CN117230313B - Tin-lead immersing agent and process for treating tin and lead in electronic garbage - Google Patents
Tin-lead immersing agent and process for treating tin and lead in electronic garbage Download PDFInfo
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- CN117230313B CN117230313B CN202311527930.8A CN202311527930A CN117230313B CN 117230313 B CN117230313 B CN 117230313B CN 202311527930 A CN202311527930 A CN 202311527930A CN 117230313 B CN117230313 B CN 117230313B
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 35
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 title description 15
- 238000002386 leaching Methods 0.000 claims abstract description 89
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 239000010793 electronic waste Substances 0.000 claims abstract description 34
- 125000000524 functional group Chemical group 0.000 claims abstract description 22
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000003814 drug Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 239000011133 lead Substances 0.000 abstract description 84
- 239000011135 tin Substances 0.000 abstract description 81
- 230000000694 effects Effects 0.000 abstract description 19
- 238000009854 hydrometallurgy Methods 0.000 abstract description 6
- 238000002791 soaking Methods 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 229910001432 tin ion Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 35
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- NAXKFVIRJICPAO-LHNWDKRHSA-N [(1R,3S,4R,6R,7R,9S,10S,12R,13S,15S,16R,18S,19S,21S,22S,24S,25S,27S,28R,30R,31R,33S,34S,36R,37R,39R,40S,42R,44R,46S,48S,50R,52S,54S,56S)-46,48,50,52,54,56-hexakis(hydroxymethyl)-2,8,14,20,26,32,38,43,45,47,49,51,53,55-tetradecaoxa-5,11,17,23,29,35,41-heptathiapentadecacyclo[37.3.2.23,7.29,13.215,19.221,25.227,31.233,37.04,6.010,12.016,18.022,24.028,30.034,36.040,42]hexapentacontan-44-yl]methanol Chemical compound OC[C@H]1O[C@H]2O[C@H]3[C@H](CO)O[C@H](O[C@H]4[C@H](CO)O[C@H](O[C@@H]5[C@@H](CO)O[C@H](O[C@H]6[C@H](CO)O[C@H](O[C@H]7[C@H](CO)O[C@@H](O[C@H]8[C@H](CO)O[C@@H](O[C@@H]1[C@@H]1S[C@@H]21)[C@@H]1S[C@H]81)[C@H]1S[C@@H]71)[C@H]1S[C@H]61)[C@H]1S[C@@H]51)[C@H]1S[C@@H]41)[C@H]1S[C@H]31 NAXKFVIRJICPAO-LHNWDKRHSA-N 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 229910020220 Pb—Sn Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
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- 239000002699 waste material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 150000002668 lysine derivatives Chemical class 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- OLYPWXRMOFUVGH-LURJTMIESA-N N(2)-methyl-L-lysine Chemical compound CN[C@H](C(O)=O)CCCCN OLYPWXRMOFUVGH-LURJTMIESA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
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- 231100000206 health hazard Toxicity 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- KPNBUPJZFJCCIQ-LURJTMIESA-N methyl L-lysinate Chemical compound COC(=O)[C@@H](N)CCCCN KPNBUPJZFJCCIQ-LURJTMIESA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JAYUDPKFDQGKFQ-UHFFFAOYSA-N n,n-diethylethanamine;ethanol Chemical compound CCO.CCN(CC)CC JAYUDPKFDQGKFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 nickel and iron Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Classifications
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a tin and lead soaking agent and a process for treating tin and lead in electronic garbage by using the same, and belongs to the technical field of hydrometallurgy. The tin and lead leaching agent takes a cyclic hetero-oxygen ring as a molecular skeleton, and functional groups are introduced into the structure of the agent to prepare a series of derivatives, so that the agent has the effect of efficiently leaching tin and lead in electronic waste. In the process of treating tin and lead in electronic waste, the concentration of electronic waste powder and ore pulp are controlled within a reasonable range, leaching agents and pH regulators are sequentially added into the electronic waste powder, tin, lead and alloys thereof in the electronic waste are efficiently converted into metal ions, meanwhile, the electronic waste powder slurry is adjusted to a proper pH value, and the selective leaching of tin and lead in the electronic waste is realized by controlling the types, the numbers, the positional relationship and the spatial three-dimensional structures of functional groups in the molecular structure of the leaching agents so that the tin ions and the lead ions are complexed with the functional groups in the leaching agents in a specific mode.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a tin and lead soaking agent and a process for treating tin and lead in electronic waste by using the same.
