CN109266860A - A kind of innoxious recovery method of throwaway substrates recycling - Google Patents
A kind of innoxious recovery method of throwaway substrates recycling Download PDFInfo
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- CN109266860A CN109266860A CN201811232750.6A CN201811232750A CN109266860A CN 109266860 A CN109266860 A CN 109266860A CN 201811232750 A CN201811232750 A CN 201811232750A CN 109266860 A CN109266860 A CN 109266860A
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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
- C22B7/001—Dry processes
- C22B7/004—Dry processes separating two or more metals by melting out (liquation), i.e. heating above the temperature of the lower melting metal component(s); by fractional crystallisation (controlled freezing)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
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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
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The present invention relates to a kind of innoxious recovery methods of throwaway substrates recycling, by crushing to obtain metal powder and non-metal powder to throwaway substrates progress tin bath dismantling, level-one crushing, standard screen screening, high-voltage electrostatic sorting, waterpower separation by shaking table, second level, then leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and drying process are successively carried out to metal powder and obtain copper powder, and non-metal powder is recycled；The copper in throwaway substrates can be prepared into refined copper powder by means of the present invention, and the good composite plate of substrate processability of throwaway substrates can be utilized, recycling and reusing not only is carried out to material valuable in throwaway substrates, and it reduces pollution, this method brought by conventional process and has applications well prospect.
Description
Technical field
The present invention relates to a kind of processing method of waste, in particular to a kind of innoxious recycling side of throwaway substrates recycling
Method.
Background technique
Throwaway substrates are the important components of electronic waste, data show that, throwaway substrates account for electronic waste total amount
4% or so；The average annual growth rate of world's printed wire board industry is 8-9%, and the growth rate in China is 14.4%；Up to the present,
For the wiring board in the whole world about 40% all in domestic product, China has become world's second largest wiring board producing country；Base is printed in production
A large amount of leftover pieces and 1%-2% flaw product throwaway substrates will be generated as one of electron wastes, wherein accumulateing during plate
Metalliferous grade is tens times or even hundred times of native deposits；Substrate is the mixed of glass fiber reinforced plastics and various metals
Object is closed, wherein metal and nonmetallic combine closely, separate hardly possible.
In throwaway substrates include thousands of substances, many substances be all it is poisonous and hazardous, some are with very high time
Receive value；Therefore, a large amount of generations and removal process of electron wastes, will cause significant impact to environment and human health；
The Transport and environmental behaviour of noxious material in throwaway substrates removal process are studied, there are mainly three types of substance sources for discovery: electronics
The hyle for including in waste；Auxiliary material used in recovery technology；The by-product that hyle transformation generates；Specific packet
It includes: filling the percolate of generation, disassemble the particulate matter of generation, burn the flying dust and residue of release, scolding tin and other is removed in amalgamation
The smog generated is burned, dismantling is crushed the waste water generated, waste water caused by Cyanide Leaching, other leachings and amalgamation.
For this purpose, being torn open using pretreating process to discarded substrate the present invention is based on the principle that waste resource recycles
Solution, separating twice and sorting, obtain metal powder, metal powder is successively carried out leaching process, extraction processing, extraction process,
Copper powder is made in crystallization treatment, reduction treatment and drying process；Meanwhile non-metal powder filling is prepared using physical method
Composite plate.
Summary of the invention
The non-metal powder extracted in throwaway substrates is mainly made of substrate reinforcements and toner, wherein glass
Fiber has good reinforcing effect, provides premise for the filling recycling of non-metal powder；And contain in substrate containing higher
The copper of amount, therefore resource utilization can be carried out to the metal powder of acquisition, the copper high efficiente callback in substrate is utilized.
A kind of innoxious recycling side of throwaway substrates recycling proposed the purpose of the present invention is to solve background technique
Method, this method successively use following steps:
1) substrate discarded on electronic equipment is fitted into batches in electric heating detin furnace, carries out detin, then removed in throwaway substrates
Electronic component；
2) substrate by detin and after removing carries out level-one pulverization process；
3) smashed powder is screened by standard screen, sub-elect mesh number less than 16 mesh, 16~100 mesh and be greater than
The powder of 100 mesh these three mesh numbers；
4) mesh number is passed through into high-voltage electrostatic sorting less than 16 mesh powders, isolating not will be completely dissociated particle and metal powder, together
When, mesh number is sorted between 16~100 mesh and greater than 100 mesh powders by waterpower shaking table, isolates metal powder
End and non-metal powder；
5) particle that not will be completely dissociated isolated in step 4) is subjected to second level pulverization process, smashed material carries out step 3)
Standard screen screened；Meanwhile the metal powder isolated in step 4) successively being carried out to leaching process, extraction processing, is mentioned
Processing, crystallization treatment, reduction treatment and drying process are taken, copper powder is made；The non-metal powder that step 4) is isolated is ground
It is milled to 200 mesh of partial size, is passed through with resin, calcium carbonate powder and is mixed, preheats, is hot-forming, demoulding preparation composite plate.
