CN104388694A - Environment-friendly method for smelting high quality anode plate from low-grade copper by adopting low-cost equipment - Google Patents
Environment-friendly method for smelting high quality anode plate from low-grade copper by adopting low-cost equipment Download PDFInfo
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- CN104388694A CN104388694A CN201410603658.1A CN201410603658A CN104388694A CN 104388694 A CN104388694 A CN 104388694A CN 201410603658 A CN201410603658 A CN 201410603658A CN 104388694 A CN104388694 A CN 104388694A
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Abstract
The invention relates to an environment-friendly method for smelting a high quality anode plate from low-grade copper by adopting low-cost equipment and belongs to the technical field of copper processing. The best level of dust in smoke discharged to the air when scrap copper is smelted by the existing independent oxidation reduction furnace and a smoke treatment system thereof reaches up to 30mg/m<3>, but 80-95% of the dust is PM2.5 fine particles, and the dust contains dioxin with higher toxicity, thereby being unmatched with the change of the increasingly strict fine particle concentration requirement of people. The environment-friendly method for smelting the high quality anode plate from low-grade copper by adopting the low-cost equipment has the advantages that the low-grade copper raw material is possible to be used for smelting the high-quality anode plate by adopting the low-cost equipment, concentration of the dust in industrial waste gas discharged when the low-grade copper raw material is used for continuously smelting the high-quality anode plate by adopting the low-cost equipment is lower than 0.500mg/m<3> by virtue of a comprehensive smoke treatment system composed of a cyclone quenching dust collector, a smoke temperature regulator, a bag-type dust collector, a wet desulphurization and denitrification tower, a raining filter, a variable frequency fan and a sewage flocculation sedimentation tank and an integrated technology, and no dioxin is detected.
Description
Background technology
On the one hand, though heavy metal smelting smoke dust controlling exhaust pollution is through effort extremely hard and bitter in a large number, achieve significant progress, copper reverberatory furnace is smelted dust concentration in discharge flue dust and is reached 30mg/m
3, be better than GB907-1996 regulation Copper making reverberatory furnace dust lower than 200mg/m
3standard value.But existing result of study shows to reach 30mg/m in dust concentration
3flue dust in 80 ~ 95% be PM2.5 fine particle.
On the other hand, since nearly two more than ten years, Copper fabrication in China every year with double-digit speed increment, Copper fabrication product plays an increasingly important role in Chinese national economy and high-tech sector, but the bottleneck of restriction China Copper fabrication industry development is the raw-material shortage of high-purity copper, China's copper ore concentrates natural resources shortage, from copper scap, recycled copper, the copper material of regenerating high purity is inevitable selection, but enter the unavoidable mixed flame retardant etc. containing plastics, brominated aromatic hydrocarbons in the copper scap of stove, recycled copper, therefore smelt copper scap, recycled copper can produce dioxin.The generation of dioxin will be propagated by the catalysis ， dioxin containing metal ion fine particles such as Cu and is attached on PM2.5 fine particle.Up to the present, yet there are no the research and development of the emission-reduction technology of copper reverberatory furnace smelting smoke dust Zhong dioxin.
Well-known PM2.5 directly enters deep lung, produces important harm to human life health.About PM2.5, national standard " ambient air quality " GB3095-2012 particulate matter (particle diameter is less than or equal to 2.5 μm) specifies 24 hour average concentration 35 μ g/m
3for one-level, 75 μ g/m
3for secondary, standard came into effect from January 1st, 2016.But the situation is tense for the existing Air quality of China, higher than 75 μ g/m
3the weather of slight pollution, intermediate pollution, serious pollution, severe contamination happens occasionally.Dioxin is highly toxic substance, larger to the harm of human body.Therefore, relative to the optimum level of existing low-grade copper reverberatory furnace smelting smoke dust process, to the low-grade copper raw material containing recycled copper, one of copper scap adopt low cost equipment smelting technology, further research and development significantly reduce PM2.5 discharge in flue dust concentration, significantly cut down dioxin concentration simultaneously and even eliminate the method that dioxin produces, there is great social benefit.
Smelt the higher positive plate of purity for minimizing electrolysis process cost and time, energy-saving and emission-reduction have active effect.
Summary of the invention
The object of the invention is to adopt reverberatory furnace to add the airborne release dust content 30mg/m of flue dust treatment system optimum for prior art
3but wherein 80 ~ 95% are PM2.5 fine particle and melt the present situation containing there is dioxin in copper scap low-grade copper raw material flue dust, invent a kind of method to make to adopt low cost equipment to smelt high-quality positive plate and become possibility, and in the waste gas significantly cutting down discharge fine particle concentration, eliminate dioxin.
