CN109500053A - A kind of method that scrap concrete prepares copper powder - Google Patents
A kind of method that scrap concrete prepares copper powder Download PDFInfo
- Publication number
- CN109500053A CN109500053A CN201811232744.0A CN201811232744A CN109500053A CN 109500053 A CN109500053 A CN 109500053A CN 201811232744 A CN201811232744 A CN 201811232744A CN 109500053 A CN109500053 A CN 109500053A
- Authority
- CN
- China
- Prior art keywords
- solution
- concentration
- powder
- copper powder
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000000605 extraction Methods 0.000 claims abstract description 74
- 238000002386 leaching Methods 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 56
- 230000008569 process Effects 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000012545 processing Methods 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000005485 electric heating Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000002211 L-ascorbic acid Substances 0.000 claims description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052927 chalcanthite Inorganic materials 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 18
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000010949 copper Substances 0.000 description 39
- 229910052802 copper Inorganic materials 0.000 description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 12
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- -1 Yi Jitong Chemical compound 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000010793 electronic waste Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention relates to a kind of method that scrap concrete prepares copper powder, by waste printed circuit board carry out pretreating process discarded circuit board is disassembled, separating twice and sorting, obtain metal powder；Then leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and drying process are successively carried out to metal powder obtain copper powder, recycling and reusing not only is carried out to material valuable in waste printed circuit board, 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 method that a kind of scrap concrete prepares copper powder.
Background technique
Circuit board is primarily referred to as on nonconducting substrate first according to printing made of being pre-designed by electron printing
The copper-clad plate that part, route and the two are combined into, usual circuit board specifically include that printed circuit board, capacitor, resistance, integrate
The components such as block；Circuit board is the basis of modern electronics industry, and components are indispensable in nearly all electronic product
It is needed to connect；And with the development of electronic product, footprint is increasing, and requires circuit board as company
It connects；The continuous propulsion of information age, emerges a large amount of high in technological content electronic product, and update speed constantly adds
Fastly, there is data to show that thus bring electronic waste is increased every year with 18% speed, become speedup is most fast in the world rubbish it
One；The electronic product kept updating gives people more user experiences, also brings mankind's great convenience, but electronics is useless
Gurry also brings significant wastage that is potentially hazardous, and causing resource simultaneously to environment.
And these " wastes " are even more the huge treasure-house of resource from the point of view of recycling angle；Electron wastes are from resource reclaim
From the perspective of, potential value is very high, is one containing the rare precious metals such as gold, silver, platinum, rhodium, Yi Jitong, iron, aluminium, zinc, nickel etc.
The resource collective of base metal；And the noble metal gold, silver contained in waste and old circuit board and non-ferrous metal copper etc., with common metal
Ore is compared, and metal content will be higher by decades of times or even hundreds times, and the component of circuit board is very complicated, and in waste and old circuit board
Metal species are more and content is rich.
The disposal of resources for realizing electron wastes, can not only protect ecological environment for the survival of mankind, while again can
Realize the recycling of valuable constituent contained by electron wastes, therefore Disposal of Electronic Wastes processing technique is with important
Application value is resource high-efficiency recycling and reusing and environmental pollution prevention and control field important content.
Summary of the invention
The method that a kind of scrap concrete proposed the purpose of the present invention is to solve background technique prepares copper powder, it is first
First discarded circuit board is disassembled using pretreating process, separating twice and sorting, obtains metal powder；Then to metal
Powder successively carries out leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and drying process, and metallic copper is made
Powder.
Wherein, the pretreating process the following steps are included:
1) circuit board discarded on electronic equipment is fitted into batches in electric heating detin furnace, carries out detin, then remove discarded circuit
Electronic component on plate；
2) circuit board 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, 3) smashed material enters step
Standard screen sorted again.