As further restriction of the invention, composite plate is prepared specifically: first by after resin heating and melting, stirred
It mixes, mixing speed 600r/min, stirring 5min forms resin grout liquid, until grainless powder；By uniform paste resin
Liquid pours into the screw batch mixer of the non-metal powder and calcium carbonate powder that are previously charged into, makes non-metal powder and resin grout liquid
Come into full contact with fusion；Then the upper and lower pressure head of hydraulic press is warming up to 140 DEG C, after constant temperature 1h on a hydraulic press, on push-down head uniformly
Release agent is spread in painting, then nonmetallic mixture is placed between the upper and lower pressure head of hydraulic press, starting hydraulic press keep constant temperature and
Constant pressure is molded the composite plate being opened after 5min up to curing molding.
As further restriction of the invention, resin is acrylic resin, the mass percent of the non-metal powder
Content is 10-40%, and the mass percentage content of the total amount of the calcium carbonate powder and non-metal powder is 75%, and the holding is permanent
Determining temperature is 140 DEG C, and the constant pressure is 6Mpa.
It is limited as of the invention further, leaching process specifically: by the metal powder as in reactor, so
The CuSO that concentration is 19.5g/L is added afterwards4The C that HCl solution that solution, concentration are 1.8mol/L, concentration are 0.3mol/L4H11N
Solution, control mixing speed is in 400~600rpm, and 55 DEG C of temperature, extraction time 6h.
As further restriction of the invention, extraction processing specifically: add diluent into extractant and prepare volume
The organic extract liquid that score is 15%；Sulfuric acid solution is added into the solution after leaching and sodium hydroxide solution adjusts solution ph
Range is 2.0, and the organic extract liquid is added into the solution after adjustment pH, controls extraction time 30min.
As further restriction of the invention, extraction process specifically: solution extracted is imported in reactor, to
The sulfuric acid solution that concentration is 2mol/L is added in reactor, controls reaction time 1h.
As further restriction of the invention, crystallization treatment specifically: by said extracted processing acquired solution by steaming
After being dealt into the 50% of original volume, it is put into and carries out crystallizing obtained CuSO in crystallizer4· 5H20 crystal controls temperature at -2~4 DEG C
Between；Extraction raffinate is recycled by regulating vitriol oil concentration after crystallization.
As further restriction of the invention, CuSO is made in crystallization treatment4·5H20 crystal is added in reactor, adjusts
The concentration of whole solute is 0.6mol/L, and controlling temperature in reactor is 75 DEG C, and alkaline solution is then added into reactor, is adjusted
PH value is 14, and glucose solution is added into the reactor, is stirred to react 60min；Mass fraction is added under agitation
For 0.03 gelatin, being then slowly added into molar concentration is 0.3mol/L ascorbic acid solution, after standing for 24 hours after reaction 60min
Isolate supernatant.
It as further restriction of the invention, is dried specifically: it is dry to carry out vacuum to the copper powder after reduction treatment
Dry processing after copper powder deionized water or dehydrated alcohol after drying wash superfine cupper powder 6 times of preparation, then is dried in vacuo
Processing, can be prepared by copper powder.
The present invention is by carrying out tin bath dismantling, level-one crushing, standard screen screening, high-voltage electrostatic sorting, water to throwaway substrates
Power separation by shaking table, second level crush to obtain metal powder and non-metal powder, and leaching process, extraction are then successively carried out to metal powder
It takes processing, extraction process, crystallization treatment, reduction treatment and drying process to obtain copper powder, and non-metal powder is carried out again
It utilizes；Copper in throwaway substrates can be prepared into refined copper powder by means of the present invention, and the base of throwaway substrates can be utilized
The good composite plate of plate processability not only carries out recycling and reusing to material valuable in throwaway substrates, and reduces tradition
Pollution, this method brought by processing have applications well prospect.