A kind of low-grade copper of the present invention smelts the environment protection method of high-quality positive plate low cost equipment, and low cost equipment comprises a shaft furnace, at least two oxidized stills, at least two reduction furnaces, a set of flue dust total systems, and technical characteristic of the present invention is:
Copper content 60wt% and above low-grade copper raw material can be normal and melting continuously becomes copper content to be greater than 99.10wt% high-quality positive plate, and low-grade copper raw material is at least one of following raw materials according: recycled copper, copper scap, the secondary blister copper smelted by copper scap, the blister copper smelted by copper matte regulus; Pass through at least two reserved row's copper mouths between shaft furnace and oxidized still and add a cover thermal insulation chute to be connected, shaft furnace continuous melting low-grade copper, at least two oxidized stills accept the copper melt of shaft furnace in turn to its rated capacity, respectively cupric oxide liquation; Again by cupric oxide liquation by the reserved row's copper mouth of oxidized still with add a cover thermal insulation chute and be transported to reduction furnace, reduce in reduction furnace, be then incubated, be finally cast into high-quality positive plate;
Shaft furnace fusing low-grade copper, consider that reduction furnace flue dust enters the impact bottom shaft furnace, by the air of multiple shaft furnace burner and the adjustment of fuel quantity supply, realize the lapse of temperature from top to bottom of whole stock column, and only melt bottom stock column, the burner descending most row to be responsible for melting bottom stock column at shaft furnace forms cyclic high-temperature gas-flow, this cyclic high-temperature gas-flow is reductibility, bottom continuous fusing low-grade copper stock column, stock column is constantly descending, require to add dry low-grade copper packing material block according to low-grade copper furnace run at the top of shaft furnace, maintain whole stock column height substantially constant, and this cyclic high-temperature gas-flow sweeps along a low-grade copper liquation tiltedly descending journey, then turn back above copper melt stream, cyclic high-temperature gas-flow is left in the combustion gas that wherein part is turned back on the one hand, then along shaft furnace stock column up one section, and by shaft furnace utilidor, high temperature blower enters reduction furnace respectively, the burner that the amount that this part turns back combustion gas descends row to be responsible for melting bottom stock column most by shaft furnace supplements to cyclic high-temperature gas-flow, on the other hand after low-grade copper liquation and cyclic high-temperature gas jet separation by inertia through the path of the shortest high temperature the most smoothly, pass through the oxidized still arranging copper mouth, add a cover thermal insulation chute, enter preheating, add a cover thermal insulation chute to have reductibility combustion gas to work in coordination with, ensure the proper flow of low-grade copper liquation, this cyclic high-temperature gas-flow, this adds a cover the reductibility combustion gas 1120 ~ 1400 DEG C of thermal insulation chute, and controls two temperature respectively and increase along with the reduction of copper content in raw material, when by one of them row's copper mouth and add a cover copper melt that thermal insulation chute flows into an oxidized still reach the rated capacity of this oxidized still time, reduce the fuel of shaft furnace burner corresponding with this row's copper mouth and the supply of air, make the fusing bottom the cooling of this cyclic high-temperature gas-flow, time-out shaft furnace stock column, this row's copper mouth of shutoff, then carries out the oxidation of copper melt in this oxidized still, open the Pai Tongkou be connected with the oxidized still of another preheating that shaft furnace is reserved simultaneously, control the shaft furnace burner relative with this row's copper mouth and form another cyclic high-temperature gas-flow, restart bottom fusing shaft furnace stock column, by this row's copper mouth and communicate with it add a cover a thermal insulation chute oxidation fire grate copper melt backward, until reach the specified copper melt amount of this oxidized still, then suspend the fusing of shaft furnace low-grade copper stock column, in normal melting continuously process, the bottom of continuous melting low-grade copper raw material stock column like this, respectively at different oxidized still oxidation low-grade copper liquation, respectively at the reduction of different reduction furnaces, insulation casting high-quality positive plate, flameless combustion mode taked by oxidized still burner, reduction furnace burner,
The combustion gas controlling shaft furnace is reductibility, reduction furnace combustion gas is reductibility, the combustion gas of oxidized still is oxidisability, and shaft furnace flue dust enters reduction furnace respectively by its utilidor, high temperature blower; Reduction furnace flue dust enters bottom shaft furnace, partly and enters respectively by its utilidor, high temperature blower part the oxidized still matched with it; Oxidized still flue dust by its utilidor, enter flue dust main pipeline, flue dust total system after discharge; This flue dust main pipeline outside weld tracheae, good lagging material is housed outside tracheae, at least two kinds of tracheaes utilize the high-temperature smoke flow through in this flue dust main pipeline to divide nitrogen to heat to dry air, dry sky respectively, preheated air distributes to by control that shaft furnace burner is combustion-supporting, oxidized still burner is combustion-supporting, reduction furnace burner is combustion-supporting, flue dust thermoswitch uses as required, pre-hot nitrogen passes into the even spray apparatus of gas just in the reduction furnace of reduction process by security solenoid valve, evenly enter copper melt pond, accelerate the reduction of copper melt; Pass into the even spray apparatus of gas just in the oxidized still of oxidising process containing the dry empty oxygen rich gas of oxygen that divides by security solenoid valve, evenly enter copper melt pond, accelerate the oxidising process of low-grade copper liquation; Control shaft furnace gas blower, reduction furnace gas blower, flue dust total system frequency modulation blower fan stop shaft furnace flue dust, reduction furnace flue dust, oxidized still flue dust uncontrollable discharge and escape;
Flue dust total system is made up of whirlwind chilling fly-ash separator, flue dust thermoswitch, sack cleaner, wet desulphurization denitrating tower, the strainer that drenches with rain, frequency modulation blower fan, sewage flocculation settling tank;