Background
Printed Circuit Boards (PCBs) are one of the most complex and valuable components in Electrical and Electronic Equipment (EEEs). However, the discarded printed circuit board belongs to electronic waste, and contains more than 40 metals, such as metals harmful to the environment (e.g. Pb, cr, as, cd and Hg) and other metals with economic value (e.g. Cu, au, ag and Pd). The recovery of metals from electronic waste is of great importance both for environmental protection and for resource reuse.
In contrast to recovering metal from natural resources, secondary resources must completely remove their harmful metal components before the plastic substrate is incinerated. Hydrometallurgy has been successfully used to recover valuable metals (such as Cu, au, ag and Pd) in electronic waste, but few other metals, such as base metals and toxic metals, have been studied. While noble metals (Au, ag and Pd) represent the main profitable space for electronic waste recovery, research into other metals is beneficial to confirm the contribution and value of electronic waste recovery work from an environmental point of view, such as base metals Sn, heavy metals Pb.
Electronic waste typically includes ECs (resistors, capacitors, chips, etc.), solder masks, solder materials, metal coatings, and polymeric substrates. The traditional commercial Pb-Sn alloy (63% Sn-37% Pb) has low cost, good performance and melting temperature (183 ℃) and is the main raw material of most welding materials.
At present, the technology for treating Pb-Sn welding materials in electronic garbage is mainly based on a pyrogenic process, and utilizes the characteristic of low melting points of tin and lead to heat at high temperature so as to melt the Pb-Sn welding materials to form tin and lead vapor, thereby recycling the Pb-Sn welding materials. The most obvious defect of the process is that the harm to the health of workers is great in the production process. At the same time, the environment is seriously polluted.
To solve the above problems, hydrometallurgical processes have significant advantages, but there are still corresponding problems.
For example, jadhav and Hocheng (Jadhav, u., hocheng, h., 2015, hydrometallurgical recovery of metals from large printed circuit board pieces, sci, rep, 5, 14574) use a high concentration (10M) sodium hydroxide solution to dissolve the solder mask, which is inefficient, long in leaching time, high in sodium hydroxide consumption, and high in energy consumption, and cannot meet the expected requirements of the enterprise. To achieve efficient leaching of tin-lead, some researchers have used a combination of oxidizing agents (e.g., hydrogen peroxide and Sn 4+ ) The combined acids (e.g., methanesulfonic acid (MSA) and hydrochloric acid) or the use of oxidizing acids (e.g., nitric acid) dissolve the Sn-Pb solder according to the redox reaction. However, the acids used in the method may release toxic gases (such as nitrogen oxide gas), and at the same time, other metals, such as nickel and iron, are often leached together in the process of leaching the Sn-Pb solder, which is unfavorable for the purification of subsequent metals.
In conclusion, the current agents used in the hydrometallurgical process for treating tin and lead in electronic waste have the limitations of poor metal leaching selectivity, low aging, high energy consumption and the like. In view of the above, it is necessary to design a leaching agent and a process for treating tin and lead in electronic waste to solve the above problems.
Disclosure of Invention
The invention aims to provide a tin and lead soaking agent and a process for treating tin and lead in electronic waste by using the same, wherein the tin and lead soaking agent takes a cyclic hetero-oxygen ring as a molecular skeleton, the agent is modified on the basis of ensuring the solubility of the agent in water, functional groups are introduced into the structure of the agent, and functions are given to the agent through the synergistic effect among the functional groups, so that a series of derivatives are prepared, and the effect of efficiently leaching tin and lead in the electronic waste is achieved. In the process for treating lead and tin in electronic garbage, the invention ensures that chelating action is generated between the cyclic hetero-oxygen ring and tin and lead ions by strictly controlling leaching conditions and strictly controlling the types of cyclic hetero-oxygen rings in the molecular structure of a leaching medicament and introducing functional groups of specific types, quantity and spatial arrangement, thereby greatly shortening the time for dissolving the tin and the lead while ensuring the effect of leaching the tin and the lead.
In order to achieve the aim of the invention, the invention provides a tin-and-lead-immersing medicament, wherein the tin-and-lead-immersing medicament is prepared by introducing functional groups into a molecule framework by taking a cyclic hetero-oxygen ring, and the structure of the tin-and-lead-immersing medicament comprises one or more of the following general formulas:
in R, R 7 、R 8 、R 9 And R is 10 Respectively represent functional groups introduced into the molecular skeleton.
The general formula A is as follows 1 General formula A 2 General formula A 3 One of the following:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Respectively represent functional groups introduced into the molecular skeleton.
