CN104975178A - Technology for non-acidification recycling of palladium in waste circuit board - Google Patents
Technology for non-acidification recycling of palladium in waste circuit board Download PDFInfo
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- CN104975178A CN104975178A CN201410133646.7A CN201410133646A CN104975178A CN 104975178 A CN104975178 A CN 104975178A CN 201410133646 A CN201410133646 A CN 201410133646A CN 104975178 A CN104975178 A CN 104975178A
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- palladium
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- circuit board
- waste circuit
- copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides a technology for non-acidification recycling of palladium in a waste circuit board based on current situation that an effective recycling method for palladium in a waste circuit board is scarce. The technology specifically comprises a pretreatment process, an enrichment process, a non-acidification liquid making process, a base metal separation process and a reducing process and is characterized by comprising the following steps: dissolving the metal part separated from the waste circuit board in a mixed solution prepared from copper salt and chloride salt, wherein the dissolved copper enters the solution to enrich palladium; separating and dissolving the enriched palladium with excess mixed solution; extracting palladium with an extraction agent; and performing reduction and precipitation to obtain sponge palladium with purity of 96-98%. The technology has the advantages of low cost, high efficiency, easy operation, mild reaction conditions and no strong acid or strong oxidant, and is an environment-friendly recycling method for palladium in a waste circuit board.
Description
Technical field
The present invention relates to a kind of cleaning and reclaiming method of the palladium utilized in discarded circuit board, belong to the solid waste process new technology in environment protection and comprehensive utilization of resources field, be particularly suitable for all kinds of environmentally friendly recycling containing palladium waste material.
Background technology
The Main Economic power of discarded circuit board process comes from the recovery of wherein valuable metal, wherein copper is the metal that in discarded circuit board, content is maximum, content accounts for 20% of discarded circuit board, there is high recovery value, silver and gold are mainly used in electronic devices and components and contact element, and palladium is the necessary starting material of wiring board hole metallization.Copper and precious metal (mainly gold and silver and palladium) account for more than 95% of wiring board total value, and for the wiring board bare board removing components and parts, palladium accounts for about 50% of its value.Therefore, the recovery of palladium has great importance for wiring board resource utilization.
In recent years, the study hotspot that wiring board reclaims is hydrometallurgy.But existing research mainly concentrates on the recovery of copper, gold and silver and other common metal.The research of Palladium recovery aspect is little, and in addition, existing method can not overcome the shortcoming of hydrometallurgy, and such as, length consuming time, Financial cost high causing can not operate in reality, use a large amount of acid and strong oxidizer etc.In wiring board, the committed step of Palladium recovery is palladium and being separated of other metals, being particularly separated of palladium and copper.In wiring board, copper content is high, and the character of copper and palladium is comparatively close.The method efficiency of existing selective dissolution copper is lower, and the part of copper can be caused to run off.Therefore, a committed step of Palladium recovery is the enrichment of palladium and the selective dissolution of copper.In precious metal recovery process, solvent extraction is the effective ways reclaiming low content of noble metal.It has a series of advantage, and such as, good selectivity, gained metal purity is high, utilizes multi-stage solvent extraction can realize the higher rate of recovery.The extraction agent of the palladium that current use is more has hydroxy derivatives, the organophosphorous extractant of dialkyl sulfide, dialkyl sulphoxide, ketoxime, quinoline.Wherein dialkyl sulfide has best selectivity and high extraction efficiency, obtains more concern.The present invention for starting material, by enrichment, without operations such as acidifying liquid making, base metal separation, extracting and separating, realizes the clean recovery of palladium with printed-wiring board (PWB) in waste and old electric electric product, establish a kind of easy and simple to handle, efficiency is high, the novel method of environmental protection.
Summary of the invention
The efficient recovery method that the object of the invention is for palladium in discarded circuit board is rare, traditional method organic efficiency is low, and need to use strong acid lixiviate, produce the present situation of secondary pollution simultaneously, there is provided that a kind of environmental friendliness, efficiency are high, cost is low, the Palladium recovery method of easy handling, the clean and effective realizing palladium in discarded circuit board reclaims.It is characterized in that: the discarded circuit board removing components and parts is heat-treated, be separated into metal component and nonmetallic ingredient through broken, sorting.Metal component copper sulfate in shortage and sodium chloride solution process, elemental copper is dissolved and then enriched palladium, then use excessive copper sulfate and sodium chloride solution that palladium is dissolved, then use isoamyl sulfide (S201) extraction of palladium, obtain sponge target finally by reduction.Concrete technology comprises following procedures:
1. pretreatment process: discarded circuit board is processed 30min at 270-330 DEG C of temperature, make Metals of Discarded Printed Circuit Boards and nonmetally to dissociate, obtain metal component and nonmetallic ingredient through cracking and sorting, metallic member for extracting palladium, nonmetallic ingredient otherwise processed or sale.
2. palladium enrichment operation: by CuSO
45H
2o and saturated sodium-chloride are that the ratio of 1:4.8 – 6 (g:ml) mixes with mass volume ratio, obtain reaction solution, then join in reaction solution by the metal-powder that 1 step obtains, under 30-60 DEG C of condition, stirring reaction 20-30min, in the process, controls copper and CuSO in metal powder
45H
2copper mol ratio ([Cu]/[Cu in O
2+]) being greater than 1.4, copper is converted into cuprous chloride, and palladium is enriched in non-dissolved residue.