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, reduction treatment specifically: CuSO is made in crystallization treatment4·5H20 crystal
It is added in reactor, the concentration for adjusting solute is 0.6mol/L, and controlling temperature in reactor is 75 DEG C, is then added into reactor
Enter alkaline solution, adjustment pH value is that glucose solution is added in 14, Xiang Suoshu reactor, is stirred to react 60min；In stirring condition
The lower gelatin that mass fraction is added and is 0.03, being then slowly added into molar concentration is 0.3mol/L ascorbic acid solution, reaction
It is stood after 60min and isolates supernatant afterwards for 24 hours.
It is further limited as of the invention, the recycling technique in step 5) specifically: isolate step 4)
Non-metal powder and toner, sawdust powder and additive carry out mixed processing, and mixed material carries out fusion treatment,
The fusion material that fusion treatment is crossed is in fragment shape, then cool down, crush, sieve and at mould compression process, can be prepared by finished product
Plastic plate.
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 by waste printed circuit board carry out tin bath dismantling, level-one crushing, standard screen screening, high-voltage electrostatic sorting,
A series of processing such as waterpower separation by shaking table, second level crushing obtain metal powder and non-metal powder, then successively to metal powder
It carries out leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and drying process and obtains copper powder；Using this
The method of invention not only carries out recycling and reusing to material valuable in waste printed circuit board, recycles the copper in waste printed circuit board
Standby refined copper powder, also pollution brought by reduction conventional process, this method 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 waste printed circuit board, obtain metal powder and Fei Jin
Belong to powder, convenient for the subsequent recycling to metal material in substrate and nonmetallic materials.
2, the present invention carries out leaching process, extraction processing, extraction process, crystallization treatment, also to treated metal powder
Original place reason and drying process obtain copper powder.
Detailed description of the invention
Fig. 1 is the flow diagram for the method that scrap concrete proposed by the present invention prepares copper powder.
Fig. 2 is that scrap concrete proposed by the present invention prepares in the method for copper powder each parameter and leaching rate in leaching process
Relational graph.
Fig. 3 is that scrap concrete proposed by the present invention prepares in the method for copper powder each parameter and leaching rate in extraction processing
Relational graph.
Specific embodiment
It is next combined with specific embodiments below that the present invention is further described.
A kind of method that scrap concrete prepares copper powder, this method in turn include the following steps:
1) circuit board discarded on electronic equipment is fitted into batches in electric heating detin furnace, carries out detin, then remove discarded circuit
Electronic component on plate；
2) circuit board 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, 3) smashed material enters step
Standard screen sorted again.
The purpose for using electric heating detin furnace to be disassembled is: 1) for prevent subsequent recovery work in because heating etc. links hair
The harm such as raw leakage, release toxic and harmful gas, need premature removal circuit board to have the component of dangerous substance, such as:
Capacitor, battery, capacitor etc.；2) the upper electronic component disassembled from circuit board greatly still has very high exploitation value
Value can carry out recycling and reusing to the part for concentrating, not only can effectively save limited resources but also can reduce production cost.
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 waste printed circuit board, and makes each object
Matter component is also more uniform, and broken circuit board powder is capable of increasing effective contact area with leachate, improves metallic copper
Leaching rate.
Fig. 2 gives the relational graph of each parameter and leaching rate in the leaching process of metal powder removal process, illustrates
It is as follows:
Control reaction temperature is 25 DEG C, speed of agitator 500r/min, HCl concentration is 1.8mol/L, C4H11N concentration is
0.3mol/L changes and CuSO is added4Concentration studies various concentration CuSO4Influence to copper ion leaching rate in circuit board；CuSO4
The size of concentration is affected to copper ion leaching rate, so in initial reaction stage, as CuSO in reactor4When concentration is lower,
Leaching effect is unobvious；And with CuSO4The raising of concentration is reacted opposite and is accelerated, when extraction time is 12h, obtains CuSO4It is molten
The relational graph of liquid concentration and copper leaching rate, referring to fig. 2 in the part (a).
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.
Control reaction temperature is 25 DEG C, speed of agitator 500r/min, CuSO4 concentration is 19.5g/L, C4H11N concentration is
0.3mol/L changes and HCl concentration is added, has studied influence of the various concentration HCl to copper leaching rate in circuit board, show that hydrochloric acid is dense
Degree and the relational graph of copper leaching rate, referring to fig. 2 in the part (b).
