride process, and the carbide of calcium melt that contains elemental silicon of discharge is produced acetylene gas, calcium carbide clinker with reclaiming the dissolving with hydrochloric acid that HCl makes, CaCl through the water coolant decomposition
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
Technical scheme advantage of the present invention is directly to utilize natural Mineral resources or contains Al
2O
3, SiO
2, CaO waste be raw material, the energy gasifies based on the coal metallurgical process, Coal Chemical Industry product and combustion gas--steam cogeneration step comprehensive utilization, based on melting and reducing and optimizing network resource utilization, the manufacturing of collection product, Energy conversion and social waste renewable resources three big functions are the demoncal rations of recycling economy in the metallurgical process of new generation capable of circulation of one, are the mining and metallurgy eco industrial parks of Sustainable development.
Positively effect of the present invention is: the metallurgical process of metallic aluminium, industrial silicon and the fusion process of calcium carbide be the coal gasification course of coal gas, Coal Chemical Industry, the clean generating of coal just, compare with traditional industry at aspects such as energy-saving and emission-reduction, comprehensive utilizations, incomparable economic benefit and immeasurable social benefit are arranged.
Embodiment
The method of mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas is that high-silica diaspore ore, coal gangue pre-treatment and gasification are integrated, CaCl
2The chlorination of fused salt electric heating process is produced low price aluminum chloride and calcium carbide and elemental silicon and is founded integrated, contain the natural Mineral resources of aluminium, calcium, silicon or founding and metallurgical process of waste, the coal gasification course of the clean generating of gasification, Coal Chemical Industry, coal just, melted gangue directly is a metallurgical raw material.
High-silica diaspore ore, coal gangue found processing in conjunction with gasification, adopt the granularity of sophisticated slag tap pressurization lurgi gasifier, mineral aggregate and coal can select 2～20mm, moisture in mineral aggregate and the coal does not hinder in operation, carry part fine coal and tar and mineral fine with industrial oxygen and go into the burner hearth melting layer through nozzle, under the pressure of 2.0～3.0MPa and hot conditions, fuse and coal gasification, mineral aggregate decomposes and the sintering fusing when making high heating value gas, purifies coal gas as synthetic gas or fuel gas-steam generating.
Bauxite and coal and industrial oxygen slag tap pressurized gasification, the proportion of raw materials principle is as the C and the Al of reductive agent total amount
2O
3Mol ratio be 3: 1, with SiO
2Mol ratio be 2: 1, with contained H
2The mol ratio of O is 1: 1, and C and O act as a fuel
2Mol ratio be 2: 1, be pressure 2.0～3.0MPa with bunker coal and industrial oxygen control slag tap pressurized gasification condition, 1500～1900 ℃ of melt oxidation layer temperature.Its principal reaction is:
C+O
2＝CO
2 CO
2+C→2CO C+H
2O→CO+H
2
2Al
2O
3+3SiO
2+12C→Al
4O
4C+3SiC+8CO↑
CaCl
2Fused salt and high-silica diaspore ore carbon containing slag directly mix, aluminum chloride is at a low price produced in the chlorination of carbon reduction electric heating process, and the electric heating process chlorination furnace is taked the type of heating of industrial silicon, calcium carbide, electric heating process melting aluminum silicon alloy, adopts single-phase acyclic type, single-phase bipolar formula or the heating of three-phase three-pole ore-smelting furnace, CaCl
