Background technology
The reductor of steel-making has multiple, and commonly used have aluminium, ferrosilicon and an Alsimin.Wherein, big (the about 4.0g/cm of the density of Alsimin
3), in molten steel, be difficult for come-up, long duration of contact with molten steel, aluminium is difficult for scaling loss, can improve the deoxidation effect of aluminium, is the reductor of pleased use of present steel mill.The production of Alsimin has two kinds of methods, promptly mixes method and electric heating process.The method of mixing is that fine aluminium and ferrosilicon melting are by a certain percentage formed, and shortcoming is that aluminium and ferrosilicon all are the high energy consumption products, and silicon and aluminium all have certain scaling loss during melting, so production cost is higher.Electric heating process is produced the Alsimin raw material and is mainly contained kaolin, bauxitic clay, and iron filings and bituminous coal and other contain the mineral of aluminium, silicon.In the hot stove in ore deposit, directly go back the original production Alsimin, this method technology is complicated, and facility investment is bigger, but production cost is relatively low, is fit to large-scale commercial prodn.Alumina content is lower than silicon oxide in the kaolin, and aluminium content is higher than silicon in the ferrosilicoaluminum that electric heating process is produced usually, allocate bauxitic clay into; The cost of bauxitic clay is higher, and especially China's bauxite resource is limited, and adding in recent years, electrolytic aluminum project and aluminum oxide project constantly start; Demand to the bauxitic clay raw material is doubled and redoubled; By this tempo, do not need what years, China's bauxitic clay resource will face exhaustion.
Produce a large amount of aluminium lime-ash in the aluminium course of processing; The cindery processing of aluminium will be passed through secondary refining or mechanical means usually and extract metallic aluminium; After extracting aluminium, still remain a large amount of aluminium ashes, still contain the metallic aluminium of 15-30% in the remaining aluminium ash, be unworthy that because of grade is low further extracting aluminium discards.Only the area, Shanghai just produces more than 50,000 ton of aluminium scrap ash every year, and environmental protection has been proposed serious challenge.Its staple is metallic aluminium and aluminiferous compound; Wherein to be converted to aluminium sesquioxide be about 70% to aluminium content; Be in the bauxitic clay within the aluminium sesquioxide content range, the metallic aluminium that exists in the aluminium ash need not reduction, can directly get into Alsimin; Reduce the add-on of reductive agent, reduced production cost.Copper ashes is the sub product that copper is smelted, and one ton of copper of every production produces 2.2 tons copper ashes approximately, and China's copper output was about 4,000,000 tons in 2009, calculated with this, and China's copper ashes approximately reaches 8,800,000 tons.The copper ashes staple is iron and silicon-dioxide, and iron substitutes iron filings also can directly get into Alsimin, further reduced production cost, and silicon-dioxide can be reduced into Pure Silicon Metal, is the principal constituent of Alsimin.With aluminium ash and copper ashes is main raw material, produces Alsimin through the ratio of adjusting both, has overcome the limitation of single waste composition, and really having accomplished turns waste into wealth.
Literature search through to prior art finds that publication number is that the Chinese patent of CN1053450 discloses a kind of prescription and production technique thereof with the producing silica-alumina iron by use of ore-heating method alloy, and its prescription composition mainly contains bauxitic clay, red bauxite, silica, iron filings and bituminous coal etc.Adopt electric heating process production ferrosilicoaluminum to overcome tradition and mix the method long flow path, the deficiency that production cost is high, but this patent has adopted resource raw materials such as bauxitic clay, red bauxite, silica, and cost is higher.Also find in the retrieval; Publication number goes on foot also original production Alsimin for the CN1066687 Chinese patent discloses with the hot stove in ore deposit direct; In batching, adopt raw material to add again and be pressed into piece or ball through the broken thorough mixing of fine powder; Make to be reduced agent and closely to contact with reductive agent, the ore of selecting for use a gipsite and a diaspore to add kaolin isoreactivity aluminium sesquioxide is done raw material.But the main raw material(s) of this patent remains bauxite, and another feed kaolin also is the resource mineral.
Aspect the regenerated using of aluminium ash, publication number is that the Chinese patent of CN1088622 discloses the method for making duraluminum as the very low aluminium slag of the aluminium content of trade waste (the described aluminium ash of again) of utilizing.With the compound stalk forming thing of aluminium slag, block silica is main raw material, is reductive agent with the stone coal, in the hot stove in ore deposit, produces the Al-Si-Fe alloy.This patent is that aluminium slag regenerated resource development and utilization provides a thinking, but because the limitation of aluminium slag composition, this resource raw material of ground silica has still been used in the source of silicon; Reductive agent is used hard coal; Cost is higher, and the hard coal volatile matter is lower, the reduction reaction poor activity.Further find that also publication number is a kind of smelting reduction process of producing steel making deoxidant Al-Si-Fe alloy for the CN1328165 Chinese patent discloses in the retrieval.This method is that the aluminium slag with the aluminium that contains different content of different batches and aluminium sesquioxide is mixed into the metastable aluminium ground-slag of Chemical Composition; This aluminium ground-slag, ground silica, iron rust and carbon dust are processed block mixing moulding thing with useless heavy oil as tackiness agent; Again this mixing moulding thing is put into Reaktionsofen; Under 1400~1800 ℃ of temperature, carry out 1~2 hour fusion reduction reaction, thereby obtain AL-Si-Fe alloy.This patent has been used the wasted aluminium slag, but same limitation because of aluminium slag composition, this resource raw material of ground silica has still been used in the source of silicon, and reductive agent adopts carbon dust, and cost is very high, and the carbon dust volatile matter is lower, and reactive behavior is not high on the contrary.