The general formula A 1 Wherein R is 1 Is thatOr->；
When R is 1 Is thatWhen R is 2 Is->Or->；
When R is 1 Is thatWhen R is 2 Is->Or->Wherein, the method comprises the steps of, wherein,the connection site between the functional group and the cyclic hetero-oxygen ring is shown in the following description.
The general formula A 2 Wherein R is 3 Is thatOr->，R 4 Is->。
The saidGeneral formula A 3 Wherein R is 5 Is thatOr->；
When R is 5 Is thatWhen R is 6 Is->Or->；
When R is 5 Is thatWhen R is 6 Is->Or->。
In the general formula B, R 7 Is thatOr->Or (b)；
When R is 7 Is thatWhen R is 8 Is CH to CH 2 OH or->；
When R is 7 Is thatWhen R is 8 Is CH to CH 2 OH or->；
When R is 7 Is thatWhen R is 8 Is CH to CH 2 OH or->。
In the general formula C, R 9 Is thatOr->Or (b)；
When R is 9 Is thatWhen R is 10 Is CH to CH 2 OH or->；
When R is 9 Is thatWhen R is 10 Is CH to CH 2 OH or->；
When R is 9 Is thatWhen R is 10 Is CH to CH 2 OH or->。
The invention also provides a process for treating tin and lead in electronic garbage by adopting the tin-lead immersing agent, which comprises the following steps:
s1, crushing electronic waste to be detected to a particle size smaller than 50 meshes to obtain a material, adding water into the material, and stirring to obtain ore pulp with preset concentration;
s2, adding one or more of the leaching agents into the ore pulp to enable the leaching agents to reach a preset concentration;
s3, adding sodium hydroxide, and adjusting the pH value of the ore pulp to 10-14; stirring and leaching tin and lead.
As a further improvement of the invention, in the step S1, the part with the granularity smaller than 50 meshes in the material accounts for 90% of the total mass of the mineral powder, and the mass concentration of the material is 5% -30%.
In the step S2, the preset concentration of the leaching agent in the ore pulp is 0.01-0.1mol/L.
In the step S3, the temperature of ore pulp is 20-80 ℃ during stirring; the stirring time is 0.5-6h.
In the steps S1 and S3, the stirring speed is 100-300r/min.
The beneficial effects of the invention are as follows:
(1) The invention provides a tin-lead immersing medicament, which takes a cyclic hetero-oxygen ring as a molecular skeleton, modifies the medicament on the basis of ensuring the solubility of the medicament in water, introduces functional groups on the structure of the medicament, and endows the medicament with functions through the synergistic effect among the functional groups to prepare a series of derivatives, so that the medicament has the effect of efficiently leaching tin and lead in a circuit board. The tin-lead immersing agent is used for treating the electronic garbage, so that the health hazard to personnel caused by the exceeding of tin and lead concentration in the working environment in the traditional pyrogenic process of treating the electronic garbage can be effectively avoided; meanwhile, the defect that toxic gas is generated in the tin and lead dissolving process in the traditional acid leaching process is avoided.
(2) The invention expands the variety of traditional leaching agents and provides thinking and screening directions for the subsequent search of novel leaching agents which can be used industrially and on a large scale.
(3) The process for treating lead and tin in electronic garbage provided by the invention has the advantages that the leaching conditions are strictly controlled, meanwhile, the types of the cyclic hetero-oxygen ring in the molecular structure of the leaching medicament are strictly controlled, and the functional groups with specific types, numbers and spatial arrangements are introduced, so that the chelating effect with tin and lead ions is realized, the tin and lead removing effect is ensured, and meanwhile, the time for dissolving tin and lead is greatly shortened.
Drawings
FIG. 1 is a diagram showing the morphology and element distribution of the materials before the experiment.
FIG. 2 is a tin-lead immersion agent B 5 After the action, the material morphology is shown.
FIG. 3 is a tin-lead immersion agent B 5 After the action, the material elements form a graph.
FIG. 4 is a tin-lead immersion agent C 1 The action mechanism 1 of (2).
FIG. 5 is a tin-lead immersion agent C 1 The mechanism of action of (2) is shown in figure 2.
FIG. 6 is a scheme for furan cyclic acid synthesis.
Fig. 7 is a diagram of a circuit for synthesizing a tin-plated lead medicament.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a tin-and lead-immersing medicament, which is prepared by introducing functional groups into a molecule framework by taking a cyclic hetero-oxygen ring, and has the structure comprising one or more of the following general formulas:
general formula A general formula B general formula C
In R, R 7 、R 8 、R 9 And R is 10 Respectively represent functional groups introduced into the molecular skeleton.
