CN101928832A - Method for treating copper-nickel containing solid waste - Google Patents
Method for treating copper-nickel containing solid waste Download PDFInfo
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- CN101928832A CN101928832A CN201010177570XA CN201010177570A CN101928832A CN 101928832 A CN101928832 A CN 101928832A CN 201010177570X A CN201010177570X A CN 201010177570XA CN 201010177570 A CN201010177570 A CN 201010177570A CN 101928832 A CN101928832 A CN 101928832A
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Abstract
The invention relates to a method for treating copper-nickel containing filter mud generated through the waste water treatment of printed-circuit board production enterprises, belonging to the field of non-ferrous metal production realized by treating non-ore raw materials. The method comprises the following steps of: pretreating the filter mud into charging materials, and then adding quartz/limestone and carbon; carrying out reduction smelting treatment at 1150-1250 DEG C; and then respectively treating obtained liquid materials, waste gases and waste residues. The invention greatly improves the problem of environmental pollution caused by cupolette production and has wide raw material adaptation range; the granularity of the filter mud ranges from 0.1mm to 100mm, and the water content thereof is 75-80 percent; and in addition, a detection result shows that the invention has good separation effect of non-ferrous metals and impurities and high recovery rate of the non-ferrous metals.
Description
Technical field
The invention belongs to and handle non-ore starting material, be specifically related to the method for the filter mud that a kind of wastewater treatment of handling printed circuit board manufacturing enterprise produces to produce non-ferrous metal or its compound field.
Background technology
High speed development along with Chinese national economy, non-ferrous metals industry develop into China's electric power, traffic, building, electronic information, the development of relevant industries such as national defense industry and new high-tech industry provides to be supported and greatly promotes, China has become the world today and has mainly contained non-ferrous metal country of consumption, occupy important position in international non-ferrous metal market, but, China's non-ferrous metal raw material supply wretched insufficiency, this has become the bottleneck of China's Development of Non-Ferrous Metals Industry, and on the other hand, in the final filter mud that produces of the wastewater treatment of printed circuit board manufacturing enterprise, the cupric of its butt filter mud (nickel) amount is but up to about 10%, and ore grade such as copper reach 1% very high extraction value is just arranged, therefore, the wastewater treatment of printed circuit board manufacturing enterprise produces contains valency non-ferrous metal filter mud (cupric, nickeliferous mud) having high recycling is worth.But in fact very complicated because of the nickeliferous filter mud of the cupric of collecting source, component difference is very big, and metal content is lower, and existing treatment process all is limited to little soaring smelting furnace basically, and the shortcoming that little soaring smelting furnace exists has: the less (0.5m of stove hearth area
2About), there is not any dust arrester installation, furnace gas is directly discharged from furnace roof, yields poorly, the energy consumption height, the rate of recovery is low, and environmental pollution is big, and smelting furnace material is the higher-grade furnace charge substantially, and is comparatively single.Therefore, provide the method that solves little soaring smelting shortcoming imperative.
Summary of the invention
For overcoming the shortcoming and defect that above-mentioned prior art exists, the present invention aims to provide the method for the high nickeliferous solid waste of Treatment of Copper of a kind of environment-protection low-consumption rate of recovery.
The technical solution used in the present invention is:
The method of the nickeliferous solid waste of a kind of Treatment of Copper, described method in turn includes the following steps:
(1) with the copper-nickel containing solid waste pre-treatment for going into the stove furnace charge, described copper-nickel containing solid waste is handled the filter mud that produces from printed circuit board wastewater,
(2) go into the stove furnace charge and carry out the retailoring processing, process is: join carbon, flux, furnace charge in the reducing and smelting furnace successively, flux is quartzite and/or Wingdale, by weight furnace charge: quartzite: Wingdale=1:0.05-0.1:0.05-0.1 feeds intake, and the carbon incendiary is pressed 35-40m simultaneously
3/ m
2Minute speed blast air, be that 1150-1250 carries out retailoring 24 hours ℃ following every days continuously and handles in temperature, handle the furnace charge total amount 24 hours every days is 55 tons/m
2, obtain liquid material, slag and flue gas,
(3) the retailoring processing obtains the liquid material and obtains time blister copper, inferior thick nickel, matte or ice nickel through the cooling casting; Retailoring is handled the furnace slag granulating that obtains and is handled the back recovery; The flue gas emptying after exhaust treatment system is handled that produces is handled in retailoring.