2The charge ratio of fused salt and high-silica diaspore ore carbon containing slag is as the criterion with the atomic molar ratio of Cl and Al at 1: 1, reductive agent C and CaCl
2Mol ratio be 2: 1 and Al
4O
4The mol ratio of C is 3: 1, with SiO
2Mol ratio be 2: 1,1600～2000 ℃ of melting bed temperature are controlled in electric heating process heating, upper strata chlorination gasification section temperature keeps more than 1600 ℃, elemental silicon generation of middle lower floor and CaC
2Melting section temperature keeps 1800 ℃～2000 ℃.Produce in low price aluminum chloride and carbide of calcium melting and the incorporate metallurgical process of elemental silicon melting in the electric heating chlorination, easily gasification evaporable AlCl carries CO and leaves reaction zone on the one hand, reduce the dividing potential drop of CO gas, the carrying out that helps reduction reaction also can reduce the temperature of reaction, CaCl on the other hand
2When finishing chlorination reaction, to CaC
2It catalysis and booster action, CaCl with the generation of elemental silicon
2Under temperature gasification condition more than 1600 ℃, CaC
2The generation approach mainly be the calcium steam and the generation of the carbon effect under high temperature CaC that produces behind the AlCl
2, this generation approach is thermopositive reaction, generates each mole CaC
2Emit the heat of 60.6KJ, under 2000～2100 ℃ of high temperature, generate one mole of CaC with CaO and C
2The heat that absorbs 4656KJ is compared, and power consumption and temperature of reaction reduce greatly, CaC
2Extremely strong reductibility is at high temperature arranged, and easily reduction-oxidation silicon generates elemental silicon, and a large amount of elemental silicons are mixed into CaC
2In, reduced CaC
2Fusing point is easy to deslagging.The principal reaction of each section can be expressed as:
Al
4O
4C+2CaCl
2+7C→4AlCl+2CaC
2+4CO
Al
4O
4C+2CaCl
2+3SiC→4AlCl+2Ca+3Si+4CO
SiO
2+CaC
2→Ca+Si+2CO
Ca+2C→CaC
2
Carbon reduction electric heating process chlorination output is the mixed gas of primary product with AlCl and CO, absorbs AlCl with the KCl high-temperature molten salt of recycle and separates with coal gas, and the coal gas of purification is as synthetic gas or fuel gas-steam generating, and KCl fused salt top temperature rises to 1300 ℃; Cooling KCl absorbs melt, and low price aluminum chloride once fork is separated, and the KCl fused salt is isolated crude aluminum liquid and AlCl
3The condensation solid; Adopt aluminum chloride fork solution at a low price, with the impure solid AlCl of condensation
3, purify being warming up to crude aluminum liquid reaction more than 800 ℃ with removing dust under the hot conditions more than 800 ℃ through distillation, be converted into purified AlCl gas again, fork is separated and is produced fine aluminium and AlCl under cryogenic vacuum degree 1KPa condition then
3For solving the superfluous problem of commodity industry aluminum chloride, adopt divergent solution direct H when AlCl secondary high-temperature gasification
2Reduction, superfine aluminium power is produced in condensation rapidly, progressively aluminium liquid casting ingot is produced in condensation.Its chemical reaction is:
AlCl
3 (gas)+ 2Al
(liquid)=3AlCl
(gas)
2AlCl
(gas)+ H
2 (gas)=2Al
(Gu or liquid)+ 2HCl
(gas)
Reclaim HCl gas and produce the hydrochloric acid recycle.