The general formula A is as follows 1 General formula A 2 General formula A 3 One of the following:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Respectively represent functional groups introduced into the molecular skeleton.
The general formula A 1 Wherein, when R is 1 Is that，R 2 Is->The method comprises the steps of carrying out a first treatment on the surface of the Or when R 1 Is->，R 2 Is thatWhen A is 1 The structure is A 1-1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>Representing the position of attachment of the functional group to the cyclic hetero-oxygen ringPoints are the same as above and will not be described again;
general formula A 1 Wherein, when R is 1 And R is 2 Are allWhen A is 1 The structure is A 1-2 ；
General formula A 1 Wherein, when R is 1 Is that，R 2 Is->The method comprises the steps of carrying out a first treatment on the surface of the Or when R 1 Is->，R 2 Is thatWhen A is 1 The structure is A 1-3 ；
General formula A 1 Wherein, when R is 1 And R is 2 Are allWhen A is 1 The structure is A 1-4 ；
The general formula A 2 Wherein, when R is 3 Is that，R 4 Is->When A is 2 The structure is A 2-1 ；
General formula A 2 Wherein, when R is 3 Is that，R 4 Is->When A is 2 The structure is A 2-2 。
The general formula A 3 In,
when R is 5 Is that，R 6 Is->The method comprises the steps of carrying out a first treatment on the surface of the Or when R 5 Is->，R 6 Is thatWhen A is 3 The structure is A 3-1 ；
General formula A 3 Wherein, when R is 5 And R is 6 Are allWhen A is 3 The structure is A 3-2 ；
General formula A 3 Wherein, when R is 5 Is that，R 6 Is->The method comprises the steps of carrying out a first treatment on the surface of the Or when R 5 Is->，R 6 Is thatWhen A is 3 The structure is A 3-3 ；
General formula A 3 Wherein, when R is 5 And R is 6 Are allWhen A is 3 The structure is A 3-4 。
Namely, the molecular structure corresponding to the general formula A is one of the following structural formulas:
TABLE 1 molecular Structure of formula A
In the general formula B, when R 7 Is CH to CH 2 OH，R 8 Is thatThe method comprises the steps of carrying out a first treatment on the surface of the Or when R 7 Is that，R 8 Is CH to CH 2 In the case of OH, the B structure is B 1 ；
In the general formula B, when R 7 And R is 8 Are allWhen B is the structure B 2 ；
In the general formula B, when R 7 Is CH to CH 2 OH，R 8 Is thatThe method comprises the steps of carrying out a first treatment on the surface of the Or when R 7 Is that，R 8 Is CH to CH 2 In the case of OH, the B structure is B 3 ；
In the general formula B, when R 7 And R is 8 Are allWhen B is the structure B 4 ；
In the general formula B, when R 7 Is CH to CH 2 OH，R 8 Is thatThe method comprises the steps of carrying out a first treatment on the surface of the Or when R 7 Is that，R 8 Is CH to CH 2 In the case of OH, the B structure is B 5 ；
In the general formula B, when R 7 And R is 8 Are allWhen B is the structure B 6 。
Namely, the molecular structure corresponding to the general formula B is one of the following structural formulas:
TABLE 2 molecular Structure of formula B
In the general formula C, when R 9 Is that，R 10 Is CH to CH 2 OH; or when R is 9 Is CH to CH 2 OH，R 10 Is thatIn the case of C, the structure is C 1 ；
In the general formula C, when R 9 And R is 10 Are allIn the case of C, the structure is C 2 ；/>
In the general formula C, R 9 Is that，R 10 Is CH to CH 2 OH; or when R 9 Is CH to CH 2 OH，R 10 Is thatIn the case of C, the structure is C 3 ；
In the general formula C, when R 9 And R is 10 Are allIn the case of C, the structure is C 4 ；
In the general formula C, when R 9 Is that，R 10 Is CH to CH 2 OH; or when R 9 Is CH to CH 2 OH，R 10 Is thatIn the case of C, the structure is C 5 ；
In the general formula C, when R 9 And R is 10 Are allIn the case of C, the structure is C 6 。
Namely, the molecular structure corresponding to the general formula C is one of the following structural formulas:
TABLE 3 molecular Structure of formula C
The invention also provides a process for treating tin and lead in electronic garbage, which adopts any of the multifunctional group leaching agents to leach tin and lead, and comprises the following steps:
s1, crushing electronic waste to be detected to a particle size smaller than 50 meshes to obtain a material, and adding water into the material to stir to obtain ore pulp with preset concentration.
In the above steps, the stirring speed is preferably 100-300r/min, and the mass concentration of the ore pulp is preferably 5% -30%.