As preferred version, according to the method for the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, its granularity of described filter mud is that 0.1mm-100mm and water content are 75-80%.The main chemical compositions of filter mud is inorganics classes such as metal species such as copper, nickel and quartz.The contriver discovers that method of the present invention is more suitable for handling the filter mud that possesses These characteristics.
As preferred version, method according to the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, described pre-treatment is: adopt boiling rotary drying method, process is for being thermal source fuel with carbon (carbon is that the fragmentation of aluminium anode scrap obtains in the aluminium industrial production), and filter mud is dry in boiling heating stove-rotary kiln drying device, and drying temperature is 800-900 ℃, reduce to about 25% to the water content of filter mud, deliver to again and be pressed into brick shape furnace charge in the brick press.Go into the specification of stove furnace charge and can make the furnace charge that specification is 240 * 115 * 53mm brick shape furnace charge or other specifications according to needs of production.
As preferred version, according to the method for the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, in the described retailoring: furnace charge moves from top to bottom, the reducing and smelting furnace bottom tuyeres is the melting area, furnace charge arrives the tuyere zone fusing, and air blasts through the air port, makes the carbon burning at tuyere zone, the high-temperature furnace gas that produces moves from bottom to top, with the furnace charge antikinesis, carry out heat exchange, furnace charge is heated gradually and finishes the retailoring process.
As preferred version, according to the method for the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, described reducing and smelting furnace adopts full water jacket structure.What the present invention adopted is smelting industry advanced person's jacket structure for water mode reducing and smelting furnace, and its water coolant drains into back pool from high-order water tower.Therefore, for the present invention, equipment does not have special requirement, easier realization industrialized production of the present invention.
As preferred version, method according to the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, described furnace charge arrives the tuyere zone fusing, furnace charge after the fusing handle to be realized separating of liquid material and slag through the cupola well sedimentation, and along with the continuous fusing of furnace charge, the furnace charge face constantly descends, constantly replenish furnace charge, make furnace charge and reducing and smelting furnace furnace roof maintenance level.Slag is made Water Quenching after the slag notch stage is emitted, shrend water is from the water tower cooling circulating water.The liquid material is emitted from the discharge port stage after cool off and be cast into piece ingot (through casting die), obtains time blister copper, inferior thick nickel, matte or ice nickel.The described furnace charge that constantly replenishes is: by per hour 4 batches be metered into furnace charge in reducing and smelting furnace, handle the furnace charge amount 24 hours every days is 55 tons/m
2
As preferred version, method according to the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, described flue gas is treated to through exhaust treatment system: flue gas is through heavy ash tube, sack cleaner combination treatment, remove the heavy metal in the flue gas, emptying behind induced draft fan, washing tower, thionizer and chimney again.Wherein, more preferably, desulfurization can adopt China Patent No. to carry out desulfurization for the limestone-gypsum method that ZL200510050693.6 provides, and desulfuration efficiency can reach more than 90%.
As preferred version, method according to the nickeliferous solid waste of Treatment of Copper of the present invention, wherein, through the flue dust that heavy ash tube, sack cleaner combination treatment are collected, its zinc oxide content is lower than 60% return and enter reducing and smelting furnace after brick press is made brick shape furnace charge; Its zinc oxide content is higher than 60% sell as product.Can realize the production cost optimization like this.
Characteristics at copper-nickel containing solid waste of the present invention: the final filter mud that produces of printed circuit board manufacturing enterprise wastewater treatment, its water content height and granularity are very thin, in order to guarantee the ventilation property of the temperature in the reducing and smelting furnace in the retailoring processing, increase furnace charge, improve furnace charge specific capacity (the unit surface unit time is handled the furnace charge amount), the present invention at first needs filter mud is done pre-treatment, at first adopt boiling rotary drying method that the filter mud water content is reduced significantly, and then filter mud sent into be pressed into brick shape in the brick press and go into the stove furnace charge.Adopt reduction method to carry out retailoring then to going into the stove furnace charge, described retailoring is to add carbon fuel in reducing and smelting furnace, its burning liberated heat makes the furnace charge fusing, form the carbon monoxide reducing atmosphere simultaneously, make the metal oxide reduction of copper or nickel, the liquid material that retailoring obtains (liquid copper or liquid nickel) obtains time blister copper through casting die (cooling of copper and mickel liquid metal is cast into the piece ingot), inferior thick nickel, matte or ice nickel, the slag that retailoring obtains is recycled through Water Quenching, and the flue gas that retailoring obtains is recycled through exhaust treatment system.The present invention mainly by adopting boiling heating stove-rotary kiln drying device-reducing and smelting furnace that cupric (nickel) mud is carried out harmless treatment, realizes the purpose of the high and low energy consumption of the non-ferrous metal rate of recovery, environmental protection.