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.
Control reaction temperature be 25 DEG C, speed of agitator 500r/min, CuSO4Concentration 19.5g/L, HCl concentration 1.8mol/
L changes C in leachate4H11N concentration, has studied C4H11Influence of the N concentration to copper leaching rate in circuit board, extraction time are
12h obtains C4H11The relational graph of N concentration and copper leaching rate, referring to fig. 2 in the part (c).
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.
Control CuSO4 concentration is 19.5g/L, HCl concentration 1.8mol/L, C4H11N concentration 0.3mol/L, speed of agitator are
500r/min, adjustment system reaction temperature are respectively as follows: 25 DEG C, 35 DEG C, 45 DEG C, 55 DEG C, 65 DEG C, have studied under condition of different temperatures
Influence to copper ion leaching rate, as a result such as part (d) in Fig. 2.
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℃。
Control CuSO4Concentration is that 19.5g/L, HCl concentration are 1.8mol/L, C4H11N concentration is 0.3mol/L, speed of agitator
It is 55 DEG C for 500r/min, temperature, changes extraction time within the scope of 1~10h, obtained extraction time to the shadow of copper leaching rate
It rings, as a result such as part (e) in Fig. 2.
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.
Control CuSO4Concentration is that 19.5g/L, HCl concentration are 1.8mol/L, C4H11N concentration is 0.3mol/L, temperature 55
DEG C, under the conditions of extraction time 6h, change mixing speed, obtain influence of the mixing speed to copper leaching rate, as a result as in Fig. 2
(f) part.
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 circuit board in liquid phase by solid phase, to recycle copper simultaneously from waste printed circuit board
Copper powder is prepared to have laid a good foundation.
Fig. 3 gives the relational graph of each parameter and leaching rate in the extraction processing of metal powder removal process, illustrates
It is as follows:
It partially can be seen that by (a) in Fig. 3, when pH value is in 0.2~0.8 range, the extraction yield of copper ion is smaller, and pH value
When more than 0.8, the extraction yield increasing degree of copper is larger；When initial pH value reaches 2.0, the extraction yield of copper reaches 99% or more.
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.
It partially can be seen that by (b) in Fig. 3, extractant volume fraction increases to 15% by 5%, and the extraction yield of copper is by 98.83%
99.88% is increased to, continues to increase extractant concentration, corresponding extraction yield raising is no longer obvious, and reason is that excessive extractant is led
Solution viscosity is caused to increase, mobility is deteriorated, and hinders the further progress of extraction process, comprehensively considers extraction cost and extraction effect
The many factors such as fruit, slective extraction agent volume fraction are 15%.
Partially can be seen that by (c) in Fig. 3, extractant is stronger to copper extracting power, extract 10min after copper extraction yield just
Reach 93.81%, has continued to extend extraction time, extraction of copper does not change substantially, it can thus be concluded that extraction time is more than out
10min can realize extraction equilibrium substantially, to guarantee ideal extraction of copper, determine that optimum extraction time is 30min, the extraction of copper
Rate is taken to reach 99.88%.
According to the above analysis result, it can be deduced that, the factor for influencing extraction of copper mainly has: the concentration of extractant, extraction
The factors such as time, initial pH；Therefore, extraction processing is set specifically: diluent preparation volume fraction is added into extractant is
15% organic extract liquid；Sulfuric acid solution is added into the solution after leaching and sodium hydroxide solution adjusting solution ph range is
2.0, the organic extract liquid is added into the solution after adjustment pH, controls 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 that Portugal is added in 14, Xiang Suoshu 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, first level flour to waste printed circuit board from above-mentioned analysis of the invention
Broken, standard screen screening, high-voltage electrostatic sorting, waterpower separation by shaking table, second level a series of processing such as crush and obtain metal powder and non-
Metal powder, then metal powder is successively carried out leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and
Drying process obtains copper powder；Not only material valuable in waste printed circuit board is recycled again using method of the invention
It utilizes, recycles the copper in waste printed circuit board for refined copper powder, also pollution brought by reduction conventional process, this method has 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 (8)
1. a kind of method that scrap concrete prepares copper powder, which is characterized in that first using pretreating process to discarded circuit
Plate disassembled, separating twice and sorting, obtains metal powder；
Then leaching process, extraction processing, extraction process, crystallization treatment, reduction treatment and drying are successively carried out to metal powder
Copper powder is made in processing.
