CN110306054A - A kind of recovery method of old circuit board valuable metal - Google Patents
A kind of recovery method of old circuit board valuable metal Download PDFInfo
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- CN110306054A CN110306054A CN201810230098.8A CN201810230098A CN110306054A CN 110306054 A CN110306054 A CN 110306054A CN 201810230098 A CN201810230098 A CN 201810230098A CN 110306054 A CN110306054 A CN 110306054A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/025—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper, or baths
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/003—Bath smelting or converting
- C22B15/0032—Bath smelting or converting in shaft furnaces, e.g. blast furnaces
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention discloses a kind of recovery method of old circuit board valuable metal, this method is achieved by the steps of: 1) carrying out detin processing to waste printed circuit board, obtain wiring board tabula rasa；2) above-mentioned wiring board tabula rasa is crushed, then successively carries out iron removal by magnetic separation, eddy current separation except aluminium, obtain iron charge, aluminium material and wiring board broken material respectively；3) pyrolysis processing is carried out to above-mentioned wiring board broken material, obtains cupric carbon dust；4) oxygen-enriched air smelting processing is carried out to above-mentioned thermal decomposition product cupric carbon dust, obtains blister copper phase, flue dust phase and slag phase；5) valuable metal in above-mentioned flue dust phase, blister copper phase and slag phase is further recycled, obtains zinc, lead, copper, gold, silver, palladium valuable metal；The present invention carries out low temperature pyrogenation to wiring board broken material and melting is handled, final recycling obtains valuable metal, effectively raises the rate of recovery of valuable metal in this way by first carrying out low temperature detin, broken, iron removal by magnetic separation, eddy current separation except aluminium to waste printed circuit board.
Description
Technical field
The invention belongs to the recovery technology fields of valuable metal, and in particular to a kind of recycling of old circuit board valuable metal
Method.
Background technique
With the fast development of electronics industry and information high-tech industry, the update of electronic product and service life are got over
Come shorter, a large amount of electronic product is abandoned, and a large amount of electron wastes are formd.In electron wastes especially wiring board
It, will be to ecological environment and people if dealt with improperly containing elements such as a large amount of poisonous and harmful substances such as heavy metal lead, mercury, cadmium, chromium
Class health, which is constituted, greatly to threaten；In addition, including always producing the discarded PCBs with import, just having more than 600,000 every year in China
The useless PCBs of ton needs to handle；And since the average life of electronic product reduces, this number is also being risen year by year；According to report
Road contains about 500 grams of metallic silvers, 50 grams of gold, 196 kilograms of copper, 20 kilograms of lead, 20 kilograms of nickel, 100 in 1 ton of discarded circuit board
Kilogram iron, 80 kilograms of aluminium etc.；Therefore, the valuable metal effectively in recycling waste printed circuit board is a critically important project.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of recovery method of old circuit board valuable metal, solution
The recovery rate of valuable metals determined in waste printed circuit board in the prior art is low, the halfway problem of recycling.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows: a kind of old circuit board valuable metal
Recovery method, this method are achieved by the steps of:
Step 1, detin processing is carried out to waste printed circuit board, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to the step 1 is crushed, then successively carries out iron removal by magnetic separation, eddy current point
Blanking aluminium obtains iron charge, aluminium material and wiring board broken material respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that the step 2 obtains, obtains thermal decomposition product cupric carbon dust；
Step 4, electroplating sludge, copper scap, lime stone, quartz, sodium bicarbonate, lump coal and the step 3 are obtained
Thermal decomposition product cupric carbon dust is simultaneously uniformly mixed, then mixed material is continuously added to oxygen-enriched side-blowing bath by measuring chute and belt and is melted
Melting processing is carried out in refining, obtains the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead and stanniferous respectively
The slag phase of lead and zinc；
Step 5, the method by the method for gravitational dust collection and bag-type dust, the method for electrolysis and wet separation is right respectively
The flue dust phase of Zn accumulation tin-lead, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc that the step 4 obtains
It is handled, obtains zinc, lead, copper, gold, silver, palladium valuable metal.
Preferably, in the step 1, the temperature of the detin processing is 180~230 DEG C.
Preferably, in the step 2, the partial size of the wiring board broken material is 0~2cm.