The beneficial effects of the present invention are:
1, it can be realized the separation to material in substrate by a series of processing of throwaway substrates, obtain metal powder and nonmetallic
Powder, convenient for the subsequent recycling to metal material in substrate and nonmetallic materials.
2, the present invention to treated metal powder successively carries out leaching process, extraction processing, extraction process, crystallization at
Purification copper powder is made in reason, reduction treatment and drying process, and copper powder purity is up to 96% or more.
3, the present invention is by adding various ingredients into non-metal powder, and through the invention in treatment process can be real
The now recycling of non-metal powder and the good composite plate of processability.
Detailed description of the invention
Fig. 1 is the flow diagram of the innoxious recovery method of throwaway substrates recycling proposed by the present invention.
Fig. 2 be in the innoxious recovery method of throwaway substrates recycling proposed by the present invention in leaching process each parameter to leaching
The relational graph of rate.
Specific embodiment
It is next combined with specific embodiments below that the present invention is further described.
Embodiment one
A kind of innoxious recovery method of throwaway substrates recycling, this method in turn include the following steps:
This method successively uses following steps:
1) substrate discarded on electronic equipment is fitted into batches in electric heating detin furnace, carries out detin, then removed in throwaway substrates
Electronic component；
2) substrate by detin and after removing carries out level-one pulverization process；
3) smashed powder is screened by standard screen, sub-elect mesh number less than 16 mesh, 16~100 mesh and be greater than
The powder of 100 mesh these three mesh numbers；
4) mesh number is passed through into high-voltage electrostatic sorting less than 16 mesh powders, isolating not will be completely dissociated particle and metal powder, together
When, mesh number is sorted between 16~100 mesh and greater than 100 mesh powders by waterpower shaking table, isolates metal powder
End and non-metal powder；
5) particle that not will be completely dissociated isolated in step 4) is subjected to second level pulverization process, smashed material carries out step 3)
Standard screen screened；Meanwhile the metal powder isolated in step 4) successively being carried out to leaching process, extraction processing, is mentioned
Processing, crystallization treatment, reduction treatment and drying process are taken, copper powder is made；The non-metal powder that step 4) is isolated is ground
It is milled to 200 mesh of partial size, is passed through with resin, calcium carbonate powder and is mixed, preheats, is hot-forming, demoulding preparation composite plate.
Wherein, composite plate is prepared specifically: first by after resin heating and melting, be stirred, mixing speed 600r/
Min, stirring 5min forms resin grout liquid, until grainless powder；Uniform resin grout liquid is poured into be previously charged into it is non-
In the screw batch mixer of metal powder and calcium carbonate powder, comes into full contact with non-metal powder with resin grout liquid and merge；Then
The upper and lower pressure head of hydraulic press is warming up to 140 DEG C, after constant temperature 1h on a hydraulic press, uniformly applied on push-down head and spread release agent, then will
Nonmetallic mixture is placed between the upper and lower pressure head of hydraulic press, and starting hydraulic press keeps constant temperature and constant pressure, is molded 5min
It is opened the composite plate up to curing molding afterwards.
Each component is specific in the present invention are as follows: the resin is acrylic resin, the quality percentage of the non-metal powder
It is 10-40% than content, the mass percentage content of the total amount of the calcium carbonate powder and non-metal powder is 75%, the holding
Steady temperature is 140 DEG C, and the constant pressure is 6Mpa
The purpose for using electric heating detin furnace to be disassembled is: 1) for prevent subsequent recovery work in because heating etc. links let out
The harm such as leakage, release toxic and harmful gas, need premature removal substrate to have the component of dangerous substance, such as: capacitor, electricity
Pond, capacitor etc.；2) the upper electronic component disassembled from substrate greatly still has very high utility value, can incite somebody to action
It concentrates and recycling and reusing is carried out to the part, not only can effectively save limited resources but also production cost can be reduced.
Wherein, level-one pulverization process selects force mechanism predominantly to split broken and shearing gyratory crusher that is grinding, described
It is mainly that the impact type impacted and be ground rotates grater that second level pulverization process, which selects force mechanism,.
The present invention uses two-stage crushing, i.e., level-one coarse powder is broken and second level fine powder attrition process combines, in coarse powder process
Force mechanism is selected to split shearing gyratory crusher broken and based on grinding；It is main using force mechanism during fine powder
Impact type to impact and being ground rotates grater.