S2, adding one or more of the leaching agents into the ore pulp to enable the leaching agents to reach a preset concentration.
In the above step, the preset concentration of the leaching agent is preferably 0.01-0.1mol/L.
S3, adding sodium hydroxide, and adjusting the pH value of the ore pulp to 10-14; stirring and leaching tin and lead.
In the above steps, the temperature of the ore pulp is preferably 20-80 ℃, the stirring time is preferably 0.5-6h, and the stirring speed is preferably 100-300r/min.
In the leaching process, under the condition that an oxidant is not required to be additionally introduced, the tin and the lead undergo oxidation-reduction reaction and then undergo complexation reaction with a leaching agent to enter a solution phase, and finally the purpose of removing the tin and the lead in the electronic garbage is realized.
The present invention will be described with reference to specific examples in which a waste printed circuit board (one of electronic waste) containing metal resources, the main components of which are shown in table 4, was selected. Wherein Au, ag, pt, pd is in g/t.
TABLE 4 major Components of waste Circuit Board
| Element(s) | Au* | Ag* | Pt* | Pd* | Cu | Fe |
| Content (wt%) | 38.08 | 246.36 | 0.13 | 3.10 | 18.95 | 4.41 |
| Element(s) | Sn | Ni | Zn | Pb | Al | Cd |
| Content (wt%) | 3.62 | 0.30 | 2.43 | 1.70 | 2.77 | <0.005 |
Example 1
The embodiment provides a process for treating tin and lead in electronic garbage by tin immersion and lead medicament, which comprises the following steps:
s1, preparing ore pulp:
the waste printed circuit board (electronic garbage) is crushed, screened, uniformly mixed and reduced until the particle size is smaller than 50 meshes to obtain the material, and the part of the material with the particle size smaller than 50 meshes is ensured to account for 90 percent of the total mass of the material. And then adding water into the materials and stirring at the stirring speed of 100r/min to obtain ore pulp with the mass concentration of 10%.
S2, adding a tin-dipping and lead-adding medicament:
adding leaching agent A into ore pulp prepared in step S1 1-1 The total concentration of the leaching agent in the ore pulp is 0.05mol/L.
S3, adjusting the pH value of a leaching system:
and (3) adding sodium hydroxide into the ore pulp in the step S2, and adjusting the pH value of the ore pulp to 13. After the temperature is restored to the room temperature, stirring is carried out for 4 hours at the temperature of the ore pulp of 50 ℃, the stirring speed is 100r/min, and tin and lead are leached.
Examples 2 to 22
Embodiments 2-22 provide a process for treating tin and lead in electronic waste by using tin-dipping and lead-adding agents, which is different from embodiment 1 only in that in step S2, the types of added tin-dipping and lead-adding agents are different, and the other agents are substantially the same as embodiment 1, and are not described herein.
The leaching rates of tin and lead in examples 1 to 22 are shown in Table 5:
TABLE 5 leaching Rate of tin and lead in examples 1-22
；/>
；/>
；/>
As is clear from table 5, the leaching agent has an effect of leaching tin and lead. The introduction of the annular furan structure improves the dissolving capacity of the leached medicament to the greatest extent, and simultaneously, the lone pair electrons on the oxygen atoms on the furan ring are mutually cooperated with the functional groups, so that the effect of chelating metal ions is achieved.
Tin-immersion, lead preparation B as in example 15 5 For example, the morphology and elemental composition of the materials before and after the experiment are shown in fig. 1, fig. 2 and fig. 3.
Tin-immersion and lead-acid agent C as in example 17 1 The mechanism of action is shown in figures 4 and 5, for example.
Examples 23 to 26 and comparative examples 1 to 4
Examples 23-26 and comparative examples 1-4 respectively provide a process for treating tin and lead in electronic waste by using tin-leaching and lead-leaching agents, and compared with examples 1-2, the difference is that in step S1, examples 23 and 25 and comparative examples 1 and 3 are different from example 1 in pulp concentration, and the other examples are substantially the same as example 1, and are not described herein; examples 24 and 26 and comparative examples 2 and 4 were similar to example 2 except that the slurry concentration in step S1 was different from that in example 2, and the details thereof were not repeated here.