2. the method that a kind of scrap concrete according to claim 1 prepares copper powder, it is characterised in that: the leaching process
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.
3. the method that a kind of scrap concrete according to claim 2 prepares copper powder, it is characterised in that: the extraction processing
Specifically: the organic extract liquid that diluent preparation volume fraction is 15% is added into extractant；It is added into the solution after leaching
It is 2.0 that sulfuric acid solution and sodium hydroxide solution, which adjust solution ph range, and organic extraction is added into the solution after adjustment pH
Liquid is taken, extraction time 30min is controlled.
4. the method that a kind of scrap concrete according to claim 3 prepares copper powder, it is characterised in that: the extraction process
Specifically: solution extracted is imported in reactor, the sulfuric acid solution that concentration is 2mol/L is added into reactor, control is anti-
1h between seasonable.
5. the method that a kind of scrap concrete according to claim 4 prepares copper powder, it is characterised in that: the crystallization treatment
Specifically: by said extracted processing acquired solution after be evaporated to original volume 50%, the crystallization system that carries out is put into crystallizer
Obtain CuSO4·5H20 crystal controls temperature between -2~4 DEG C；Extraction raffinate is recycled by regulating vitriol oil concentration after crystallization.
6. the method that a kind of scrap concrete according to claim 5 prepares copper powder, it is characterised in that: the reduction treatment
Specifically: CuSO is made in crystallization treatment4·5H20 crystal is added in reactor, and the concentration for adjusting solute is 0.6mol/L, control
Temperature is 75 DEG C in reactor, and alkaline solution is then added into reactor, and adjustment pH value is to be added in 14, Xiang Suoshu reactor
Glucose solution is stirred to react 60min；The gelatin that mass fraction is 0.03 is added under agitation, is then slowly added into and rubs
Your concentration is 0.3mol/L ascorbic acid solution, stands after reaction 60min and isolates supernatant afterwards for 24 hours.
7. the method that a kind of scrap concrete according to claim 6 prepares copper powder, it is characterised in that: the drying process
Specifically: vacuum drying treatment is carried out to the copper powder after reduction treatment, the copper powder after drying is washed with deionized water or dehydrated alcohol
After superfine cupper powder 6 times for washing preparation, then vacuum drying treatment is carried out, can be prepared by copper powder.
8. the method that a kind of scrap concrete according to claim 1 prepares copper powder, it is characterised in that: the pretreatment work
Skill the following steps are included:
1) circuit board discarded on electronic equipment is fitted into batches in electric heating detin furnace, carries out detin, then remove discarded circuit
Electronic component on plate；
2) circuit board 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, 3) smashed material enters step
Standard screen sorted again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811232744.0A CN109500053A (en) | 2018-10-23 | 2018-10-23 | A kind of method that scrap concrete prepares copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811232744.0A CN109500053A (en) | 2018-10-23 | 2018-10-23 | A kind of method that scrap concrete prepares copper powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109500053A true CN109500053A (en) | 2019-03-22 |
Family
ID=65745847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811232744.0A Pending CN109500053A (en) | 2018-10-23 | 2018-10-23 | A kind of method that scrap concrete prepares copper powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109500053A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1136020A (en) * | 1997-07-15 | 1999-02-09 | Justy:Kk | Treatment of waste printed circuit board |
| CN102172597A (en) * | 2010-12-24 | 2011-09-07 | 广州有色金属研究院 | Discarded circuit board full-value recycling method |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN105886775A (en) * | 2016-04-14 | 2016-08-24 | 上海第二工业大学 | Method for improving microbial leaching of metal copper in waste circuit board through graphene modified carbon cloth electrode system |