Through retrieving existing patent and document, do not find that with aluminium ash and copper ashes composite wastes be the report of main material production Alsimin.
Summary of the invention
The present invention is in order to solve above-mentioned technical problem; A kind of method of utilizing aluminium ash and copper ashes composite wastes for the main material production Alsimin is disclosed; Make it overcome the limitation of independent a kind of solid waste composition; Both reduce the production cost of Alsimin, consumed the waste that causes environmental pollution easily again.
The method that the present invention utilizes aluminium ash and copper ashes to produce Alsimin may further comprise the steps:
(1) raw materials pretreatment:
A. aluminium ash granularity is less than 100 orders, said aluminium ash major ingredient weight percent: Al
2O
3Content 25~50wt%, Al content 15~30wt%, SiO
2Content 5~15wt%, MgO content 5~10wt%, TiO
2Content 1~3wt%, Fe
2O
3Content 2~6wt%, CaO content 2~6wt%; B. with the copper ashes ball milling to particle diameter less than 3mm, said copper ashes major ingredient weight percent: Cu content 0.2~0.7wt%, Fe content 20~40wt%, Fe
3O
4Content 1~5wt%, SiO
2Content 30~45wt%, Al
2O
3Content 1~5wt%, CaO content 5~10wt%, MgO content 1~3wt%; C. reductive agent adopts bituminous coal, with the bituminous coal ball milling to particle diameter less than 3mm, said bituminous coal major ingredient weight percent: fixed carbon content 55~65wt%, volatile content 26~32wt%, the ash content of coal<7wt%;
(2) batching and briquetting:
According to aluminium ash 30~45wt%: copper ashes 30~50wt%: the weight proportion raw material of bituminous coal 18~30wt%, and the spent pulping liquor of 15~22wt% that adds raw material weight is as wedding agent, mixed ball, and oven dry pellet;
(3) electric heating process prepares Alsimin:
Dried pellet is sent into the hot stove in ore deposit, under temperature 2000-2800 ℃ high temperature, smelt, every at a distance from 2 hours, adopt the graphite arc burner to open the once furnace eye, emit Alsimin, slagging-off back ingot casting is left standstill in oxygen blast deliming in 10 minutes.
Wherein, the temperature in the step (3) is preferably 2000-2200 ℃.
Further, the spent pulping liquor that the wedding agent in the said step (2) adopts the paper mill to produce wherein contains active substance sulfonated lignin content >=55%.
Described pellet is dried moisture content less than 2%.
Compared with prior art; The present invention utilizes aluminium ash and copper ashes composite wastes as main raw material; Overcome the limitation of independent a kind of solid waste composition; Reductive agent adopts the higher and cheap bituminous coal of reactive behavior, through rational proportion, adopts electric heating process production to be used for the Alsimin of steel making deoxidant.Employing aluminium ash and copper ashes are that the major ingredient weight percent of the Alsimin of main material production is: aluminium content 35~50%, silicone content 15~35%, iron 25~40%, Ti<1%.
Embodiment
Elaborate in the face of embodiments of the invention down: present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
The method of utilizing aluminium ash and copper ashes to produce Alsimin may further comprise the steps.
(1) raw materials pretreatment:
The main raw material composition is:
Aluminium ash major ingredient weight percent: Al
2O
3Content 25~50wt%, Al content 15~30wt%, SiO
2Content 5~15wt%, MgO content 5~10wt%, TiO
2Content 1~3wt%, Fe
2O
3Content 2~6wt%, CaO content 2~6wt%.Aluminium ash granularity need not ball milling less than 100 orders.
Copper ashes major ingredient weight percent: Cu content 0.2~0.7wt%, Fe content 20~40wt%, Fe
3O
4Content 1~5wt%, SiO
2Content 30~45wt%, Al
2O
3Content 1~5wt%, CaO content 5~10wt%, MgO content 1~3wt%.With the copper ashes ball milling to particle diameter less than 3mm.
Reductive agent adopts bituminous coal, major ingredient weight percent: fixed carbon content 55~65wt%, volatile content 26~32wt%, the ash content of coal<7wt%.The bituminous coal ball milling is arrived less than 3mm.
(2) batching and briquetting:
Prepare burden according to weight percent: aluminium ash 30~45wt%, copper ashes 30~50wt% and bituminous coal 18~30wt%.15~22wt% according to raw material weight adds spent pulping liquor as wedding agent, and mixed ball is dried moisture content less than 2%.