Preferably, in the step 3, the temperature when pyrolysis processing is 450~600 DEG C.
Preferably, in the step 3, the mass percentage of copper is 15~50% in the cupric carbon dust, the quality of carbon
Percentage composition is 10~15%, and gold, silver and palladium content are respectively 15-400g/t, 200-500g/t and 5-15g/t, tin, lead and zinc
Mass percent be respectively 2-3%, 1-2% and 2-3%.
Preferably, in the step 4, the electroplating sludge, copper scap, lime stone, quartz, sodium bicarbonate, lump coal, cupric
Carbon dust is weighed by mass percentage, wherein electroplating sludge 10~30%, copper scap 10~20%, lime stone 5~10%,
Quartzy 5~15%, sodium bicarbonate 1~5%, lump coal 5~15%, cupric carbon dust 20~50%.
Preferably, in the step 4, the calcium oxide content in the lime stone is greater than 50%；Silica in quartz
Content is greater than 85%；The calorific value of lump coal is greater than 25MJ/Kg, and volatile matter is less than 25%, and ash content is less than 15%.
Preferably, in the step 4, the temperature of the oxygen-enriched side-blowing bath melting is 1250~1350 DEG C.
Preferably, in the step 4, in the oxygen-enriched side-blowing bath fusion process, control slag phase in silica alumina ratio be 1.8~
2.8。
Preferably, in the step 4, the mass percent of the blister copper Xiang Zhongtong is 93~95%, 20~600g/t of gold,
Silver 300~800g/t, 5~50g/t of palladium；Tin 5~10% in the flue dust phase, the mass percent of lead are 5~10%, the matter of zinc
Measuring percentage is 10~20%；The mass percentage content of copper is lower than 0.6% in the slag phase, and the mass percentage content of tin is low
In 0.1%.
Compared with prior art, the present invention is by first carrying out low temperature detin, broken, iron removal by magnetic separation, whirlpool electricity to waste printed circuit board
Flow point blanking aluminium carries out low temperature pyrogenation to wiring board broken material, then carries out oxygen-enriched air smelting processing to thermal decomposition product cupric carbon dust, most
Recycling obtains valuable metal eventually, effectively raises the rate of recovery of valuable metal in this way, and at low cost；Process of the present invention is simple,
It is easy to operate, it is worth of widely use.
Detailed description of the invention
Fig. 1 is a kind of process flow chart of the recovery method of old circuit board valuable metal of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
A kind of recovery method of old circuit board valuable metal provided by the invention, this method are achieved by the steps of:
Step 1, detin processing is carried out to waste printed circuit board at 180~230 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium and dissipates
Backing；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 450~600 DEG C, obtains cupric
Mass percentage is 15~50%, the mass percentage of carbon is 10~15%, gold content, silver content and palladium content are respectively
15-400g/t, 200-500g/t and 5-15g/t, tin, lead and zinc mass percent be respectively 2-3%, 1-2% and 2-3%
Thermal decomposition product cupric carbon dust；
Step 4, following components is weighed respectively by mass percentage: electroplating sludge 10~30%, copper scap 10~20%, stone
The thermal decomposition product that lime stone 5~10%, quartz 5~15%, sodium bicarbonate 1~5%, lump coal 5~15%, the step 3 obtain contains
Copper carbon dust 20~50% is simultaneously uniformly mixed, then mixed material is continuously added to oxygen-enriched side-blowing bath melting by measuring chute and belt
In (select oxygen-enriched side-blowing bath melting that there are following features herein, 1, preferable to adaptability to raw material, 20~90% grades can be handled
Raw material；2, environmental protection condition is good；3, heat and mass is good；4, fuel economy is high；5, flexible operation can work continuously also all
The operation of phase property；Oxygen-rich concentration rises to 70-80%, and traditional blast furnace process sample concentration is no more than 30%, therefore
The rate of driving of oxygen-enriched side-blowing bath melting will be big it is more, efficiency wants high more), the progress melting processing at 1250~1350 DEG C
(during being somebody's turn to do, silica alumina ratio is 1.8~2.8 in slag phase), obtains blister copper phase, enrichment zinc-tin and the lead of enriching Cu gold and silver and palladium respectively
Flue dust phase and slag phase containing tin-lead and zinc；Wherein, the mass percent of blister copper Xiang Zhongtong is 93~95%, gold 20~
600g/t, silver 300~800g/t, 5~50g/t of palladium；Tin 5~10% in flue dust phase, the mass percent of lead are 5~10%, zinc
Mass percent be 10~20%；The mass percentage content of copper is lower than 0.6% in slag phase；The mass percentage content of tin is low
In 0.1%.