The leaching rates of tin and lead in examples 23 to 26 and comparative examples 1 to 4 are shown in Table 6:
TABLE 6 leaching rates of tin and lead in examples 23-26 and comparative examples 1-4
| Examples | Pulp concentration (%) | Leaching Rate of tin (%) | Leaching yield of lead (%) |
| Example 1 | 10 | 93 | 95 |
| Example 2 | 10 | 94 | 95 |
| Example 23 | 5 | 97 | 96 |
| Example 24 | 5 | 95 | 98 |
| Example 25 | 30 | 91 | 92 |
| Example 26 | 30 | 90 | 93 |
| Comparative example 1 | 1 | 97 | 96 |
| Comparative example 2 | 1 | 95 | 96 |
| Comparative example 3 | 40 | 84 | 87 |
| Comparative example 4 | 40 | 86 | 82 |
As can be seen from table 6, under the same conditions, as the concentration of the slurry increases, the leaching rates of tin and lead decrease, and the phenomenon causes can be summarized as follows: firstly, as the concentration of ore pulp is increased, the mass transfer between the reaction liquid and the solid is affected in the leaching process; secondly, as the concentration of ore pulp is increased, the relative molar ratio of leached medicament to leached metal in minerals is changed, and when the concentration of ore pulp reaches 40%, the dosage of medicament is relatively insufficient, so that the leaching rate of tin and lead is affected. In addition, when the concentration of the pulp is too low (< 5%) under the same conditions, the industrial production is not facilitated, for example, water resources are wasted, and a large amount of wastewater is generated, so that the environmental protection cost of enterprises is further increased for realizing the environmental protection discharge of the wastewater.
The other tin and lead leaching agents have similar influence on tin and lead leaching rates along with different concentrations of ore pulp.
Examples 27 to 30 and comparative examples 5 to 12
Examples 27-30 and comparative examples 5-12 provide a process for treating tin and lead in electronic waste with tin-and lead-leaching agents, which is different from examples 1-2 in that examples 27, 29 and comparative examples 5, 7, 9 and 11 are different from example 1 in concentration of tin-and lead-leaching agents in step S2, and are otherwise substantially the same as example 1, and are not repeated herein; examples 28 and 30 and comparative examples 6, 8, 10 and 12 were similar to example 2 except that the concentration of the tin-plated and lead-plated agents in step S2 was different from that in example 2, and the details thereof were not repeated here.
The leaching rates of tin and lead in examples 27 to 30 and comparative examples 5 to 12 are shown in Table 7:
TABLE 7 leaching rates of tin and lead in examples 27-30 and comparative examples 5-12
| Examples | Concentration of agent (mol/L) | Leaching Rate of tin (%) | Leaching yield of lead (%) |
| Example 1 | 0.05 | 93 | 95 |
| Example 2 | 0.05 | 94 | 95 |
| Example 27 | 0.01 | 91 | 87 |
| Example 28 | 0.01 | 90 | 90 |
| Example 29 | 0.1 | 93 | 96 |
| Example 30 | 0.1 | 93 | 98 |
| Comparative example 5 | 0.005 | 90 | 79 |
| Comparative example 6 | 0.005 | 88 | 72 |
| Comparative example 7 | 0.001 | 65 | 42 |
| Comparative example 8 | 0.001 | 67 | 38 |
| Comparative example 9 | 0 | 12 | 4 |
| Comparative example 10 | 0 | 9 | 6 |
| Comparative example 11 | 0.2 | 93 | 95 |
| Comparative example 12 | 0.2 | 92 | 95 |
As is clear from Table 7, the leaching rates of tin and lead increased with the increase in the concentration of the tin-and lead-leaching agent (from 0.001mol/L to 0.1 mol/L). When the concentration of the tin-lead-immersing agent is too low (less than or equal to 0.001 mol/L), the tin-lead immersing effect is reduced relative to the optimal condition, but the effect is still obvious, and the reason is presumed to be that the introduced tin-lead-immersing agent has the effect of catalyzing tin and lead to be dissolved in the tin-lead dissolving process. When no tin-and lead-leaching agent was introduced (comparative examples 9, 10), it was found that: under the same conditions, tin and lead cannot be leached effectively. Furthermore, the designed tin-lead immersing agent has tin-lead dissolving effect and tin-lead catalyzing effect. When the concentration of the multi-tin-leaching and lead medicament is too high (more than or equal to 0.2 mol/L), the tin and lead leaching effect is stable and is not improved.
Other tin and lead leaching agents have similar influences on tin and lead leaching rates according to different concentrations.
Examples 31 to 32 and comparative examples 13 to 14
Examples 31-32 and comparative examples 13-14 provide a process for treating tin and lead in electronic waste with tin-and lead-leaching agents, which is different from example 1 in that in step S3, the pH of the pulp is different, and the other processes are substantially the same as in example 1, and are not repeated here.