Shaft furnace flue dust utilidor and the shaft furnace joint height bottom shaft furnace accounts for the half of whole shaft furnace height to 2/3rds, gap more than this joint, between shaft furnace inwall and the low-grade copper raw material added from top is less than the gap between the following shaft furnace inwall in this joint and shaft furnace stock column, escapes from shaft furnace top by stopping shaft furnace flue dust to the control of shaft furnace high temperature blower; Shaft furnace flue dust enters reduction furnace burner combustion certainly, part former shaft furnace flue dust enters oxidized still burner combustion and then enters the comprehensive total system of flue dust, the former shaft furnace flue dust of part also reenters shaft furnace with reduction furnace flue dust, reenter reduction furnace, reenters oxidized still etc., shaft furnace flue dust at least experiences higher than 850 DEG C, more than 6s in this process, wherein experiences more than 1120 DEG C more than temperature 4s;
The flue dust temperature when entering whirlwind chilling fly-ash separator controlling to discharge from oxidized still is 500 DEG C ~ 550 DEG C, on the one hand, the flue dust entrance bypass of this whirlwind chilling fly-ash separator enters the dry freezing air of high pressure, with flue dust abundant combination cooling rapidly, drive flue dust mixed gas high speed rotating simultaneously, in the moving process upwards of rotation limit, limit, flue dust mixed gas forces high speed heat-shift with the metallic conduit of logical water coolant in whirlwind chilling fly-ash separator again, by regulating temperature and the gas velocity of dry freezing air, regulate temperature and the flow velocity of the water coolant led in metallic conduit, make flue dust mixed gas in 0.2s, drop to 195 DEG C ~ 200 DEG C, on the other hand, particulate matter large in flue dust mixed gas under the influence of centrifugal force limit rotation limit enters the hopper of whirlwind chilling fly-ash separator downwards, is automatically cleared when large particulate matter reaches a certain amount of by viewing window, logical water-cooled tube pipeline outer wall in whirlwind chilling fly-ash separator keeps clean by low frequency acoustic wave soot blower, efficient high-speed and flue dust mixed gas heat-shift,
Subsequently, flue dust mixed gas enters flue dust thermoswitch, by detecting the temperature of flue dust mixed gas in advance, take dry freezing air, the preheating of flue dust main pipeline part dry air to regulate the temperature of flue dust mixed gas, make its before leaving sack cleaner temperature higher than the dew point of flue dust mixed gas;
The wet desulphurization denitrating tower that flue dust mixed gas is come in and gone out through the control flue dust mixed gas that tower surface is airtight, enter its strainer that drenches with rain of coming in and going out of airtight control, strainer flue dust mixed gas movement velocity of just having entered to drench with rain reduces more than at least 50% immediately, the strainer that drenches with rain spray raindrop amount is at least 200mm/h, speed speed before contact deluge device base plate of spray raindrop reaches 1.0m/s ~ 5.0m/s strainer that drenches with rain and is made up of multiple lattice, often between adjacent two lattice, most of area is separated by dividing plate, in the general orientation of flue dust mixed gas motion, the single lattice end is provided with filtering net, flue dust mixed gas enters next lattice through filtering net, the 180 ° of changes of flue dust mixed gas motion general orientation, motion like this, repeatedly change direction, flue dust mixed gas is at the processed at least 10min in strainer that drenches with rain, finally entered air by frequency modulation blower fan, flue dust mixed gas is in turbulent flow drenching with rain in strainer, adjacent two lattice have flue dust mixed gas switching fabric, ensure that the position of flue dust simulation model for mixing gases flows drenches with rain the position of the upper, middle and lower in single lattice of strainer relatively all the time in change, ensure that flue dust mixed gas is caught in the rain strainer even processing, filtering net has good filtering function to PM2.5, filtering net does not stop the fine particle having complete rain film strips to walk to retain, flue dust mixed gas is caught in the rain from high temperature, and strainer sprays low temperature very soon, reach capacity from drying humidity at once in the raindrop of disperse, and the fine particle cohesion be in the flue dust mixed gas under dew point is grown up, and the favourable net that is filtered retains, finally enter the dust of air lower than 0.500mg/m
3, could not dioxin be detected,
The rainwater of strainer of drenching with rain recycles, regular moisturizing, and regular sewage pumps into sewage flocculation settling tank, and the mud of collection could not detect dioxin, and mud is concentrated subsequently and carried out landfill;
The furnace slag granulating cooling of oxidized still, reduction furnace, ball milling and physical separation, wet processing, Metallurgical processing afterwards, reclaims valuable metal.
A kind of low-grade copper of the present invention smelts the environment protection method of high-quality positive plate low cost equipment, this flue dust total system being applied in except the dust treatment of smelting high-quality positive plate containing the upper low-grade copper raw material of low cost equipment except shaft furnace, smelting the dust treatment of high-quality positive plate except containing higher-grade copper raw material on the low cost equipment except shaft furnace, entering the dust of air lower than 0.500mg/m after process
3, can not dioxin be detected.
Compared with prior art, the present invention has following remarkable superiority:
1. pair low-grade copper, optimum airborne release level smelted by existing reverberatory furnace is 30mg/m
3, but patent of the present invention adopts the low cost smelting equipment containing flue dust total system, and flue dust airborne release dust concentration is lower than 0.500mg/m
3; To low-grade copper, the existing invention technology containing shaft furnace can't be smelted in industry, therefore yet there are no in existing Copper making and reports the technology of dust disposal;
2. when containing copper scap, recycled copper in low-grade copper, because being easily mixed into the flame retardant etc. of plastics, brominated aromatic hydrocarbons, existing smelting and dust treatment technology produce dioxin certainly in flue dust, the technology of the present invention makes to be discharged into through flue dust total system of the present invention process the existence eliminating dioxin in the flue dust of air, can't detect dioxin, there is great social benefit.