The purpose of separating twice processing is: sufficiently dissociateing various material compositions in throwaway substrates, and makes each substance
Component is also more uniform, and broken substrate powder is capable of increasing effective contact area with leachate, improves the leaching of metallic copper
Rate.
In order to carry out recycling and reusing to the non-metal powder of acquisition, setting non-metal powder obtains recovery method are as follows:
Non-metal powder and toner, sawdust powder and the additive that step 4) is isolated carry out mixed processing, mixed
Material carries out fusion treatment, and the fusion material that fusion treatment is crossed is in fragment shape, then cool down, crush, sieve and make at molding
Processing, can be prepared by finished plastic plate.
Wherein, mixed processing specifically: first resin is crushed, toner is made, by hexamethylenetetramine and sawdust powder
It is sent into mixing machine and is mixed with the ratio of mass ratio 9:1, after 45min, mixture is sent into pulverizer and is crushed；Then
Each component is sequentially added to mixer, incorporation time 60min, feeding sequence is sawdust powder, talcum powder, non-metal powder
End, the hexamethylenetetramine for being mixed with wood powder and other components, are finally added toner while agitating.
Wherein, the material component mass percent in the mixer is added are as follows: 35-40% toner, 5-15% sawdust
Powder, 10-40% non-metal powder, 5-25% calcium carbonate, 0.6% talcum powder, 7% hexamethylenetetramine, 1.6% stearic acid.
Wherein, fusion treatment specifically: mixed material is subjected to mixing operation on single screw rod reciprocating spiral extruder,
The temperature of fusion treatment is controlled at 95-105 DEG C, mixes each component further, under conditions of being heated and pressurizeed, resin infiltration
It penetrates into filler and goes and be uniformly mixed each component.
Meanwhile in order to carry out recycling and reusing to the metal powder of acquisition, the present invention passes through to the gold screened
Belong to powder successively to carry out leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and be dried obtained purification
Copper powder.
Wherein, leaching process specifically: by the metal powder as in reactor, it is 19.5g/L that concentration, which is then added,
CuSO4The C that HCl solution that solution, concentration are 1.8mol/L, concentration are 0.3mol/L4H11N solution, control mixing speed exist
400~600rpm, 55 DEG C of temperature, extraction time 6h.
Wherein, extraction processing specifically: the organic extraction that diluent preparation volume fraction is 15% is added into extractant
Liquid；It is 2.0 that sulfuric acid solution and sodium hydroxide solution adjusting solution ph range are added into the solution after leaching, to after adjustment pH
Solution in be added the organic extract liquid, control extraction time 30min.
Wherein, extraction process specifically: import solution extracted in reactor, concentration is added into reactor is
The sulfuric acid solution of 2mol/L controls reaction time 1h.
Wherein, crystallization treatment specifically: by said extracted processing acquired solution after be evaporated to original volume 50%,
It is put into and carries out crystallizing obtained CuSO in crystallizer4· 5H20 crystal controls temperature between -2~4 DEG C；Extraction raffinate passes through after crystallization
Regulating vitriol oil concentration is recycled.
Wherein, CuSO is made in crystallization treatment4·5H20 crystal is added in reactor, and the concentration for adjusting solute is 0.6mol/
L, controlling temperature in reactor is 75 DEG C, alkaline solution is then added into reactor, adjustment pH value is 14, to the reactor
Middle addition glucose solution, is stirred to react 60min；The gelatin that mass fraction is 0.03 is added under agitation, then slowly
Addition molar concentration is 0.3mol/L ascorbic acid solution, stands after reaction 60min and isolates supernatant afterwards for 24 hours.
Wherein, it is dried specifically: vacuum drying treatment is carried out to the copper powder after reduction treatment, the copper powder after drying is used
After prepared by deionized water or dehydrated alcohol washing superfine cupper powder 6 times, then vacuum drying treatment is carried out, can be prepared by copper powder.
Embodiment two
What is different from the first embodiment is that the non-metal powder isolated is ground to 200 mesh of partial size, with resin, calcium carbonate powder
By mixing, preheating, hot-forming, demoulding preparation composite plate, wherein the mass percentage content of the non-metal powder is
20%, the mass percentage content of the total amount of the calcium carbonate powder and non-metal powder is 75%.