The present invention compared with prior art has following having a few:
1, the present invention changes the little soaring smelting furnace production technology that original solid waste falls behind, and adopts boiling rotary method drying-environmental protection reduction furnace to carry out the harmless treatment process technology, greatly improved the problem of environmental pollution that small cupola production causes; 2, the solid waste open pile shines mode to adopt boiling-rotary method dry technology to change in the past, reduces pollutions such as airborne dust, improves regional environment; 3, boiling-rotary method dry technology solid waste drying temperature low (800-900 ℃) adapts to raw material range wide (the filter mud granularity is that 0.1mm-100mm and water content are 75-80%); 4, reducing and smelting furnace adopt rational formula (furnace charge: quartzite: Wingdale=1:0.05-0.1:0.05-0.1) (weight ratio), the slag type is reasonable, non-ferrous metal and impurity good separating effect; 5, non-ferrous metal rate of recovery height contains non-ferrous metal≤0.3%(weight percent in the slag); 6, adopt carbon fuel (calorific value 〉=9000kcal/kg), cut down the consumption of energy, burnt rate≤14%, industry optimal parameter.
Description of drawings
Fig. 1 is the process flow sheet of the nickeliferous solid waste method of Treatment of Copper of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
The explanation of major equipment and raw material:
The manufacturing of upright factory is revolved in boiling heating stove (KF-30 type) Nanjing;
(Φ 3m * 25m) manufacturing of upright factory is revolved in Nanjing to the rotary kiln drying device;
Desulphurization system Lixiang Science and Technology Co., Ltd., Hangzhou.
The filter mud that the filter mud of using among the embodiment produces from printed circuit board manufacturing enterprise wastewater treatment in Zhejiang Province and the peripheral provinces and cities scope.After testing, the main chemical composition content (%) of filter mud sees Table 1.
The chemical ingredients (%) that table 1 filter mud is main
| Composition | Cu（Ni） | Fe | Zn | SiO 2 | H 2O | Other |
| Content (%) | 3～5 | 1～2 | 1～3 | 5～6 | 75～80 | 5 |
Its specification of the carbon of using among the embodiment meets the chemical ingredients shown in the table 2 and forms.
Table 2 fuel carbon (aluminum electrolytic residual electrode) main chemical compositions (%)
| Title | Fixed carbon | S | Ash content | Other | Q With Low(Kcal/Kg) |
| Carbon | ≥95 | 0.5 | 3 | 1.5 | ≥9000 |
Embodiment 1
Production Flow Chart is referring to Fig. 1.It is the process operation pattern of producing median year greatly that present embodiment provides, the processing parameter that relates among all embodiment, those skilled in the art all can shown in make reasonable adjustment in the scope, thereby realize effective processing to copper-nickel containing solid waste.
In filter mud input boiling heating stove and rotary kiln drying device, in temperature is 800-900 ℃ of following 24 hours successive drying, detect in the drying process filter mud water content reduce to can drying is good below 25% filter mud deliver to by endless belt conveyor and be pressed into brick shape furnace charge in the brick press, this brick shape furnace charge is 240mm * 115mm * 53mm standard square specification, goes into the stove furnace charge as reducing and smelting furnace.The required thermal source of rotary kiln drying is from the carbon powder burning that produces in the reduction furnace melting carbon shattering process of the present invention.After dry the water content of solid waste is dropped to below 25% by 75～80%, the flue dust that produces in the rotary kiln is handled emptying then through sack cleaner and induced draft fan successively.