Embodiment
Embodiment 1
The blister copper that the copper scap of raw copper content 60.0wt% and copper matte regulus are smelted, what low cost was equipped is configured to 1 shaft furnace, 2 oxidized stills, 2 reduction furnaces, 1 cover flue dust total systems, fuel oil heavy oil, the combustion gas controlling shaft furnace is reductibility, reduction furnace combustion gas is reductibility, the combustion gas of oxidized still is oxidisability, and shaft furnace flue dust enters reduction furnace respectively by its utilidor, high temperature blower, reduction furnace flue dust enters bottom shaft furnace, partly and enters respectively by its utilidor, high temperature blower part the oxidized still matched with it, oxidized still flue dust by its utilidor, enter flue dust main pipeline, flue dust total system after discharge, this flue dust main pipeline outside weld tracheae, good lagging material is housed outside tracheae, at least two kinds of tracheaes utilize the high-temperature smoke flow through in this flue dust main pipeline to divide nitrogen to heat to dry air, dry sky respectively, preheated air distributes to by control that shaft furnace burner is combustion-supporting, oxidized still burner is combustion-supporting, reduction furnace burner is combustion-supporting, flue dust thermoswitch uses as required, pre-hot nitrogen passes into the even spray apparatus of gas just in the reduction furnace of reduction process by security solenoid valve, evenly enter copper melt pond, accelerate the reduction of copper melt, pass into the even spray apparatus of gas just in the oxidized still of oxidising process containing the dry empty oxygen rich gas of oxygen that divides by security solenoid valve, evenly enter copper melt pond, accelerate the oxidising process of low-grade copper liquation, control shaft furnace gas blower, reduction furnace gas blower, flue dust total system frequency modulation blower fan stop shaft furnace flue dust, reduction furnace flue dust, oxidized still flue dust uncontrollable discharge and escape, shaft furnace fusing low-grade copper, consider that reduction furnace flue dust enters the impact bottom shaft furnace, by the air of multiple shaft furnace burner and the adjustment of fuel quantity supply, realize the lapse of temperature from top to bottom of whole stock column, and only melt bottom stock column, the burner descending most row to be responsible for melting bottom stock column at shaft furnace forms cyclic high-temperature gas-flow, this cyclic high-temperature gas-flow is reductibility, bottom continuous fusing low-grade copper stock column, stock column is constantly descending, require to add dry low-grade copper packing material block according to low-grade copper furnace run at the top of shaft furnace, maintain whole stock column height substantially constant, and this cyclic high-temperature gas-flow sweeps along a low-grade copper liquation tiltedly descending journey, then turn back above copper melt stream, cyclic high-temperature gas-flow is left in the combustion gas that wherein part is turned back on the one hand, then along shaft furnace stock column up one section, and by shaft furnace utilidor, high temperature blower enters reduction furnace respectively, the burner that the amount that this part turns back combustion gas descends row to be responsible for melting bottom stock column most by shaft furnace supplements to cyclic high-temperature gas-flow, on the other hand after low-grade copper liquation and cyclic high-temperature gas jet separation by inertia through the path of the shortest high temperature the most smoothly, pass through the oxidized still arranging copper mouth, add a cover thermal insulation chute, enter preheating, add a cover thermal insulation chute to have reductibility combustion gas to work in coordination with, ensure the proper flow of low-grade copper liquation, this cyclic high-temperature gas-flow, this adds a cover the reductibility combustion gas 1400 DEG C of thermal insulation chute, when by one of them row's copper mouth and add a cover copper melt that thermal insulation chute flows into an oxidized still reach the rated capacity of this oxidized still time, reduce the fuel of shaft furnace burner corresponding with this row's copper mouth and the supply of air, make the fusing bottom the cooling of this cyclic high-temperature gas-flow, time-out shaft furnace stock column, this row's copper mouth of shutoff, then carries out the oxidation of copper melt in this oxidized still, in normal melting continuously process, the bottom of continuous melting low-grade copper raw material stock column, respectively at different oxidized still oxidation low-grade copper liquation, respectively at the reduction of different reduction furnaces, insulation casting high-quality positive plate, flameless combustion mode taked by oxidized still burner, reduction furnace burner, flue dust total system is made up of whirlwind chilling fly-ash separator, flue dust thermoswitch, sack cleaner, wet desulphurization denitrating tower, the strainer that drenches with rain, frequency modulation blower fan, sewage flocculation settling tank, shaft furnace flue dust utilidor and the shaft furnace joint height bottom shaft furnace accounts for 60% of whole shaft furnace height, gap more than this joint, between shaft furnace inwall and the low-grade copper raw material added from top is less than the gap between the following shaft furnace inwall in this joint and shaft furnace stock column, escapes from shaft furnace top by stopping shaft furnace flue dust to the control of shaft furnace high temperature blower, shaft furnace flue dust enters reduction furnace burner combustion certainly, part former shaft furnace flue dust enters oxidized still burner combustion and then enters the comprehensive total system of flue dust, the former shaft furnace flue dust of part also reenters shaft furnace with reduction furnace flue dust, reenter reduction furnace, reenters oxidized still etc., shaft furnace flue dust at least experiences 855 DEG C, 6.5s in this process, wherein experiences more than 1130 DEG C more than temperature 4.3s, the flue dust temperature when entering whirlwind chilling fly-ash separator controlling to discharge from oxidized still is 500 DEG C, on the one hand, the flue dust entrance bypass of this whirlwind chilling fly-ash separator enters the dry freezing air of high pressure, with flue dust abundant combination cooling rapidly, drive flue dust mixed gas high speed rotating simultaneously, in the moving process upwards of rotation limit, limit, flue dust mixed gas forces high speed heat-shift with the metallic