Embodiment three
It is unlike the embodiments above, the non-metal powder isolated is ground to 200 mesh of partial size, with resin, Paris white
End is by mixing, preheating, hot-forming, demoulding preparation composite plate, wherein the mass percentage content of the non-metal powder is
30%, the mass percentage content of the total amount of the calcium carbonate powder and non-metal powder is 75%.
Example IV
It is unlike the embodiments above, the non-metal powder isolated is ground to 200 mesh of partial size, with resin, Paris white
End is by mixing, preheating, hot-forming, demoulding preparation composite plate, wherein the mass percentage content of the non-metal powder is
40%, the mass percentage content of the total amount of the calcium carbonate powder and non-metal powder is 75%.
Comparative example
It first by after acrylic resin heating and melting, is stirred, mixing speed 600r/min, stirring 5min forms paste resin
Liquid, until grainless powder；Uniform resin grout liquid is poured into the screw batch mixer for the calcium carbonate powder being previously charged into
In, it comes into full contact with calcium carbonate powder with resin grout liquid and merges；Then the upper and lower pressure head of hydraulic press is warming up to 140 DEG C, constant temperature 1h
Afterwards on a hydraulic press, uniformly applied on push-down head and spread release agent, then by nonmetallic mixture be placed in the upper and lower pressure head of hydraulic press it
Between, starting hydraulic press keeps 140 DEG C of steady temperature and the constant pressure of 6Mpa, is opened after being molded 5min up to curing molding
Composite plate.
It is tested by the performance of the composite plate prepared to embodiment one to five, obtains non-metal powder in the following table 1
Influence of the Different adding amount to composite plate performance.
The various performances of composite plate when the Different adding amount of 1 non-metal powder of table
As it can be seen from table 1 when the partial size of non-metal powder is that (non-metal powder of 200 mesh has 200 mesh since partial size is smaller
Conducive to being uniformly distributed for component, it is not easy to form defect inside plate) when, the impact strength of composite plate is added with non-metal powder
The increase of amount occurs first enhancing, reduces the trend enhanced again；But when the non-metal powder of 200 mesh is added excessive, and having can
Agglomeration can be formed.
As can also be seen from Table 1, when the additive amount for the non-metal powder that partial size is 200 mesh is 20%, composite plate impact is strong
Spend it is best, be 6.3KJ/m2, when this additional amount for being primarily due to the non-metal powder that partial size is 200 mesh is 20%, composite plate it is each
Mixture ratio is more uniform, it is not easy to occur to reunite so that the shock resistance of composite plate is preferable.
Rockwell hardness is the ability for reflecting material and resisting irrecoverable deformation under external force, the addition of non-metal powder
The influence to the Rockwell hardness of composite plate is measured as it can be seen from table 1 composite plate prepared by the non-metal powder that partial size is 200 mesh
Rockwell hardness is influenced smaller by additive amount variation, and the little particle that this is primarily due to filler in composite plate is less, and mixture is easy
Hole is formed, plate is not fine and close, hardness is low.
Each performance of the composite plate of different additional amounts, the composite plate tool of the additional amount of 20% non-metal powder is comprehensively compared
There is relatively good mechanical performance, performance meets the requirement of market application.
In addition, Fig. 2 gives the relational graph of each parameter and leaching rate in the leaching process in metal powder removal process.
It partially can be seen that from (a) in Fig. 2, the leaching rate of copper ion is with CuSO4The increase of concentration and increase rapidly, instead
It should continue, leaching rate is accelerated, and leaching rate is continuously improved；But with CuSO4Continuing growing for concentration causes in solution
CuSO4Remaining meltage reduce, to influence the leaching content of copper, also increase cost recovery；Comprehensive leaching rate and economic effect
Benefit maximizes both sides and considers, final choice CuSO4Solution concentration are as follows: 19.5g/L.
It partially can be seen that from (b) in Fig. 2, the leaching of copper takes the lead in reducing after increasing, when HCl concentration increases to 1.8mol/L
When, leaching efficiency reaches 97.1%；And when HCl concentration is more than 1.8mol/L, leaching rate starts to decline instead, this be by
Cause solution viscosity, density, salinity to increase in continuing to increase for HCl concentration, causes effective H of the participation reaction in solution+Drop
Low, reaction slows down；In addition, HCl excessive concentration is but also a large amount of hydrochloric acid volatilizations increase process costs, taking into account the above, selection is soaked
Best HCl concentration is 1.8mol/L in liquid out.