| CN107377575A (en) * | 2016-05-17 | 2017-11-24 | 陕西安信显像管循环处理应用有限公司 | Useless circuit board processing system and its processing method |
-
2018
- 2018-10-23 CN CN201811232744.0A patent/CN109500053A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1136020A (en) * | 1997-07-15 | 1999-02-09 | Justy:Kk | Treatment of waste printed circuit board |
| CN102172597A (en) * | 2010-12-24 | 2011-09-07 | 广州有色金属研究院 | Discarded circuit board full-value recycling method |
| CN102363890A (en) * | 2011-10-26 | 2012-02-29 | 广州有色金属研究院 | Method for recovering metal copper in waste circuit board |
| CN105886775A (en) * | 2016-04-14 | 2016-08-24 | 上海第二工业大学 | Method for improving microbial leaching of metal copper in waste circuit board through graphene modified carbon cloth electrode system |
| CN107377575A (en) * | 2016-05-17 | 2017-11-24 | 陕西安信显像管循环处理应用有限公司 | Useless circuit board processing system and its processing method |
Non-Patent Citations (2)
| Title |
|---|
| 杨乐: "废旧电路板中湿法冶金回收铜并制备超细铜粉的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 江勇: "废弃印刷线路板绿色回收与资源化工艺的研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101698904B (en) | Method for extracting sulfide minerals of nonferrous metals and method for recycling sulfur in extracted filtered residues thereof | |
| CN101928838B (en) | Method for removing and recovering arsenic from lead anode slime | |
| CN103451438B (en) | A kind of microwave treatment that adopts extracts the method reclaiming copper and selenium from copper anode mud | |
| CN107012332A (en) | A kind of method that metal is reclaimed in nickeliferous, cobalt refuse battery and cupric electron wastes collaboration | |
| CN104328281A (en) | Method for efficient separation and recycling of precious metals in waste circuit board | |
| CN104131167A (en) | Method for recovering selenium and manganese in manganese anode slime by using microwaves | |
| CN105886768A (en) | Method for efficiently enriching precious metal from electronic waste | |
| CN115084704A (en) | Method for separating and recovering valuable components of waste ternary batteries | |
| Zhang et al. | Recover value metals from spent lithium-ion batteries via a combination of in-situ reduction pretreatment and facile acid leaching | |
| CN108950218A (en) | A method of recycling gold, silver and copper from waste printed circuit board | |
| CN102031378A (en) | Method for recovering metal silver from waste plasma display panel (PDP) glass plate | |
| CN109500053A (en) | A kind of method that scrap concrete prepares copper powder | |
| CN109735717A (en) | A kind of microwave reinforced method for leaching valuable element in recycling copper weld pool cigarette ash | |
| CN109338106A (en) | A kind of waste printed circuit board resource utilization reuse method | |
| CN113528837B (en) | Method for removing impurity metals by pretreating and sorting waste circuit board copper powder | |
| CN109266860A (en) | A kind of innoxious recovery method of throwaway substrates recycling | |
| CN100410394C (en) | Mehtod for producing zinc concentrate and lead concentrate using zinc oxide ore and zinc slag | |
| CN106282610A (en) | From containing the method for recovery indium liquid crystal indium concentrate | |
| CN108070528B (en) | A kind of recovery system and recovery method of spent resin powder | |
| CN113481371A (en) | Method for efficiently recovering antimony, bismuth, copper and silver from silver separating slag of lead anode slime | |
| CN111748694A (en) | Method for enriching and recovering vanadium resource in vanadium-rich slag | |
| CN105907976B (en) | One kind Recover palladium from waste mobile phone electronic component（Pd）Method | |
| CN105039741B (en) | Enrichment and separation method for tin element in multi-metal mixed resources of waste printed circuit board | |
| CN111004921A (en) | Method for recovering copper in scrap copper smelting slag | |
| CN105274567B (en) | The production technology of high-frequency electrolysis high-purity silver |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190322 |
|
| WD01 | Invention patent application deemed withdrawn after publication |