Carbon-flux-brick shape furnace charge joins in the reducing and smelting furnace in turn by skip hoist, and flux is quartzite and Wingdale, and each composition proportion scope is by weight: furnace charge: quartzite: Wingdale=1:0.05-0.1:0.05-0.1.Carbon burning liberated heat is enough to make the furnace charge fusing, forms certain reducing atmosphere simultaneously, and this reducing atmosphere is a carbon monoxide, and furnace charge moves from top to bottom, and the reducing and smelting furnace bottom tuyeres is the melting area, and furnace charge reaches the tuyere zone fusing.Air blasts through the air port, presses 35-40m
3/ m
2Minute speed blast air, make the carbon burning at tuyere zone, produce high temperature, high-temperature furnace gas moves from bottom to top, with the furnace charge antikinesis, carry out heat exchange, furnace charge is heated gradually and finishes various smelting processes, thereby obtain liquid copper or liquid nickel, slag, flue gas, smelted products such as flue dust, the retailoring temperature is 1150-1250 ℃ (process control of retailoring is regulated air quantity and carbon consumption according to temperature), continuous retailoring in 24 hours, the furnace charge of described reducing and smelting furnace tuyere zone melting is through the cupola well sedimentation, and slag separates with copper or nickel clarification, and slag is emitted shrend from the slag notch stage, shrend water is recirculated water tower cooler water, liquid copper of gained or liquid nickel are emitted through casting die from the discharge port stage and are obtained time blister copper, inferior thick nickel, matte or ice nickel, along with the continuous fusing of furnace charge, the furnace charge face constantly descends, constantly replenish furnace charge (by per hour 4 batches be metered into furnace charge in reducing and smelting furnace, handle the furnace charge total amount 24 hours every days and can reach 55 tons/m
2, make retailoring furnace roof and furnace charge keep the fixed horizontal plane of weighing apparatus.
Reducing and smelting furnace adopts full water jacket structure, and water coolant drains near the back pool of power house near the high-order water tower the power house.
The flue gas of discharging from the reducing and smelting furnace top enters exhaust treatment system, respectively after sinking ash tube, sack cleaner combination treatment, removing heavy metal flue dust wherein, after induced draft fan, washing tower, thionizer and chimney emptying.By heavy ash tube, the collected flue dust of sack cleaner, its zinc oxide content is lower than 60% return and enter reducing and smelting furnace after brick press is made brick shape furnace charge, and zinc oxide content is higher than 60% sell as product.
After testing, non-ferrous metal content is low in the slag, and the annual detected result sees Table 3.
Table 3
Slag can be sold to cement production enterprise or shipyard derusting by sandblast.
Claims (9)
1. the method for the nickeliferous solid waste of Treatment of Copper is characterized in that, described method in turn includes the following steps:
(1) with the copper-nickel containing solid waste pre-treatment for going into the stove furnace charge, described copper-nickel containing solid waste is handled the filter mud that produces from printed circuit board wastewater,
(2) go into the stove furnace charge and carry out the retailoring processing, process is: join carbon, flux, furnace charge in the reducing and smelting furnace successively, flux is quartzite and/or Wingdale, by weight furnace charge: quartzite: Wingdale=1:0.05-0.1:0.05-0.1 feeds intake, and the carbon incendiary is pressed 35-40m simultaneously
3/ m
2Minute speed blast air, be that 1150-1250 carries out retailoring 24 hours ℃ following every days continuously and handles in temperature, handling the furnace charge amount every day is 55 tons/m
2, obtain liquid material, slag and flue gas,
(3) the retailoring processing obtains the liquid material and obtains time blister copper, inferior thick nickel, matte or ice nickel through the cooling casting; Retailoring is handled the furnace slag granulating that obtains and is handled the back recovery; The flue gas emptying after exhaust treatment system is handled that produces is handled in retailoring.
2. the method for the nickeliferous solid waste of Treatment of Copper according to claim 1 is characterized in that, its granularity of described filter mud is that 0.1mm-100mm and water content are 75-80%.
3. the method for the nickeliferous solid waste of Treatment of Copper according to claim 1, it is characterized in that, described pre-treatment is: adopt boiling rotary drying method, process is for being thermal source fuel with the carbon, filter mud is dry in boiling heating stove-rotary kiln, drying temperature is 800-900 ℃, reduces to below 25% to the water content of filter mud, delivers to and is pressed into brick shape furnace charge in the brick press.
4. the method for the nickeliferous solid waste of Treatment of Copper according to claim 1, it is characterized in that, in the described retailoring: furnace charge moves from top to bottom, the reducing and smelting furnace bottom tuyeres is the melting area, and furnace charge arrives the tuyere zone fusing, and air blasts through the air port, make the carbon burning at tuyere zone, the high-temperature furnace gas that produces moves from bottom to top, and with the furnace charge antikinesis, furnace charge is heated gradually and finishes the retailoring process.