The leaching rates of tin and lead in examples 31 to 32 and comparative examples 13 to 14 are shown in Table 8:
TABLE 8 leaching rates of tin and lead in examples 31-32 and comparative examples 13-14
| Examples | pH value of | Leaching Rate of tin (%) | Leaching yield of lead (%) |
| Example 1 | 13 | 93 | 95 |
| Example 31 | 10 | 47 | 32 |
| Example 32 | 14 | 93 | 94 |
| Comparative example 13 | 9 | — | 21 |
| Comparative example 14 | 8 | — | — |
As is clear from table 8, the leaching agent had no leaching effect on tin and lead at a pulp pH of 8. Under the condition that the pH value of ore pulp is 9, the leaching agent has no leaching effect on tin. With the rising of the pH value of the ore pulp, when the pH value of the ore pulp is more than or equal to 10, the leaching effect on tin and lead is achieved. When the pH value of ore pulp is more than or equal to 13, the leaching rate of tin and lead reaches the peak value.
Other tin and lead leaching agents have similar influences on tin and lead leaching rates along with different pH values.
Examples 33 to 34 and comparative example 15
The embodiments 33-34 and the comparative example 15 provide a process for treating tin and lead in electronic waste by using tin-dipping and lead-chemical agents, which is different from the embodiment 1 in that the preset temperature is different in the step S3, and the other steps are substantially the same as the embodiment 1, and are not repeated herein.
The leaching rates of tin and lead in examples 33 to 34 are shown in Table 9:
TABLE 9 leaching rates of tin and lead in examples 33-34 and comparative example 15
| Examples | Preset temperature (DEG C) | Leaching Rate of tin (%) | Leaching yield of lead (%) |
| Example 1 | 50 | 93 | 95 |
| Example 33 | 20 | 90 | 91 |
| Example 34 | 80 | 96 | 97 |
| Comparative example 15 | 90 | 87 | 91 |
As is clear from Table 9, the increase in temperature is favorable for the leaching effect of tin and lead, but when the temperature is too high (90 ℃ C. Gtoreq.) the leaching effect of tin and lead starts to decrease, mainly because: firstly, the leached medicament reacts with other metals; secondly, under the high temperature condition, the chelate of tin and lead is subjected to oxidation-reduction reaction with air (oxygen) in the solution to be converted into hydroxides of high-valence tin and lead, and the hydroxides of high-valence tin and lead have poor solubility and are separated out from a leaching system. During the test, when the preset temperature is 90 ℃, a large amount of white substances can be observed during the leaching process.
The other tin and lead soaking agents have similar influence on the leaching rate of tin and lead along with different preset temperatures.
Example 35
This embodiment provides a tin-and lead-immersing agent A 1-3 The preparation method comprises the following specific steps:
s1, synthesizing furan cyclic acid
Furan ring dihydric alcohol and thionyl chloride are mixed according to a mole ratio of 1: and (3) adding 0.5 into an ether solution, and reacting for 4 hours at room temperature to obtain the chlorodiol. Then adding sodium cyanide under the condition that the pH is more than or equal to 10, wherein the molar ratio of the sodium cyanide to the chlorodiol is 1:0.8, 48h. And finally, adding dilute hydrochloric acid, maintaining the pH of the system at 3-6, heating and dissolving for 2h, and performing cold separation and purification to obtain furan cyclic acid.