Adopt aluminum chloride fork solution at a low price, when AlCl secondary high-temperature gasification, the H that is purifying
2And O
2Flame on the AlCl oxydrolysis directly produce high-purity ultra-fine alumina, the gas-phase reaction condition is: gaseous state AlCl and H
2The mole proportioning be 1: 0.5～0.55 and O
2The mole proportioning be 1: 1.5～1.65,900～1250 ℃ of control reaction temperature are collected aluminum oxide through vapor phase process complete reaction postcooling, reclaim HCl gas and excessive O
2Its chemical reaction is:
2AlCl
(gas)+ H
2 (gas)+ 3/2O
(gas)=Al
2O
3 (Gu)+ 2HCl
(gas)
Adopt aluminum chloride fork solution at a low price, when AlCl secondary high-temperature gasification, with the NH that purifies
3Solid/liquid/gas reactions is directly produced high-purity ultra-fine aluminum nitride, under the gas-phase reaction condition is: gaseous state AlCl and NH
3The mole proportioning be 1: 1.05～1.15,1000～1300 ℃ of control reaction temperature are collected aluminium nitride through vapor phase process reaction postcooling.Its chemical reaction is:
AlCl
(gas)+ NH
3 (gas)=AlN
(Gu)+ HCl
(gas)+ H
2 (gas)
Produce in the process of low price aluminum chloride in the chlorination of carbon reduction electric heating process, the carbide of calcium melt that contains elemental silicon of discharge obtains calcium carbide, calcium carbide through broken, water decomposition system acetylene gas through cooling, the dissolving with hydrochloric acid that lime-ash makes with the HCl that reclaims, CaCl
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
Embodiment 1
The sillimanite of selecting the high-silica diaspore ore class for use is a raw material, adopt the granularity of sophisticated slag tap pressurization lurgi gasifier, mineral aggregate and coal can select 2～20mm, moisture in mineral aggregate and the coal does not hinder in operation, carry part fine coal and tar and mineral fine with industrial oxygen and go into the burner hearth melting layer through nozzle, under the pressure of 2.0～3.0MPa and hot conditions, fuse and coal gasification, mineral aggregate decomposes and the sintering fusing when making high heating value gas, purifies coal gas as synthetic gas or fuel gas-steam generating.
Sillimanite and coal and industrial oxygen slag tap pressurized gasification, the proportion of raw materials principle is as the C and the Al of reductive agent total amount
2O
3Mol ratio be 3: 1, with SiO
2Mol ratio be 2: 1, with contained H
2The mol ratio of O is 1: 1, and C and O act as a fuel
2Mol ratio be 2: 1, be pressure 2.0～3.0MPa with bunker coal and industrial oxygen control slag tap pressurized gasification condition, 1500～1900 ℃ of melt oxidation layer temperature.
CaCl
2Fused salt and sillimanite carbon containing slag directly mix, aluminum chloride is at a low price produced in the chlorination of carbon reduction electric heating process, and the electric heating process chlorination furnace is taked the type of heating of industrial silicon, calcium carbide, electric heating process melting aluminum silicon alloy, adopts single-phase acyclic type, single-phase bipolar formula or the heating of three-phase three-pole ore-smelting furnace, CaCl
2The charge ratio of fused salt and high-silica diaspore ore carbon containing slag is as the criterion with the atomic molar ratio of Cl and Al at 1: 1, reductive agent C and CaCl
2Mol ratio be 2: 1 and Al
4O
4The mol ratio of C is 3: 1, with SiO
2Mol ratio be 2: 1,1600～2000 ℃ of melting bed temperature are controlled in electric heating process heating, upper strata chlorination gasification section temperature keeps more than 1600 ℃, elemental silicon generation of middle lower floor and CaC
2Melting section temperature keeps 1800 ℃～2000 ℃.
Carbon reduction electric heating process chlorination output is the mixed gas of primary product with AlCl and CO, absorbs AlCl with the KCl high-temperature molten salt of recycle and separates with coal gas, and the coal gas of purification is as synthetic gas or fuel gas-steam generating, and KCl fused salt top temperature rises to 1300 ℃; Cooling KCl absorbs melt, and low price aluminum chloride once fork is separated, and the KCl fused salt is isolated crude aluminum liquid and AlCl
3The condensation solid; Adopt aluminum chloride fork solution at a low price, with the impure solid AlCl of condensation
3, purify being warming up to crude aluminum liquid reaction more than 800 ℃ with removing dust under the hot conditions more than 800 ℃ through distillation, be converted into purified AlCl gas again, fork is separated and is produced fine aluminium and AlCl under cryogenic vacuum degree 1KPa condition then
3For solving the superfluous problem of commodity industry aluminum chloride, adopt divergent solution direct H when AlCl secondary high-temperature gasification
2Reduction, superfine aluminium power is produced in condensation rapidly, progressively aluminium liquid casting ingot is produced in condensation.Reclaim HCl gas and produce the hydrochloric acid recycle.