It partially can be seen that from (c) in Fig. 2, leaching rate is with C4H11The increase of N concentration first increases to be reduced afterwards, works as C4H11N is dense
When degree is less than 0.3mol/L, the leaching rate of copper persistently increases, and peak value is up to 97.86%；This is primarily due to C4H11The increasing of N concentration
Added with being conducive to its reacting with copper ion and react that balance is positive to be carried out with hydrochloric acid, then leaching rate rises；And work as C4H11N is dense
When degree is greater than 0.3mol/L, continue to increase C4H11N concentration then needs the HCl consumed in more many body system to react, HCl amount
It reduces, directly results in system pH increase, then participate in effective H of reaction in solution+Concentration decline, reaction rate decline, leaching rate
It reduces；Taking into account the above, best C is selected4H11N concentration is determined as 0.3mol/L.
It partially can be seen that from (d) in Fig. 2, reaction temperature is affected to the leaching rate of copper ion, as temperature is by 25
DEG C 55 DEG C being risen to, copper ion leaching rate is gradually increasing, continues to increase temperature, after system temperature is higher than 55 DEG C, leaching rate
Increase starts to slow down；In addition, as the temperature rises, will lead to the volatilization of a large amount of HCl, to sum up, select best extraction temperature for
55℃。
It partially can be seen that from (e) in Fig. 2, with the extension of extraction time, the leaching rate of copper is also increased with it, and reacts 6h
The leaching rate of copper reaches 96.4% afterwards, and leaching efficiency is higher；The too short leaching rate that will cause of extraction time is low, and extraction time is super
After crossing 6h, continue to extend extraction time, it can be seen that leaching rate ascensional range is no longer obvious, while will lead to process efficiency
Decline, the increase of production cost, so reaction 6h has substantially met the requirement that copper ion in metal powder leaches completely, so most
Determine that extraction time is 6h eventually.
From part (f) in such as Fig. 2 as can be seen that different mixing speeds have larger shadow to the leaching rate of copper in metal powder
It rings；When revolving speed is less than 200rpm, copper leaching rate is lower than 10.02%, when revolving speed control is 400rpm, copper leaching rate=
91.26%；This increase for being primarily due to mixing speed improves the dissolved oxygen amount in leachate, oxygen in oxygen and leachate in air
The rising of content accelerates Cu+It is oxidized to Cu2+Rate, the Cu of generation2+Leaching process is continued to participate in, is greatly improved
Leaching rate；When continuing growing mixing speed to 600rpm, leaching rate growth rate is gradually delayed；When revolving speed rises to 800rpm, leaching
Extracting rate is declined instead, the reason is that excessively high mixing speed, accelerates HCl, C in leachate4H11The evaporation rate of N causes
Make the reduction of both effective rate of utilization, then leaching rate declines therewith.To sum up, to prevent the powder in leaching process from depositing, stirring
Intensity is determined as 400~600rpm.
To sum up, the present invention considers influence of each parameter to the leaching rate of copper in metal powder in leaching process, final to make
It makes optimal parameter: controlling mixing speed under agitation in 400~600rpm, CuSO4 concentration 19.5g/L, HCl concentration
1.8mol/L、C4H11N concentration 0.3mol/L, 55 DEG C of temperature, extraction time 6h；The leaching efficiency of copper is up in metal powder
98.17%, precision is preferable, realizes and is transferred to copper in substrate in liquid phase by solid phase, to recycle copper from throwaway substrates and preparing
Copper powder is had laid a good foundation.
In extraction process, Cu2+The complex compound formed with extractant enters in organic phase, and the distribution of copper is with pH value
Rise and expands, therefore improve water phase pH by better facilitated extraction process, while can effectively reduce extract extraction raffinate in Cu2+Contain
Amount improves extraction yield；Meanwhile when carrying out extraction and separation, copper should be made to be extracted into organic phase to greatest extent, prevented again
Other metal ions enter organic phase, so, comprehensively consider above-mentioned both sides factor, the initial pH of extraction solution is selected as 2.0；
Meanwhile extractant is stronger to copper extracting power, the extraction yield of copper has just reached 93.81% after extraction 10min, continues to extend extraction
Time, extraction of copper do not change substantially, it can thus be concluded that extraction time is more than that 10min can realize extraction equilibrium substantially out, are
Guarantee ideal extraction of copper, determines that optimum extraction time is 30min, the extraction yield of copper reaches 99.88%；According to the above analysis
As a result, it can be deduced that, the factor for influencing extraction of copper mainly has: the factors such as concentration, extraction time, initial pH of extractant；Cause
This, is arranged extraction processing specifically: the organic extract liquid that diluent preparation volume fraction is 15% is added into extractant；To leaching
It is 2.0 that sulfuric acid solution and sodium hydroxide solution adjusting solution ph range are added in solution after out, the solution to after adjustment pH
It is middle that the organic extract liquid is added, control extraction time 30min.