S1, synthesizing tin-lead-immersing agent
Adding lysine into methanol solution, dripping sulfuric acid solution with volume fraction of 30% of 1% of total volume, heating to reflux for 12h, filtering while the solution is hot, washing with hot water for 3 times, and filtering again to obtain lysine methyl ester. Subsequently, methyl lysine was added to 5mol/L sodium hydroxide solution, and after complete dissolution, the temperature was raised to 120℃and the mixture was refluxed for 72 hours. Recrystallizing by ethanol-triethylamine (volume ratio of 50:1) to obtain the cyclic polycondensed lysine derivative. Finally, the cyclic polycondensed lysine derivative was reacted with furan cyclic acid in a molar ratio of 1:5 is added into methanol solution, the pH of the solution is adjusted to 10 by sodium hydroxide, and the solution is heated and refluxed for 6h. The solution after filtration was cold precipitated while it was hot to obtain white crystals. The solid was transferred to a methanol solution, and a 30% volume fraction sulfuric acid solution was added dropwise to the system to a pH of 6. Stirring for 30min, distilling under reduced pressure, and removing methanol to obtain tin-and lead-soaking agent A 1-3 。
In summary, the tin and lead leaching agent and the process for treating tin and lead in electronic waste provided by the invention can solve the problems of poor metal leaching selectivity, low aging, high energy consumption and the like in the existing hydrometallurgical process for treating tin and lead in electronic waste.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The tin and lead dipping medicament is characterized in that a functional group is introduced by taking a cyclic hetero-oxygen ring as a molecular skeleton, and the structure of the medicament comprises one or more of the following general formulas:
；
in R, R 7 、R 8 、R 9 And R is 10 Respectively representing functional groups introduced into the molecular skeleton;
the general formula A is as follows 1 General formula A 2 General formula A 3 One of the following:
；
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Respectively representing functional groups introduced into the molecular skeleton;
the general formula A 1 Wherein R is 1 Is thatOr->；
When R is 1 Is thatWhen R is 2 Is->Or->；
When R is 1 Is thatWhen R is 2 Is->Or->；
The general formula A 2 Wherein R is 3 Is thatOr->，R 4 Is->；
The general formula A 3 Wherein R is 5 Is thatOr->；
When R is 5 Is thatWhen R is 6 Is->Or->；
When R is 5 Is thatWhen R is 6 Is->Or->；
In the general formula B, R 7 Is thatOr->Or (b)；
When R is 7 Is thatWhen R is 8 Is CH to CH 2 OH or->；
When R is 7 Is thatWhen R is 8 Is CH to CH 2 OH or->；
When R is 7 Is thatWhen R is 8 Is CH to CH 2 OH or->；
In the general formula C, R 9 Is thatOr->Or (b)；
When R is 9 Is thatWhen R is 10 Is CH to CH 2 OH or->；
When R is 9 Is thatWhen R is 10 Is CH to CH 2 OH or->；
When R is 9 Is thatWhen R is 10 Is CH to CH 2 OH or->The method comprises the steps of carrying out a first treatment on the surface of the Wherein (1)>Represents the attachment site of the functional group to the cyclic hetero-oxygen ring.
2. A process for treating tin and lead in electronic waste, which is characterized by adopting the tin and lead leaching agent in claim 1 to leach tin and lead in the electronic waste, and comprising the following steps:
s1, crushing electronic waste to be detected to a particle size smaller than 50 meshes to obtain a material, adding water into the material, and stirring to obtain ore pulp with a mass concentration of 5% -30%;
s2, adding one or more of the tin-dipping and lead-containing agents into the ore pulp to enable the concentration of the tin-dipping and lead-containing agents to reach 0.01-0.1mol/L;
s3, adding sodium hydroxide, adjusting the pH value of the ore pulp to 10-14, stirring, and leaching tin and lead; the temperature of the ore pulp is 20-80 ℃ during stirring.
3. The process for treating tin and lead in electronic waste according to claim 2, wherein in the step S1, the part with the granularity smaller than 50 meshes in the material accounts for 90% of the total mass of the material.
4. The process for treating tin and lead in electronic waste according to claim 2, wherein in the step S3, the stirring time is 0.5-6h.
5. The process for treating tin and lead in electronic waste according to claim 2, wherein in the steps S1 and S3, the stirring speed is 100-300r/min.
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Citations (4)
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|---|---|---|---|---|
| US4851037A (en) * | 1986-01-17 | 1989-07-25 | Consiglio Nazionale Delle Ricerche | Collecting agents for the selective flotation of lead and zinc ores and a process for preparing the same |
| CN101586186A (en) * | 2009-06-19 | 2009-11-25 | 昆明理工大学 | Method for leaching chalcopyrite and corresponding leaching agent |
| US20130333524A1 (en) * | 2010-12-10 | 2013-12-19 | Prokumet Spa | Method for leaching copper oxide, replacing sulfuric acid with a non-polluting organic leaching agent |
| CN113292498A (en) * | 2021-06-16 | 2021-08-24 | 浙江工业大学 | 3-peroxybenzoic acid-1-methylimidazole chloride salt and preparation and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851037A (en) * | 1986-01-17 | 1989-07-25 | Consiglio Nazionale Delle Ricerche | Collecting agents for the selective flotation of lead and zinc ores and a process for preparing the same |
| CN101586186A (en) * | 2009-06-19 | 2009-11-25 | 昆明理工大学 | Method for leaching chalcopyrite and corresponding leaching agent |
| US20130333524A1 (en) * | 2010-12-10 | 2013-12-19 | Prokumet Spa | Method for leaching copper oxide, replacing sulfuric acid with a non-polluting organic leaching agent |
| CN113292498A (en) * | 2021-06-16 | 2021-08-24 | 浙江工业大学 | 3-peroxybenzoic acid-1-methylimidazole chloride salt and preparation and application thereof |
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