Produce in the process of low price aluminum chloride in the chlorination of carbon reduction electric heating process, the carbide of calcium melt that contains elemental silicon of discharge obtains calcium carbide, calcium carbide through broken, water decomposition system acetylene gas through cooling, the dissolving with hydrochloric acid that lime-ash makes with the HCl that reclaims, CaCl
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
Embodiment two
Selecting coal gangue for use is raw material, adopt the granularity of sophisticated slag tap pressurization lurgi gasifier, mineral aggregate and coal can select 2～20mm, moisture in mineral aggregate and the coal does not hinder in operation, carry part fine coal and tar and mineral fine with industrial oxygen and go into the burner hearth melting layer through nozzle, under the pressure of 2.0～3.0MPa and hot conditions, fuse and coal gasification, mineral aggregate decomposes and the sintering fusing when making high heating value gas, purifies coal gas as synthetic gas or fuel gas-steam generating.
Coal gangue and coal and industrial oxygen slag tap pressurized gasification, the proportion of raw materials principle is as the C and the Al of reductive agent total amount
2O
3Mol ratio be 3: 1, with SiO
2Mol ratio be 2: 1, with contained H
2The mol ratio of O is 1: 1, and C and O act as a fuel
2Mol ratio be 2: 1, be pressure 2.0～3.0MPa with bunker coal and industrial oxygen control slag tap pressurized gasification condition, 1500～1900 ℃ of melt oxidation layer temperature.
CaCl
2Fused salt and coal gangue carbon containing slag directly mix, aluminum chloride is at a low price produced in the chlorination of carbon reduction electric heating process, and the electric heating process chlorination furnace is taked the type of heating of industrial silicon, calcium carbide, electric heating process melting aluminum silicon alloy, adopts single-phase acyclic type, single-phase bipolar formula or the heating of three-phase three-pole ore-smelting furnace, CaCl
2The charge ratio of fused salt and coal gangue carbon containing slag is as the criterion with the atomic molar ratio of Cl and Al at 1: 1, reductive agent C and CaCl
2Mol ratio be 2: 1 and Al
4O
4The mol ratio of C is 3: 1, with SiO
2Mol ratio be 2: 1,1600～2000 ℃ of melting bed temperature are controlled in electric heating process heating, upper strata chlorination gasification section temperature keeps more than 1600 ℃, elemental silicon generation of middle lower floor and CaC
2Melting section temperature keeps 1800 ℃～2000 ℃.
Carbon reduction electric heating process chlorination output is the mixed gas of primary product with AlCl and CO, absorbs AlCl with the KCl high-temperature molten salt of recycle and separates with coal gas, and the coal gas of purification is as synthetic gas or fuel gas-steam generating, and KCl fused salt top temperature rises to 1300 ℃; Cooling KCl absorbs melt, and low price aluminum chloride once fork is separated, and the KCl fused salt is isolated crude aluminum liquid and AlCl
3The condensation solid; Adopt aluminum chloride fork solution at a low price, with the impure solid AlCl of condensation
3, purify being warming up to crude aluminum liquid reaction more than 800 ℃ with removing dust under the hot conditions more than 800 ℃ through distillation, be converted into purified AlCl gas again, fork is separated and is produced fine aluminium and AlCl under cryogenic vacuum degree 1KPa condition then
3For solving the superfluous problem of commodity industry aluminum chloride, adopt the direct H2 reduction when AlCl secondary high-temperature gasification of divergent solution, superfine aluminium power is produced in condensation rapidly, progressively aluminium liquid casting ingot is produced in condensation.Reclaim HCl gas and produce the hydrochloric acid recycle.