conduit of logical water coolant in whirlwind chilling fly-ash separator again, by regulating temperature and the gas velocity of dry freezing air, regulate temperature and the flow velocity of the water coolant led in metallic conduit, make flue dust mixed gas in 0.2s, drop to 195 DEG C, on the other hand, particulate matter large in flue dust mixed gas under the influence of centrifugal force limit rotation limit enters the hopper of whirlwind chilling fly-ash separator downwards, is automatically cleared when large particulate matter reaches a certain amount of by viewing window, logical water-cooled tube pipeline outer wall in whirlwind chilling fly-ash separator keeps clean by low frequency acoustic wave soot blower, efficient high-speed and flue dust mixed gas heat-shift, subsequently, flue dust mixed gas enters flue dust thermoswitch, by detecting the temperature of flue dust mixed gas in advance, take dry freezing air, the preheating of flue dust main pipeline part dry air to regulate the temperature of flue dust mixed gas, make its before leaving sack cleaner temperature higher than the dew point of flue dust mixed gas, the wet desulphurization denitrating tower that flue dust mixed gas is come in and gone out through the control flue dust mixed gas that tower surface is airtight, enter its strainer that drenches with rain of coming in and going out of airtight control, strainer flue dust mixed gas movement velocity of just having entered to drench with rain reduces at least 55% immediately, the strainer that drenches with rain spray raindrop amount is at least 200mm/h, and speed speed before contact deluge device base plate of spray raindrop reaches 1.0m/s, the strainer that drenches with rain is made up of multiple lattice, often between adjacent two lattice, most of area is separated by dividing plate, filtering net is provided with in the general orientation of flue dust mixed gas motion, the single lattice end, flue dust mixed gas enters next lattice through filtering net, the 180 ° of changes of flue dust mixed gas motion general orientation, motion like this, repeatedly change direction, flue dust mixed gas, at the processed 10min in strainer that drenches with rain, is finally entered air by frequency modulation blower fan, flue dust mixed gas is in turbulent flow drenching with rain in strainer, adjacent two lattice have flue dust mixed gas switching fabric, ensure that the position of flue dust simulation model for mixing gases flows drenches with rain the position of the upper, middle and lower in single lattice of strainer relatively all the time in change, ensure that flue dust mixed gas is caught in the rain strainer even processing, filtering net has good filtering function to PM2.5, filtering net does not stop the fine particle having complete rain film strips to walk to retain, flue dust mixed gas is caught in the rain from high temperature, and strainer sprays low temperature very soon, reach capacity from drying humidity at once in the raindrop of disperse, and the fine particle cohesion be in the flue dust mixed gas under dew point is grown up, and the favourable net that is filtered retains, the rainwater of strainer of drenching with rain recycles, regular moisturizing, and regular sewage pumps into sewage flocculation settling tank, and the mud of collection could not detect dioxin, and mud is concentrated subsequently and carried out landfill, the furnace slag granulating cooling of oxidized still, reduction furnace, ball milling and physical separation, wet processing, Metallurgical processing afterwards, reclaims valuable metal, the emission concentration of sulfide and nitride is same as the prior art, low cost equipment normally can smelt high-quality positive plate, average copper content 99.15wt%, finally enter the dust of air lower than 0.495mg/m
3, could not dioxin be detected.
Comparative example 1
To the blister copper that copper scap and the copper matte regulus of raw copper content 60.0wt% are smelted, take prior art to adopt reverberatory furnace and existing dust treatment system, dust airborne release concentration is 30mg/m
3， dioxin PCDFs toxic equivalent is at 0.200ng/g ~ 3.250ng/g.And take prior art to contain the low cost equipment of shaft furnace and existing dust treatment technology, because prior art cannot melting continuously low-grade copper raw material, all also do not have related data.
Embodiment 2
Raw material is the secondary blister copper that Cu content 72.8wt% copper scap and copper scap are smelted, fuel is Sweet natural gas, dry oxygen rich gas connects even spray apparatus top blast containing oxygen 85%, and the reductibility combustion gas of cyclic high-temperature gas-flow temperature 1360 DEG C, thermal insulation chute is at 1250 DEG C, shaft furnace flue dust utilidor and the shaft furnace joint height bottom shaft furnace accounts for 55% of whole shaft furnace height, gap more than this joint, between shaft furnace inwall and the low-grade copper raw material added from top is less than the gap between the following shaft furnace inwall in this joint and shaft furnace stock column, stops shaft furnace flue dust escape from shaft furnace top by the control of shaft furnace high temperature blower, shaft furnace flue dust enters reduction furnace certainly, oxidized still burner combustion enters flue dust total system, the former shaft furnace flue dust of part reenters shaft furnace etc. with the Some gases of reduction furnace, shaft furnace flue dust experiences 851 DEG C, 6.5s in this process, wherein experiences more than 1140 DEG C temperature 4.8s, the flue dust temperature when entering whirlwind chilling fly-ash separator controlling to discharge from oxidized still is 550 DEG C, on the one hand, the flue dust entrance bypass of this whirlwind chilling fly-ash separator enters the dry freezing air of high pressure, with flue dust abundant combination cooling rapidly, drive flue dust mixed gas high speed rotating simultaneously, in the moving process upwards of rotation limit, limit, flue dust mixed gas forces high speed heat-shift with the metallic conduit of logical water coolant in whirlwind chilling fly-ash separator again, by regulating temperature and the gas velocity of dry freezing air, regulate temperature and the flow velocity of the water coolant led in metallic conduit, make flue dust mixed gas in 0.18s, drop to 200 DEG C, subsequently, flue dust mixed gas enters flue dust thermoswitch, by detecting the temperature of flue dust mixed gas in advance, take dry freezing air, the preheating of flue dust main pipeline part dry air to regulate the temperature of flue dust mixed gas, make its before leaving sack cleaner