5. according to the method for claim 1 or the nickeliferous solid waste of 4 described Treatment of Copper, it is characterized in that described reducing and smelting furnace adopts full water jacket structure.
6. the method for the nickeliferous solid waste of Treatment of Copper according to claim 4, it is characterized in that, described furnace charge arrives the tuyere zone fusing, furnace charge after the fusing handle to be realized separating of liquid material and slag through the cupola well sedimentation, continuous fusing along with furnace charge, constantly replenish furnace charge, make furnace charge and reducing and smelting furnace furnace roof maintenance level.
7. the method for the nickeliferous solid waste of Treatment of Copper according to claim 6 is characterized in that, the described furnace charge that constantly replenishes is: by per hour 4 batches be metered into furnace charge in reducing and smelting furnace, handle the furnace charge amount 24 hours every days is 55 tons/m
2
8. the method for the nickeliferous solid waste of Treatment of Copper according to claim 1, it is characterized in that, described flue gas is treated to through exhaust treatment system: flue gas after heavy ash tube, sack cleaner combination treatment, emptying behind induced draft fan, washing tower, thionizer and chimney again.
9. the method for the nickeliferous solid waste of Treatment of Copper according to claim 8, it is characterized in that, through the flue dust that heavy ash tube, sack cleaner combination treatment are collected, its zinc oxide content is lower than 60% return and enter reducing and smelting furnace after brick press is made brick shape furnace charge; Its zinc oxide content is higher than 60% sell as product.
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| CNA2009101012791A CN101597691A (en) | 2009-07-27 | 2009-07-27 | The processing method of the nickeliferous solid waste of Treatment of Copper |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451448A (en) * | 2013-09-09 | 2013-12-18 | 梧州漓佳铜棒有限公司 | Ingredients for fire refining of scrap copper and smelting method |
| CN106834737A (en) * | 2016-12-29 | 2017-06-13 | 荆门市格林美新材料有限公司 | A kind of circuit board pyrolytic product briquetting and preparation method thereof |
| CN109811143A (en) * | 2019-01-08 | 2019-05-28 | 河套学院 | A kind of method of nickel sludge, rich scum, cullet and gypsum tailings cooperative disposal |
| CN111304450A (en) * | 2020-04-08 | 2020-06-19 | 中国恩菲工程技术有限公司 | Method and device for producing black copper from copper-containing sludge |
| CN113549772A (en) * | 2021-07-13 | 2021-10-26 | 中国瑞林工程技术股份有限公司 | Method for comprehensively recycling valuable metals from copper-containing waste materials |
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| CN101597691A (en) * | 2009-07-27 | 2009-12-09 | 富阳申能固废环保再生有限公司 | The processing method of the nickeliferous solid waste of Treatment of Copper |
| CN103372563A (en) * | 2012-04-20 | 2013-10-30 | 连云港荣鼎金属有限公司 | Waste treatment method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103451448A (en) * | 2013-09-09 | 2013-12-18 | 梧州漓佳铜棒有限公司 | Ingredients for fire refining of scrap copper and smelting method |
| CN103451448B (en) * | 2013-09-09 | 2014-08-27 | 钟文华 | Ingredients for fire refining of scrap copper and smelting method |
| CN106834737A (en) * | 2016-12-29 | 2017-06-13 | 荆门市格林美新材料有限公司 | A kind of circuit board pyrolytic product briquetting and preparation method thereof |
| CN109811143A (en) * | 2019-01-08 | 2019-05-28 | 河套学院 | A kind of method of nickel sludge, rich scum, cullet and gypsum tailings cooperative disposal |
| CN111304450A (en) * | 2020-04-08 | 2020-06-19 | 中国恩菲工程技术有限公司 | Method and device for producing black copper from copper-containing sludge |
| CN111304450B (en) * | 2020-04-08 | 2023-09-29 | 中国恩菲工程技术有限公司 | Method and device for producing black copper from copper-containing sludge |
| CN113549772A (en) * | 2021-07-13 | 2021-10-26 | 中国瑞林工程技术股份有限公司 | Method for comprehensively recycling valuable metals from copper-containing waste materials |
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Application publication date: 20101229 |