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
State the flue dust phase of Zn accumulation tin-lead, the blister copper phase of enriching Cu gold and silver and palladium and slag phase containing tin-lead and zinc of step 4 acquisition into
Row processing, obtains zinc, lead, copper, gold, silver, palladium valuable metal.
The present invention is by first carrying out low temperature detin, broken, iron removal by magnetic separation, eddy current separation except aluminium, to line to waste printed circuit board
Road plate broken material carries out low temperature pyrogenation, then carries out oxygen-enriched air smelting processing to thermal decomposition product cupric carbon dust, and final recycling obtains valuable
Metal effectively raises the rate of recovery of valuable metal in this way, and at low cost；Process of the present invention is simple, easy to operate, is worth pushing away
It is wide to use.
Embodiment 1
Step 1, detin processing is carried out to waste printed circuit board at 200 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 500 DEG C, obtains the quality hundred of cupric
Point content is 20%, the mass percentage of carbon is 12%, gold, silver and palladium content be respectively 20g/t, 300g/t and 5g/t, tin,
The mass percent of lead and zinc is respectively 2%, 1% and 2% cupric carbon dust；
Step 4, weigh following components respectively by mass percentage: electroplating sludge 20%, copper scap 15%, lime stone 8%,
Quartz 10%, sodium bicarbonate 3%, lump coal 10%, step 3 obtain thermal decomposition product cupric carbon dust 34% and be uniformly mixed, then will
Mixed material is continuously added in oxygen-enriched side-blowing bath melting by measuring chute and belt, and melting processing is carried out at 1300 DEG C (should
In the process, silica alumina ratio is 1.8~1.9 in slag phase), the blister copper phase of enriching Cu gold and silver and palladium, enrichment zinc-tin and lead are obtained respectively
Flue dust phase and slag phase containing tin-lead and zinc；Wherein, in blister copper phase cupric mass percent be 94%, gold content 30g/t,
Silver content is 400g/t, palladium content 7g/t；Stanniferous mass percent is 8% in flue dust phase, and the mass percent of lead is
7%, the mass percent of zinc is 15%；The mass percentage content of copper is 0.4% in slag phase, and the mass percentage content of tin is
0.08%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Embodiment 2
Step 1, detin processing is carried out to waste printed circuit board at 180 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 450 DEG C, obtains the quality hundred of cupric
Point content is 15%, the mass percentage of carbon is 10%, gold content, silver content and palladium content be respectively 50g/t, 350g/t and
5g/t, tin, lead and zinc mass percent be respectively 2.1%, 1.3% and 2.2% thermal decomposition product cupric carbon dust；
Step 4, weigh following components respectively by mass percentage: electroplating sludge 10%, copper scap 20%, lime stone 5%,
Quartz 15%, sodium bicarbonate 1%, lump coal 5%, the step 3 obtain thermal decomposition product cupric carbon dust 44% and be uniformly mixed, then
Mixed material is continuously added in oxygen-enriched side-blowing bath melting, melting processing is carried out at 1250 DEG C (under this condition, silicon in slag phase
Aluminium ratio is 2.1~2.3), the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead are obtained respectively and contain tin-lead
With the slag phase of zinc；Wherein, in blister copper phase cupric mass percent be 93%, gold content 87g/t, silver content 612g/t,
Palladium content is 8.7g/t；Stanniferous mass percent is 5% in flue dust phase, and the mass percent of lead is 5%, the quality percentage of zinc
Than being 10%；The mass percentage content of copper is 0.5% in slag phase, and the mass percentage content of tin is 0.09%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Embodiment 3
Step 1, detin processing is carried out to waste printed circuit board at 230 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 600 DEG C, obtains the quality hundred of cupric
Dividing content is 50%, and the mass percentage of carbon is 12%, and gold content, silver content and palladium content are respectively 100g/t, 350g/t
And 10g/t, the mass percent of tin, lead and zinc are respectively 2.1%, 1.3% and 2.2% cupric carbon dust；