Produce in the process of low price aluminum chloride in the chlorination of carbon reduction electric heating process, the carbide of calcium melt that contains elemental silicon of discharge obtains calcium carbide, calcium carbide through broken, water decomposition system acetylene gas through cooling, the dissolving with hydrochloric acid that lime-ash makes with the HCl that reclaims, CaCl
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
Claims (10)
1. the method for a mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that it comprises that coal gangue, high-silica diaspore ore pre-treatment and gasification are integrated, it is integrated that low price aluminum chloride and carbide of calcium melting and elemental silicon melting are produced in the chlorination of carbon reduction electric heating, coal and industrial oxygen and high-silica diaspore ore, coal gangue slag tap pressurized gasification, output is with CO and H
2Be main high heating value gas, purify coal gas as synthetic gas or fuel gas-steam generating, high-silica diaspore ore, coal gangue carbon containing slag and CaCl
2Fused salt batching, the chlorination of carbon reduction electric heating are produced aluminum chloride gasification product at a low price, absorb AlCl with the circulation of high temperature KCl fused salt and separate with coal gas, and cooling KCl absorption melt AlCl once fork separates and isolates crude aluminum liquid and AlCl
3, adopt low price aluminum chloride fork solution secondary fork to separate and extract fine aluminium and AlCl
3, direct H when AlCl secondary high-temperature gasification
2Superfine aluminium power (or aluminium liquid) is produced in reduction, the H that is purifying
2And O
2Flame on oxydrolysis directly produce high-purity ultra-fine alumina, with the NH that purifies
3High-purity ultra-fine aluminum nitride is directly produced in reaction, reclaims the HCl recycling, and the slag main component that the electric heating process chlorination is discharged is the carbide of calcium melt that contains elemental silicon, decomposes through water coolant and produces acetylene, and calcium carbide clinker is with reclaiming the dissolving with hydrochloric acid that HCl makes, CaCl
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
2. the method for mining metallurgy with coproduction of metal aluminium according to claim 1, silicon, acetylene and coal gas is characterized in that high-silica diaspore ore and coal and industrial oxygen slag tap pressurized gasification, and output is with CO and H
2The condition that is master's coal gas is: the batching of raw material high-silica diaspore ore and coal and oxygen, and as the C and the Al of reductive agent total amount
2O
3Mol ratio be 3: 1 and SiO
2Mol ratio be 2: 1, with contained H
2The mol ratio of O is 1: 1, and C and O act as a fuel
2Mol ratio be 2: 1, be 1500 °～1900 ℃ of pressure 2.0～3.0MPa, melt oxidation layer temperature with bunker coal and industrial oxygen control slag tap pressurized gasification condition.
3. according to the method for claim 1 or 2 mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that high-silica diaspore ore and coal and industrial oxygen slag tap pressurized gasification, output CO and H
2Be main coal gas, raw material comprises bauxite such as kaolin, clay, diaspore, boehmite, gibbsite, kyanite, andaluzite, sillimanite, coal gangue and contains Al
2O
3, SiO
2, CaO is the waste of main metal oxide.
4. the method for mining metallurgy with coproduction of metal aluminium according to claim 1 and 2, silicon, acetylene and coal gas is characterized in that CaCl
2Fused salt and high-silica diaspore ore carbon containing slag directly mix, and the condition that low price aluminum chloride is produced in the chlorination of carbon reduction electric heating is: CaCl
2The charge ratio of fused salt and high-silica diaspore ore carbon containing slag is as the criterion with the atomic molar ratio of Cl and Al at 1: 1, reductive agent C and CaCl
2Mol ratio is 2: 1, with Al
4O
4The mol ratio of C is 3: 1, with SiO
2Mol ratio be 2: 1,1600～2000 ℃ of melting bed temperature are controlled in electric heating process heating, chlorination gasification in upper strata is that main conversion zone temperature keeps more than 1600 ℃, middle lower floor elemental silicon generates and CaC
2Melting section temperature keeps 1800 ℃～2000 ℃.
5. according to the method for claim 1 or 2 or 4 described mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that carbon reduction electric heating process chlorination output is the mixed gas of primary product with AlCl and CO, KCl high-temperature molten salt absorption AlCl with recycle separates with coal gas, cooling KCl absorption melt low price aluminum chloride once fork is separated, and the KCl fused salt is isolated crude aluminum liquid and AlCl
3The condensation solid.