temperature higher than the dew point 180 DEG C of flue dust mixed gas, the wet desulphurization denitrating tower that flue dust mixed gas is come in and gone out through the control flue dust mixed gas that tower surface is airtight, enter its strainer that drenches with rain of coming in and going out of airtight control, strainer flue dust mixed gas movement velocity of just having entered to drench with rain reduces at least 78% immediately, the strainer that drenches with rain spray raindrop amount is 230mm/h, and speed speed before contact deluge device base plate of spray raindrop reaches 5.0m/s, the strainer that drenches with rain is made up of multiple lattice, often between adjacent two lattice, most of area is separated by dividing plate, filtering net is provided with in the general orientation of flue dust mixed gas motion, the single lattice end, flue dust mixed gas enters next lattice through filtering net, the 180 ° of changes of flue dust mixed gas motion general orientation, motion like this, repeatedly change direction, flue dust mixed gas, at the processed 12min in strainer that drenches with rain, is finally entered air by frequency modulation blower fan, flue dust mixed gas is in turbulent flow drenching with rain in strainer, adjacent two lattice have flue dust mixed gas switching fabric, ensure that the position of flue dust simulation model for mixing gases flows drenches with rain the position of the upper, middle and lower in single lattice of strainer relatively all the time in change, ensure that flue dust mixed gas is caught in the rain strainer even processing, filtering net has good filtering function to PM2.5, filtering net does not stop the fine particle having complete rain film strips to walk to retain, flue dust mixed gas is caught in the rain from high temperature, and strainer sprays low temperature very soon, reach capacity from drying humidity at once in the raindrop of disperse, and the fine particle cohesion be in the flue dust mixed gas under dew point is grown up, and the favourable net that is filtered retains, other is identical with embodiment 1, above-mentioned low cost equipment normally can smelt positive plate, average copper content 99.20wt%, finally enters the dust of air lower than 0.479mg/m
3, could not dioxin be detected.
Embodiment 3
Raw material is the secondary blister copper that Cu content 88.3wt% copper scap and copper scap are smelted, fuel is Sweet natural gas, dry oxygen rich gas connects even spray apparatus top blast and side-blown containing oxygen 75%, and the reductibility combustion gas of cyclic high-temperature gas-flow temperature 1340 DEG C, thermal insulation chute is at 1240 DEG C, shaft furnace flue dust experiences 857 DEG C, 6.3s in this process, wherein experiences more than 1130 DEG C temperature 4.1s, the flue dust temperature when entering whirlwind chilling fly-ash separator controlling to discharge from oxidized still is 530 DEG C, on the one hand, the flue dust entrance bypass of this whirlwind chilling fly-ash separator enters the dry freezing air of high pressure, with flue dust abundant combination cooling rapidly, drive flue dust mixed gas high speed rotating simultaneously, in the moving process upwards of rotation limit, limit, flue dust mixed gas forces high speed heat-shift with the metallic conduit of logical water coolant in whirlwind chilling fly-ash separator again, by regulating temperature and the gas velocity of dry freezing air, regulate temperature and the flow velocity of the water coolant led in metallic conduit, make flue dust mixed gas in 0.17s, drop to 200 DEG C, subsequently, flue dust mixed gas enters flue dust thermoswitch, by detecting the temperature of flue dust mixed gas in advance, take dry freezing air, the preheating of flue dust main pipeline part dry air to regulate the temperature of flue dust mixed gas, make its before leaving sack cleaner temperature higher than the dew point 180 DEG C of flue dust mixed gas, the wet desulphurization denitrating tower that flue dust mixed gas is come in and gone out through the control flue dust mixed gas that tower surface is airtight, enter its strainer that drenches with rain of coming in and going out of airtight control, strainer flue dust mixed gas movement velocity of just having entered to drench with rain reduces at least 90% immediately, the strainer that drenches with rain spray raindrop amount is 240mm/h, and speed speed before contact deluge device base plate of spray raindrop reaches 5.0m/s, the strainer that drenches with rain is made up of multiple lattice, often between adjacent two lattice, most of area is separated by dividing plate, filtering net is provided with in the general orientation of flue dust mixed gas motion, the single lattice end, flue dust mixed gas enters next lattice through filtering net, the 180 ° of changes of flue dust mixed gas motion general orientation, motion like this, repeatedly change direction, flue dust mixed gas, at the processed 11min in strainer that drenches with rain, is finally entered air by frequency modulation blower fan, flue dust mixed gas is in turbulent flow drenching with rain in strainer, adjacent two lattice have flue dust mixed gas switching fabric, ensure that the position of flue dust simulation model for mixing gases flows drenches with rain the position of the upper, middle and lower in single lattice of strainer relatively all the time in change, ensure that flue dust mixed gas is caught in the rain strainer even processing, filtering net has good filtering function to PM2.5, filtering net does not stop the fine particle having complete rain film strips to walk to retain, flue dust mixed gas is caught in the rain from high temperature, and strainer sprays low temperature very soon, reach capacity from drying humidity at once in the raindrop of disperse, and the fine particle cohesion be in the flue dust mixed gas under dew point is grown up, and the favourable net that is filtered retains, other is identical with embodiment 1, above-mentioned low cost equipment normally can smelt positive plate, average copper content 99.26wt%, finally enters the dust of air lower than 0.481mg/m
3, could not dioxin be detected.
Embodiment 4
Low-grade copper starting material are containing Cu85wt%, and containing copper scap, take without shaft furnace, only have oxidized still, reduction furnace adds flue dust total system of the present invention smelting, it is 0.480mg/m3 that flue dust enters dust concentration in air, can't detect dioxin; The purity of positive plate is close, but does not have technological method of the present invention not only environmental protection but also energy-conservation.