Step 4, weigh following components respectively by mass percentage: electroplating sludge 30%, copper scap 10%, lime stone 7%,
Quartz 8%, sodium bicarbonate 1%, lump coal 5%, the step 3 obtain thermal decomposition product cupric carbon dust 39% and be uniformly mixed, then
Mixed material is continuously added in oxygen-enriched side-blowing bath melting, melting processing is carried out at 1250 DEG C (under this condition, silicon in slag phase
Aluminium ratio is 1.9-2.0), the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead are obtained respectively and contain tin-lead
With the slag phase of zinc；Wherein, in blister copper phase cupric mass percent be 95%, gold content 123g/t, silver content 433g/t,
Palladium content is 12g/t；Stanniferous mass percent is 10% in flue dust phase, and the mass percent of lead is 10%, the quality hundred of zinc
Divide than being 20%；The mass percentage content of copper is 0.55% in slag phase, and the mass percentage content of tin is 0.05%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Embodiment 4
Step 1, detin processing is carried out to waste printed circuit board at 180 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 450 DEG C, obtains the quality hundred of cupric
Point content is 35%, the mass percentage of carbon is 10%, and gold content, silver content and palladium content are respectively 180g/t, 400g/t
And 15g/t, the mass percent of tin, lead and zinc are respectively 2.8%, 1.8% and 2.5% thermal decomposition product cupric carbon dust；
Step 4, weigh following components respectively by mass percentage: electroplating sludge 20%, copper scap 15%, lime stone 8%,
Quartz 11%, sodium bicarbonate 2%, lump coal 10%, the step 3 obtain thermal decomposition product cupric carbon dust 34% and be uniformly mixed,
Mixed material is continuously added in oxygen-enriched side-blowing bath melting again, melting processing is carried out at 1300 DEG C (under this condition, in slag phase
Silica alumina ratio is 1.9~2.1), the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead and stanniferous are obtained respectively
The slag phase of lead and zinc；Wherein, the mass percent of cupric is 94% in blister copper phase, gold content 233g/t, silver content 500g/
T, palladium content 18.7g/t；Stanniferous mass percent is 8% in flue dust phase, and the mass percent of lead is 7%, the quality of zinc
Percentage is 15%；The mass percentage content of copper is 0.58% in slag phase, and the mass percentage content of tin is 0.08%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Embodiment 5
Step 1, detin processing is carried out to waste printed circuit board at 180 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 450 DEG C, obtains the quality hundred of cupric
Point content is 25%, and the mass percentage of carbon is 10%, gold content, silver content and palladium content be respectively 24g/t, 360g/t and
11g/t, the mass percent of tin, lead and zinc are respectively 2.8%, 1.8% and 2.5% thermal decomposition product cupric carbon dust；
Step 4, following components is weighed respectively by mass percentage: electroplating sludge 25%, copper scap 10%, lime stone
10%, the thermal decomposition product cupric carbon dust 33% and mixing that quartz 7%, sodium bicarbonate 4%, lump coal 11%, the step 3 obtain are equal
It is even, then mixed material is continuously added in oxygen-enriched side-blowing bath melting, melting processing is carried out at 1250 DEG C (under this condition, slag
Silica alumina ratio is 2.2~2.4 in phase), obtain respectively the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead and
Slag phase containing tin-lead and zinc；Wherein, the mass percent of cupric is 95% in blister copper phase, gold content 30g/t, and silver content is
446g/t, palladium content 13.6g/t；Stanniferous mass percent is 10% in flue dust phase, and the mass percent of lead is 10%, zinc
Mass percent be 20%；The mass percentage content of copper is 0.54% in slag phase, and the mass percentage content of tin is
0.05%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Embodiment 6
Step 1, detin processing is carried out to waste printed circuit board at 230 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 500 DEG C, obtains the quality hundred of cupric
Point content is 20%, and the mass percentage of carbon is 12%, gold content, silver content and palladium content be respectively 40g/t, 360g/t and
12g/t, the mass percent of tin, lead and zinc are respectively 2.5%, 1.5% and 2.5% cupric carbon dust；