6. according to the method for claim 1 or 2 or 4 or 5 described mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that adopting aluminum chloride fork solution at a low price, AlCl
3Purify being warming up to crude aluminum liquid reaction more than 800 ℃ with removing dust under the high temperature more than 800 ℃ through distillation, be converted into purified AlCl gas again, the secondary fork is separated and is produced fine aluminium and AlCl under cryogenic vacuum degree 1KPa condition then
3Solid.
7. according to the method for claim 1 or 2 or 4 or 5 or 6 described mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that adopting divergent solution direct H when AlCl secondary high-temperature gasification
2Metal aluminium liquid or aluminium powder are produced in reduction, reclaim HCl gas and produce the hydrochloric acid recycle.
8. according to the method for claim 1 or 7 described mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that adopting divergent solution when AlCl secondary high-temperature gasification, the H that is purifying
2And O
2Flame on the AlCl oxydrolysis directly produce high-purity ultra-fine alumina, the gas-phase reaction condition is: gaseous state AlCl and H
2The mole proportioning be 1: 0.50～0.55, with O
2The mole proportioning be 1: 1.50～1.65,900～1250 ℃ of control reaction temperature.
9. according to the method for claim 1 or 7 described mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that adopting divergent solution when AlCl secondary high-temperature gasification, with the NH that purifies
3Solid/liquid/gas reactions is directly produced high-purity ultra-fine aluminum nitride, and the gas-phase reaction condition is: gaseous state AlCl and NH
3Mol ratio be 1: 1.50～1.15,1000～1300 ℃ of control reaction temperature.
10. according to the method for claim 1 or 2 or 4 described mining metallurgy with coproduction of metal aluminium, silicon, acetylene and coal gas, it is characterized in that the chlorination of carbon reduction electric heating produces at a low price in the aluminum chloride process, the carbide of calcium melt that contains elemental silicon of discharging, produce acetylene gas through the water coolant decomposition, calcium carbide clinker is with reclaiming the dissolving with hydrochloric acid that HCl makes, CaCl
2Recycling utilization obtains the industrial silicon through pickling impurity removal simultaneously.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234726A (en) * | 2010-05-07 | 2011-11-09 | 赖成章 | High-purity aluminum smelting method using intermediate frequency furnace |
| CN103992820A (en) * | 2014-05-16 | 2014-08-20 | 新奥科技发展有限公司 | Comprehensive utilization method of coal gangue |
| CN106241845A (en) * | 2016-08-29 | 2016-12-21 | 何顺爱 | A kind of novel ultrapure ball-aluminium oxide powder preparation method |
| CN113955757A (en) * | 2021-11-26 | 2022-01-21 | 内蒙古禹源机械有限公司 | Device and process for preparing carbon dioxide capture agent and co-producing hydrogen and alloy from carbon and gasified slag |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304613C (en) * | 2005-10-18 | 2007-03-14 | 昆明理工大学 | Vacuum carbon heat reduction aluminium smelting method |
-
2008
- 2008-03-24 CN CN2008100844353A patent/CN101255503B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234726A (en) * | 2010-05-07 | 2011-11-09 | 赖成章 | High-purity aluminum smelting method using intermediate frequency furnace |
| CN103992820A (en) * | 2014-05-16 | 2014-08-20 | 新奥科技发展有限公司 | Comprehensive utilization method of coal gangue |
| CN106241845A (en) * | 2016-08-29 | 2016-12-21 | 何顺爱 | A kind of novel ultrapure ball-aluminium oxide powder preparation method |
| CN106241845B (en) * | 2016-08-29 | 2017-12-22 | 何顺爱 | A kind of ultrapure ball-aluminium oxide powder preparation method |
| CN113955757A (en) * | 2021-11-26 | 2022-01-21 | 内蒙古禹源机械有限公司 | Device and process for preparing carbon dioxide capture agent and co-producing hydrogen and alloy from carbon and gasified slag |
| CN113955757B (en) * | 2021-11-26 | 2023-11-03 | 内蒙古禹源机械有限公司 | Device and process for preparing carbon dioxide capturing agent from gasified slag and combining hydrogen and alloy |
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