Embodiment 5
Higher-grade copper starting material are containing Cu98wt%, and take to only have oxidized still containing copper scap, reduction furnace adds flue dust total system of the present invention and smelt, it is 0.475mg/m3 that flue dust enters dust concentration in air, can't detect dioxin; The purity of positive plate is close, but does not have technological method of the present invention not only environmental protection but also energy-conservation.
Claims (2)
1. low-grade copper smelts an environment protection method for high-quality positive plate low cost equipment, and low cost equipment comprises a shaft furnace, at least two oxidized stills, at least two reduction furnaces, a set of flue dust total systems, it is characterized in that:
1) copper content 60wt% and above low-grade copper raw material can be normal and melting continuously becomes copper content to be greater than 99.10wt% high-quality positive plate, and low-grade copper raw material is at least one of following raw materials according: recycled copper, copper scap, the secondary blister copper smelted by copper scap, the blister copper smelted by copper matte regulus; Pass through at least two reserved row's copper mouths between shaft furnace and oxidized still and add a cover thermal insulation chute to be connected, shaft furnace continuous melting low-grade copper, at least two oxidized stills accept the copper melt of shaft furnace in turn to its rated capacity, respectively cupric oxide liquation; Again by cupric oxide liquation by the reserved row's copper mouth of oxidized still with add a cover thermal insulation chute and be transported to reduction furnace, reduce in reduction furnace, be then incubated, be finally cast into high-quality positive plate;
2) shaft furnace fusing low-grade copper, consider that reduction furnace flue dust enters the impact bottom shaft furnace, by the air of multiple shaft furnace burner and the adjustment of fuel quantity supply, realize the lapse of temperature from top to bottom of whole stock column, and only melt bottom stock column, the burner descending most row to be responsible for melting bottom stock column at shaft furnace forms cyclic high-temperature gas-flow, this cyclic high-temperature gas-flow is reductibility, bottom continuous fusing low-grade copper stock column, stock column is constantly descending, require to add dry low-grade copper packing material block according to low-grade copper furnace run at the top of shaft furnace, maintain whole stock column height substantially constant, and this cyclic high-temperature gas-flow sweeps along a low-grade copper liquation tiltedly descending journey, then turn back above copper melt stream, cyclic high-temperature gas-flow is left in the combustion gas that wherein part is turned back on the one hand, then along shaft furnace stock column up one section, and by shaft furnace utilidor, high temperature blower enters reduction furnace respectively, the burner that the amount that this part turns back combustion gas descends row to be responsible for melting bottom stock column most by shaft furnace supplements to cyclic high-temperature gas-flow, on the other hand after low-grade copper liquation and cyclic high-temperature gas jet separation by inertia through the path of the shortest high temperature the most smoothly, pass through the oxidized still arranging copper mouth, add a cover thermal insulation chute, enter preheating, add a cover thermal insulation chute to have reductibility combustion gas to work in coordination with, ensure the proper flow of low-grade copper liquation, this cyclic high-temperature gas-flow, this adds a cover the reductibility combustion gas 1120 ~ 1400 DEG C of thermal insulation chute, and controls two temperature respectively and increase along with the reduction of copper content in raw material, when by one of them row's copper mouth and add a cover copper melt that thermal insulation chute flows into an oxidized still reach the rated capacity of this oxidized still time, reduce the fuel of shaft furnace burner corresponding with this row's copper mouth and the supply of air, make the fusing bottom the cooling of this cyclic high-temperature gas-flow, time-out shaft furnace stock column, this row's copper mouth of shutoff, then carries out the oxidation of copper melt in this oxidized still, open the Pai Tongkou be connected with the oxidized still of another preheating that shaft furnace is reserved simultaneously, control the shaft furnace burner relative with this row's copper mouth and form another cyclic high-temperature gas-flow, restart bottom fusing shaft furnace stock column, by this row's copper mouth and communicate with it add a cover a thermal insulation chute oxidation fire grate copper melt backward, until reach the specified copper melt amount of this oxidized still, then suspend the fusing of shaft furnace low-grade copper stock column, in normal melting continuously process, the bottom of continuous melting low-grade copper raw material stock column like this, respectively at different oxidized still oxidation low-grade copper liquation, respectively at the reduction of different reduction furnaces, insulation casting high-quality positive plate, flameless combustion mode taked by oxidized still burner, reduction furnace burner,
3) combustion gas controlling shaft furnace is reductibility, reduction furnace combustion gas is reductibility, the combustion gas of oxidized still is oxidisability, and shaft furnace flue dust enters reduction furnace respectively by its utilidor, high temperature blower; Reduction furnace flue dust enters bottom shaft furnace, partly and enters respectively by its utilidor, high temperature blower part the oxidized still matched with it; Oxidized still flue dust by its utilidor, enter flue dust main pipeline, flue dust total system after discharge; This flue dust main pipeline outside weld tracheae, good lagging material is housed outside tracheae, at least two kinds of tracheaes utilize the high-temperature smoke flow through in this flue dust main pipeline to divide nitrogen to heat to dry air, dry sky respectively, preheated air distributes to by control that shaft furnace burner is combustion-supporting, oxidized still burner is combustion-supporting, reduction furnace burner is combustion-supporting, flue dust thermoswitch uses as required, pre-hot nitrogen passes into the even spray apparatus of gas just in the reduction furnace of reduction process by security solenoid valve, evenly enter copper melt pond, accelerate the reduction of copper melt; Pass into the even spray apparatus of gas just in the oxidized still of oxidising process containing the dry empty oxygen rich gas of oxygen that divides by security solenoid valve, evenly enter copper melt pond, accelerate the oxidising process of low-grade copper liquation; Control shaft furnace gas blower, reduction furnace gas blower, flue dust total system frequency modulation blower fan stop shaft furnace flue dust, reduction furnace flue dust, oxidized still flue dust uncontrollable discharge and escape;