The spent pulping liquor that said spent pulping liquor adopts the paper mill to produce contains active substance sulfonated lignin content >=55%.
(3) electric heating process prepares Alsimin:
Dried pellet is sent into the hot stove in ore deposit, smelt down at temperature 2000-2800 ℃, every at a distance from 2 hours, adopt the graphite arc burner to open the once furnace eye, emit Alsimin, slagging-off back ingot casting is left standstill in oxygen blast deliming in 10 minutes.
Embodiment 2
Aluminium ash major ingredient weight percent: Al
2O
3Content 35.65%, Al content 25.60%, SiO
2Content 10.52%, MgO content 7.82%, TiO
2Content 2.31%, Fe
2O
3Content 1.68%, CaO content 3.78%.Copper ashes major ingredient weight percent: Cu content 0.46%, Fe content 35.2%, Fe
3O
4Content 4.06%, SiO
2Content 39.2%, Al
2O
3Content 3.2%, CaO content 6.8%, MgO content 1.3% is worn into granularity less than 3mm with it.
Preferred bituminous coal is worn into granularity less than 3mm with it, the major ingredient weight percent: fixed carbon content 59.6%, volatile content 29.3%, the ash content of coal 6.71%.
Aluminium ash 40%, copper ashes 35% and bituminous coal 25% batching by weight percentage add 18% spent pulping liquor of raw material weight, mix system ball, drying.Put into the hot stove in ore deposit of 6300KVA after dried pellet and rice hull carbon are mixed together, electric arc furnace voltage 120V smelts under the high temperature of 2000 ℃ of temperature.Every at a distance from 2 hours, adopt the graphite arc burner to open the stove eye, emit Alsimin, slagging-off back ingot casting is left standstill in oxygen blast deliming in 10 minutes.
The principal element weight percent is in the Alsimin of producing: aluminium content 43.28%, silicone content 18.06%, iron level 35.13%, titanium content 0.88%.
Embodiment 3
Aluminium ash major ingredient weight percent: Al
2O
3Content 35.65%, Al content 25.60%, SiO
2Content 10.52%, MgO content 7.82%, TiO
2Content 2.31%, Fe
2O
3Content 1.68%, CaO content 3.78%.Copper ashes major ingredient weight percent: Cu content 0.46%, Fe content 35.2%, Fe
3O
4Content 4.06%, SiO
2Content 39.2%, Al
2O
3Content 3.2%, CaO content 6.8%, MgO content 1.3% is worn into granularity less than 3mm with it.
Preferred bituminous coal is worn into granularity less than 3mm with it, the major ingredient weight percent: fixed carbon content 59.6%, volatile content 29.3%, the ash content of coal 6.71%.
Aluminium ash 37%, copper ashes 40% and bituminous coal 23% batching by weight percentage add 19% spent pulping liquor of raw material weight, mix system ball, drying.Put into the hot stove in ore deposit of 6300KVA after dried pellet and rice hull carbon are mixed together, electric arc furnace voltage 120V smelts under the high temperature of 2200 ℃ of temperature.Every at a distance from 2 hours, adopt the graphite arc burner to open the stove eye, emit Alsimin, slagging-off back ingot casting is left standstill in oxygen blast deliming in 10 minutes.
The principal element weight percent is in the Alsimin of producing: aluminium content 41.06%, silicone content 20.08%, iron level 36.31%, titanium content 0.67%.
Embodiment 4
Aluminium ash major ingredient weight percent: Al
2O
3Content 35.65%, Al content 25.60%, SiO
2Content 10.52%, MgO content 7.82%, TiO
2Content 2.31%, Fe
2O
3Content 1.68%, CaO content 3.78%.Copper ashes major ingredient weight percent: Cu content 0.46%, Fe content 38.2%, Fe
3O
4Content 4.06%, SiO
2Content 39.2%, Al
2O
3Content 3.2%, CaO content 6.8%, MgO content 1.3% is worn into granularity less than 3mm with it.
Preferred bituminous coal is worn into granularity less than 3mm with it, the major ingredient weight percent: fixed carbon content 59.6%, volatile content 29.3%, the ash content of coal 6.71%.
Aluminium ash 34%, coal gangue 45% and bituminous coal 21% batching by weight percentage add 20% spent pulping liquor of raw material weight, mix system ball, drying.Put into the hot stove in ore deposit of 6300KVA after dried pellet and rice hull carbon are mixed together, electric arc furnace voltage 120V smelts under the high temperature of 2100 ℃ of temperature.Every at a distance from 2 hours, adopt the graphite arc burner to open the stove eye, emit Alsimin, slagging-off back ingot casting is left standstill in oxygen blast deliming in 10 minutes.
The principal element weight percent is in the Alsimin of producing: aluminium content 39.65%, silicone content 20.67%, iron level 36.81%, titanium content 0.61%.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; The present invention also has various changes and modifications under the prerequisite that does not break away from spirit and scope of the invention, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.