In extraction process, recovery rate is by H2SO4Concentration be affected, therefore need accurate determine under optimum extraction condition
H2SO4Concentration；Work as H2SO4During concentration is increased to 2.0mol/L by 0.5mol/L, the recovery rate of corresponding Cu is by 17.96%
→ 96.44%, continue to improve H2SO4Concentration will cause extractant to lower the extracting power to copper, therefore H is controlled in extraction process2SO4
Concentration is determined as 2.0mol/L.
Meanwhile the recovery rate of copper increases with the increase of extraction time, when extraction time is 5min, recovery rate reaches
91.32%, extraction is in a basic balance, continues to extend extraction time, recovery rate raising is no longer obvious, and to sum up extraction time is determined as
5min；Therefore, final choice extraction process specifically: solution extracted is imported in reactor, is added into reactor dense
Degree is the sulfuric acid solution of 2mol/L, controls reaction time 1h.
Then the crystallization treatment for carrying out solution, by said extracted processing acquired solution by being evaporated to the 50% of original volume
Afterwards, it is put into and carries out crystallizing obtained CuSO in crystallizer4·5H20 crystal controls temperature between -2~4 DEG C；Extraction raffinate is logical after crystallization
Sulfuric acid concentration is overregulated to be recycled.
Finally, to CuSO obtained4·5H20 crystal is restored and is dried, and specific setting reduction treatment is specific
Are as follows: CuSO45H20 crystal is made in crystallization treatment and is added in reactor, the concentration for adjusting solute is 0.6mol/L, and control is anti-
Answering temperature in device is 75 DEG C, and alkaline solution is then added into reactor, and adjustment pH value is 14, and Portugal is added into the reactor
Grape sugar juice, is stirred to react 60min；The gelatin that mass fraction is 0.03 is added under agitation, is then slowly added into mole
Concentration is 0.3mol/L ascorbic acid solution, stands after reaction 60min and isolates supernatant afterwards for 24 hours.
Be dried specifically: vacuum drying treatment carried out to the copper powder after reduction treatment, it is dry after copper powder spend from
After prepared by sub- water or dehydrated alcohol washing superfine cupper powder 6 times, then vacuum drying treatment is carried out, can be prepared by copper powder.
It can be seen that the present invention by carrying out tin bath dismantling, level-one crushing, mark to throwaway substrates from the comparison of above-mentioned performance
The screening of quasi- sieve, high-voltage electrostatic sorting, waterpower separation by shaking table, second level crush to obtain metal powder and non-metal powder, then to gold
Category powder successively carries out leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and drying process and obtains metal
Copper powder, and non-metal powder is recycled；The copper in throwaway substrates can be prepared into refined copper by means of the present invention
Powder, copper powder purity is up to 96% or more；And the good composite plate of substrate processability of throwaway substrates can be utilized, not only to useless
It abandons valuable material in substrate and carries out recycling and reusing, and reduce pollution, this method brought by conventional process and have well
Application prospect.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of innoxious recovery method of throwaway substrates recycling, which is characterized in that successively use following steps:
1) substrate discarded on electronic equipment is fitted into batches in electric heating detin furnace, carries out detin, then removed in throwaway substrates
Electronic component；
2) substrate by detin and after removing carries out level-one pulverization process；
3) smashed powder is screened by standard screen, sub-elect mesh number less than 16 mesh, 16~100 mesh and be greater than
The powder of 100 mesh these three mesh numbers；
4) mesh number is passed through into high-voltage electrostatic sorting less than 16 mesh powders, isolating not will be completely dissociated particle and metal powder, together
When, mesh number is sorted between 16~100 mesh and greater than 100 mesh powders by waterpower shaking table, isolates metal powder
End and non-metal powder；
5) particle that not will be completely dissociated isolated in step 4) is subjected to second level pulverization process, smashed material carries out step 3)
Standard screen screened；Meanwhile the metal powder isolated in step 4) successively being carried out to leaching process, extraction processing, is mentioned
Processing, crystallization treatment, reduction treatment and drying process are taken, copper powder is made；The non-metal powder that step 4) is isolated is ground
It is milled to 200 mesh of partial size, is passed through with resin, calcium carbonate powder and is mixed, preheats, is hot-forming, demoulding preparation composite plate.