Step 4, weigh following components respectively by mass percentage: electroplating sludge 20%, copper scap 14%, lime stone 5%,
Quartz 14%, sodium bicarbonate 3%, lump coal 10%, the step 3 obtain thermal decomposition product cupric carbon dust 34% and be uniformly mixed,
Mixed material is continuously added in oxygen-enriched side-blowing bath melting again, melting processing is carried out at 1300 DEG C (under this condition, in slag phase
Silica alumina ratio is 2.4~2.6), the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead and stanniferous are obtained respectively
The slag phase of lead and zinc；Wherein, the mass percent of cupric is 94% in blister copper phase, gold content 55g/t, silver content 500g/
T, palladium content 16.6g/t；Stanniferous mass percent is 8% in flue dust phase, and the mass percent of lead is 7%, the quality of zinc
Percentage is 15%；The mass percentage content of copper is 0.59% in slag phase, and the mass percentage content of tin is 0.08%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Embodiment 7
Step 1, detin processing is carried out to waste printed circuit board at 230 DEG C, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains the wiring board broken material that iron charge, aluminium material and partial size are 0~2cm respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that step 2 obtains at 600 DEG C, obtains the quality hundred of cupric
Dividing content is 50%, and the mass percentage of carbon is 15%, and gold content, silver content and palladium content are respectively 360g/t, 300g/t
And 15g/t, the mass percent of tin, lead and zinc are respectively 2.3%, 1% and 2.1% cupric carbon dust；
Step 4, weigh following components respectively by mass percentage: electroplating sludge 10%, copper scap 20%, lime stone 5%,
Quartz 15%, sodium bicarbonate 1%, lump coal 5%, the step 3 obtain thermal decomposition product cupric carbon dust 44% and be uniformly mixed, then
Mixed material is continuously added in oxygen-enriched side-blowing bath melting, melting processing is carried out at 1250 DEG C and (during melting, is controlled
Silica alumina ratio is 1.8~2.8 in slag phase), obtain the flue dust of the blister copper phase of enriching Cu gold and silver and palladium, enrichment zinc-tin and lead respectively mutually with
And the slag phase containing tin-lead and zinc；Wherein, the mass percent of cupric is 93% in blister copper phase, gold content 492g/t, silver content
For 410g/t, palladium content 20.5g/t；Stanniferous mass percent is 5% in flue dust phase, and the mass percent of lead is 5%, zinc
Mass percent be 10~%；The mass percentage content of copper is 0.58% in slag phase, and the mass percentage content of tin is
0.09%；
Step 5, by the method for gravitational dust collection and bag-type dust, the method for electrolysis, the method for wet separation respectively to institute
It states in the flue dust phase, the blister copper phase of enriching Cu gold and silver and palladium and the slag phase containing tin-lead and zinc of the Zn accumulation tin-lead of step 4 acquisition
Valuable metal be further recycled, obtain zinc, lead, copper, gold, silver, palladium valuable metal.
Experimental example
The rate of recovery for finally recycling obtained valuable metal to embodiment 1 to embodiment 7 detects, and testing result is as follows
Shown in table:
The rate of recovery detection data for the valuable metal that 1 embodiment of the present invention 1 of table to embodiment 7 finally obtains
| Zinc/% | Lead/% | Copper/% | Gold/% | Silver/% | Palladium/% | |
| Embodiment 1 | 88.0 | 87.0 | 98.0 | 99.0 | 98.0 | 99.0 |
| Embodiment 2 | 86.0 | 86.0 | 97.0 | 99.0 | 97.0 | 98.0 |
| Embodiment 3 | 85.0 | 87.0 | 98.0 | 98.8 | 97.0 | 98.0 |
| Embodiment 4 | 85.0 | 85.8 | 98.5 | 99.0 | 98.0 | 99.0 |
| Embodiment 5 | 88.0 | 86.8 | 98.7 | 99.3 | 98.0 | 99.0 |
| Embodiment 6 | 86.4 | 87.4 | 98.9 | 99.1 | 98.0 | 98.1 |
| Embodiment 7 | 87.5 | 87.0 | 98.5 | 99.2 | 98.0 | 98.0 |
| Comparative example | 83.0 | 85.0 | 97.0 | 95.0 | 95.0 | 95.0 |
Want high by the rate of recovery that data in upper table 1 can be seen that the valuable metal obtained using recovery method of the present invention
In the rate of recovery for the valuable metal that existing recovery technology obtains.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of recovery method of old circuit board valuable metal, which is characterized in that this method is achieved by the steps of:
Step 1, detin processing is carried out to waste printed circuit board, obtains wiring board tabula rasa, scolding tin and aluminium radiator fin；
Step 2, the wiring board tabula rasa obtained to the step 1 is crushed, then successively progress iron removal by magnetic separation, eddy current separation remove
Aluminium obtains iron charge, aluminium material and wiring board broken material respectively；
Step 3, pyrolysis processing is carried out to the wiring board broken material that the step 2 obtains, obtains thermal decomposition product cupric carbon dust；
Step 4, pyrolysis electroplating sludge, copper scap, lime stone, quartz, sodium bicarbonate, lump coal and the step 3 obtained
Product cupric carbon dust is simultaneously uniformly mixed, then mixed material is continuously added in oxygen-enriched side-blowing bath melting by measuring chute and belt
Carry out melting processing, obtain the blister copper phase of enriching Cu gold and silver and palladium, the flue dust phase of enrichment zinc-tin and lead respectively and containing tin-lead and
The slag phase of zinc；
Step 5, by the method for the method of gravitational dust collection and bag-type dust, the method for electrolysis and wet separation respectively to described
It the flue dust phase of Zn accumulation tin-lead that step 4 obtains, the blister copper phase of enriching Cu gold and silver and palladium and is carried out containing tin-lead and the slag phase of zinc
Processing obtains zinc, lead, copper, gold, silver, palladium valuable metal.
2. a kind of recovery method of old circuit board valuable metal according to claim 1, which is characterized in that the step
In 1, the temperature of the detin processing is 180~230 DEG C.
3. a kind of recovery method of old circuit board valuable metal according to claim 2, which is characterized in that the step
In 2, the partial size of the wiring board broken material is 0~2cm.
4. a kind of recovery method of old circuit board valuable metal according to claim 3, which is characterized in that the step
In 3, the temperature when pyrolysis processing is 450~600 DEG C.
5. a kind of recovery method of old circuit board valuable metal according to claim 4, which is characterized in that the step
In 3, the mass percentage of copper is 15~50% in the cupric carbon dust, and the mass percentage of carbon is 10~15%, gold, silver
Be respectively 15-400g/t, 200-500g/t and 5-15g/t with palladium content, the mass percent of tin, lead and zinc be respectively 2-3%,
1-2% and 2-3%.
6. a kind of recovery method of old circuit board valuable metal according to claim 5, which is characterized in that the step
In 4, the electroplating sludge, copper scap, lime stone, quartz, sodium bicarbonate, lump coal, cupric carbon dust are claimed by mass percentage
It takes, wherein electroplating sludge 10~30%, copper scap 10~20%, lime stone 5~10%, quartz 5~15%, sodium bicarbonate 1~
5%, lump coal 5~15%, cupric carbon dust 20~50%.
7. a kind of recovery method of old circuit board valuable metal according to claim 6, which is characterized in that the step
In 4, the calcium oxide content in the lime stone is greater than 50%；Dioxide-containing silica in quartz is greater than 85%；The calorific value of lump coal
Greater than 25MJ/Kg, volatile matter is less than 25%, and ash content is less than 15%.
8. a kind of recovery method of old circuit board valuable metal according to claim 7, which is characterized in that the step
In 4, the temperature of the oxygen-enriched side-blowing bath melting is 1250~1350 DEG C.
9. a kind of recovery method of old circuit board valuable metal according to claim 8, which is characterized in that the step
In 4, in the oxygen-enriched side-blowing bath fusion process, controlling silica alumina ratio in slag phase is 1.8~2.8.
10. a kind of recovery method of old circuit board valuable metal, feature described in -9 any one exist according to claim 1
In in the step 4, the mass percent of the blister copper Xiang Zhongtong is 93~95%, 20~600g/t of gold, 300~800g/ of silver
T, 5~50g/t of palladium；Tin 5~10% in the flue dust phase, the mass percent of lead are 5~10%, and the mass percent of zinc is 10
~20%；The mass percentage content of copper is lower than 0.6% in the slag phase, and the mass percentage content of tin is lower than 0.1%.
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