4) flue dust total system is made up of whirlwind chilling fly-ash separator, flue dust thermoswitch, sack cleaner, wet desulphurization denitrating tower, the strainer that drenches with rain, frequency modulation blower fan, sewage flocculation settling tank;
5) shaft furnace flue dust utilidor and the shaft furnace joint height bottom shaft furnace accounts for the half of whole shaft furnace height to 2/3rds, gap more than this joint, between shaft furnace inwall and the low-grade copper raw material added from top is less than the gap between the following shaft furnace inwall in this joint and shaft furnace stock column, escapes from shaft furnace top by stopping shaft furnace flue dust to the control of shaft furnace high temperature blower; Shaft furnace flue dust enters reduction furnace burner combustion certainly, part former shaft furnace flue dust enters oxidized still burner combustion and then enters the comprehensive total system of flue dust, the former shaft furnace flue dust of part also reenters shaft furnace with reduction furnace flue dust, reenter reduction furnace, reenters oxidized still etc., shaft furnace flue dust at least experiences higher than 850 DEG C, more than 6s in this process, wherein experiences more than 1120 DEG C more than temperature 4s;
6) the flue dust temperature when entering whirlwind chilling fly-ash separator controlling to discharge from oxidized still is 500 DEG C ~ 550 DEG C, on the one hand, the flue dust entrance bypass of this whirlwind chilling fly-ash separator enters the dry freezing air of high pressure, with flue dust abundant combination cooling rapidly, drive flue dust mixed gas high speed rotating simultaneously, in the moving process upwards of rotation limit, limit, flue dust mixed gas forces high speed heat-shift with the metallic conduit of logical water coolant in whirlwind chilling fly-ash separator again, by regulating temperature and the gas velocity of dry freezing air, regulate temperature and the flow velocity of the water coolant led in metallic conduit, make flue dust mixed gas in 0.2s, drop to 195 DEG C ~ 200 DEG C, on the other hand, particulate matter large in flue dust mixed gas under the influence of centrifugal force limit rotation limit enters the hopper of whirlwind chilling fly-ash separator downwards, is automatically cleared when large particulate matter reaches a certain amount of by viewing window, logical water-cooled tube pipeline outer wall in whirlwind chilling fly-ash separator keeps clean by low frequency acoustic wave soot blower, efficient high-speed and flue dust mixed gas heat-shift,
7) subsequently, flue dust mixed gas enters flue dust thermoswitch, by detecting the temperature of flue dust mixed gas in advance, take dry freezing air, the preheating of flue dust main pipeline part dry air to regulate the temperature of flue dust mixed gas, make its before leaving sack cleaner temperature higher than the dew point of flue dust mixed gas;
8) the wet desulphurization denitrating tower of the control flue dust mixed gas discrepancy that flue dust mixed gas is airtight through tower surface, enter its strainer that drenches with rain of coming in and going out of airtight control, strainer flue dust mixed gas movement velocity of just having entered to drench with rain reduces more than at least 50% immediately, the strainer that drenches with rain spray raindrop amount is at least 200mm/h, and speed speed before contact deluge device base plate of spray raindrop reaches 1.0m/s ~ 5.0m/s; The strainer that drenches with rain is made up of multiple lattice, often between adjacent two lattice, most of area is separated by dividing plate, filtering net is provided with in the general orientation of flue dust mixed gas motion, the single lattice end, flue dust mixed gas enters next lattice through filtering net, the 180 ° of changes of flue dust mixed gas motion general orientation, motion like this, repeatedly change direction, flue dust mixed gas, at the processed at least 10min in strainer that drenches with rain, is finally entered air by frequency modulation blower fan; Flue dust mixed gas is in turbulent flow drenching with rain in strainer, adjacent two lattice have flue dust mixed gas switching fabric, ensure that the position of flue dust simulation model for mixing gases flows drenches with rain the position of the upper, middle and lower in single lattice of strainer relatively all the time in change, ensure that flue dust mixed gas is caught in the rain strainer even processing; Filtering net has good filtering function to PM2.5, filtering net does not stop the fine particle having complete rain film strips to walk to retain; Flue dust mixed gas is caught in the rain from high temperature, and strainer sprays low temperature very soon, reach capacity from drying humidity at once in the raindrop of disperse, and the fine particle cohesion be in the flue dust mixed gas under dew point is grown up, and the favourable net that is filtered retains; Finally enter the dust of air lower than 0.500mg/m
3, could not dioxin be detected;
9) rainwater of strainer of drenching with rain recycles, regular moisturizing, and regular sewage pumps into sewage flocculation settling tank, and the mud of collection could not detect dioxin, and mud is concentrated subsequently and carried out landfill;
10) the furnace slag granulating cooling of oxidized still, reduction furnace, ball milling and physical separation, wet processing, Metallurgical processing afterwards, reclaims valuable metal.
2. a kind of low-grade copper according to claim 1 smelts the environment protection method of high-quality positive plate low cost equipment, it is characterized in that this flue dust total system being applied in except the dust treatment of smelting high-quality positive plate containing the upper low-grade copper raw material of low cost equipment except shaft furnace, smelting the dust treatment of high-quality positive plate except containing higher-grade copper raw material on the low cost equipment except shaft furnace, entering the dust of air lower than 0.500mg/m after process
3, can not dioxin be detected.
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