2. a kind of innoxious recovery method of throwaway substrates recycling according to claim 1, it is characterised in that: prepare compound
Plate specifically: first by after resin heating and melting, be stirred, mixing speed 600r/min, stirring 5min forms paste resin
Liquid, until grainless powder；Uniform resin grout liquid is poured into the non-metal powder and calcium carbonate powder being previously charged into
In screw batch mixer, comes into full contact with non-metal powder with resin grout liquid and merge；Then the upper and lower pressure head of hydraulic press is warming up to
140 DEG C, after constant temperature 1h on a hydraulic press, uniformly applied on push-down head and spread release agent, then nonmetallic mixture is placed in hydraulic press
Between upper and lower pressure head, starting hydraulic press keeps constant temperature and constant pressure, is opened answering up to curing molding after being molded 5min
Plywood.
3. a kind of innoxious recovery method of throwaway substrates recycling according to claim 2, it is characterised in that: the resin
For acrylic resin, the mass percentage content of the non-metal powder is 10-40%, the calcium carbonate powder and non-metal powder
The mass percentage content of the total amount at end is 75%, and the temperature that keeps constant is 140 DEG C, and the constant pressure is 6Mpa.
4. a kind of innoxious recovery method of throwaway substrates recycling according to claim 1, it is characterised in that: the leaching
Processing specifically: by the metal powder as in reactor, the CuSO that concentration is 19.5g/L is then added4Solution, concentration are
The HCl solution of 1.8mol/L, the C that concentration is 0.3mol/L4H11N solution controls mixing speed in 400~600rpm, temperature 55
DEG C, extraction time 6h.
5. a kind of innoxious recovery method of throwaway substrates recycling according to claim 4, it is characterised in that: the extraction
Processing specifically: the organic extract liquid that diluent preparation volume fraction is 15% is added into extractant；Into the solution after leaching
Adding sulfuric acid solution and sodium hydroxide solution adjusting solution ph range is 2.0, is had described in addition into the solution after adjustment pH
Machine extract liquor controls extraction time 30min.
6. a kind of innoxious recovery method of throwaway substrates recycling according to claim 5, it is characterised in that: the extraction
Processing specifically: solution extracted is imported in reactor, the sulfuric acid solution that concentration is 2mol/L, control are added into reactor
Reaction time 1h processed.
7. a kind of innoxious recovery method of throwaway substrates recycling according to claim 6, it is characterised in that: the crystallization
Processing specifically: by said extracted processing acquired solution after be evaporated to original volume 50%, be put into crystallizer and tied
The obtained CuSO of crystalline substance4· 5H20 crystal controls temperature between -2~4 DEG C；Extraction raffinate is carried out again by regulating vitriol oil concentration after crystallization
It utilizes.
8. a kind of innoxious recovery method of throwaway substrates recycling according to claim 7, it is characterised in that: at crystallization
It manages and CuSO is made4·5H20 crystal is added in reactor, and the concentration for adjusting solute is 0.6mol/L, controls temperature in reactor and is
75 DEG C, alkaline solution is then added into reactor, adjustment pH value is 14, and glucose solution is added into the reactor, stirs
Mix reaction 60min；The gelatin that mass fraction is 0.03 is added under agitation, being then slowly added into molar concentration is
0.3mol/L ascorbic acid solution stands after reacting 60min and isolates supernatant afterwards for 24 hours.
9. a kind of innoxious recovery method of throwaway substrates recycling according to claim 8, it is characterised in that: the drying
Processing specifically: vacuum drying treatment, copper powder deionized water or anhydrous second after drying are carried out to the copper powder after reduction treatment
After superfine cupper powder 6 times of alcohol washing preparation, then vacuum drying treatment is carried out, can be prepared by copper powder.
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Cited By (1)
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Application publication date: 20190125 |