3. palladium is without acidifying liquid making operation: again joined in reaction solution by dissolved residue non-in step 2, controls [Cu]/[Cu in solution
2+] mol ratio be less than 0.9, under 60-80 DEG C of condition, stirring reaction 30-60min, palladium all dissolves in the solution.
4. palladium and base metal separation circuit: the solution of 3 step gained is mixed (extraction phase is than O/A=1:5) with isoamyl sulfide solution, concussion extraction 2-5 minute.After solution layering, get upper strata and carry palladium organic phase, with the NH of 0.1-0.5mol/L
3h
2o(O/A=1:1), carry out secondary back extraction, palladium is with Pd (NH
3)
4cl
2form enter solution, be separated with base metal.
5. palladium reduction operation: the formic acid solution of dropping 98% concentration that blows slowly in the solution obtained in 4, add-on is pressed 1g palladium 2-3ml formic acid and is calculated, dropping limit, limit is stirred, until the palladium Restore All precipitation in solution, then suction filtration, with pure water throw out 2-3 time, under 105 DEG C of conditions, after dry 8-12h, obtain palladium sponge.
The enrichment operation of above-mentioned palladium is the rate of recovery in order to improve palladium, if the content of palladium higher (> 0.2g/kg) in wiring board, then enrichment operation can be omitted.The present invention, compared with conventional art, has clean environment firendly, mild condition, the reaction times is short, simple to operate, whole process does not use the advantage such as strong acid and strong oxidizer, is a kind of Palladium recovery method of environmental protection.
Content of the present invention is set forth further below in conjunction with Figure of description and embodiment.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of discarded circuit board non-acidizing Recover palladium.
Embodiment
The invention will be further described for embodiment plan given below; but can not be interpreted as it is limiting the scope of the invention; some nonessential improvement and adjustment that person skilled in art makes the present invention according to the content of the invention described above, still belong to protection scope of the present invention.
Embodiment 1:
Non-acidizing reclaims the technique of palladium in discarded circuit board, specifically comprises the following steps:
With reference to figure 1 technical process, take 5g CuSO45H2O, add 30mL saturated aqueous common salt, after CuSO45H2O dissolves completely, add the metal powder of 1.87g old circuit board enrichment gained, under 60 DEG C of conditions after stirring reaction 30min, suction filtration enters 120mL deionized water and obtains cuprous chloride, gets filter residue for subsequent use.Take 2.2g CuSO45H2O, add 12.7mL saturated aqueous common salt, after CuSO45H2O dissolves completely, filter residue is added, suction filtration after stirring reaction 30min under 60 DEG C of conditions.Suction filtration terminates, and filtrate and isoamyl sulfide solution (S201 is dissolved in n-dodecane, concentration 10%) are mixed (O/A=1:5), concussion extraction 2-5 minute.After solution layering, get the organic phase that palladium is carried on upper strata, the NH3H2O(O/A=1:1 with 0.1-0.5mol/L), carry out secondary back extraction.Palladium enters solution, is separated with base metal.Gained palladium strength of solution is 98.5mg/L, and palladium recovery rate is 96.9%.
Embodiment 2:
Non-acidizing reclaims the technique of palladium in discarded circuit board, specifically comprises the following steps:
With reference to figure 1 technical process, take 15g CuSO45H2O, add 90mL saturated aqueous common salt, after CuSO45H2O dissolves completely, then add the metal powder of 3.4g old circuit board enrichment gained, under 60 DEG C of conditions after stirring reaction 30min, suction filtration enters 350mL deionized water and obtains cuprous chloride.To filter containing cuprous chloride solution.Get filtrate for subsequent use.At this moment solution hydrolysis will produce a large amount of white cuprous chloride precipitations, by solution suction filtration after dark place hydrolysis 30min.Filter and terminate, filtrate and isoamyl sulfide solution (S201 is dissolved in n-dodecane, concentration 10%) are mixed (O/A=1:5), concussion extraction 2-5 minute.After solution layering, get the organic phase of upper strata supported palladium, the NH3H2O(O/A=1:1 with 0.1-0.5mol/L), carry out secondary back extraction.Palladium enters solution, is separated with base metal.Gained palladium strength of solution is 42.4mg/L, and palladium recovery rate is 97.4%.
In above-mentioned example, wiring board used is provided by one, Xiamen electronics offal treatment enterprise.This technique is applicable to the multiple recovery containing palladium in palladium waste material such as discarded TV SKD, discarded computer main board, waste mobile telephone mainboard, programme-controlled mainboard.The invention is not restricted to above-described embodiment, summary of the invention all can be implemented, and has good effect.
Claims (2)
1. non-acidizing reclaims the technique of palladium in discarded circuit board, specifically comprises the following steps:
(1) pretreatment process: discarded circuit board is processed 30min at 270-330 DEG C of temperature, makes Metals of Discarded Printed Circuit Boards and nonmetally to dissociate, obtaining metal-powder and nonmetallic ingredient through cracking and sorting;
(2) palladium enrichment operation: by CuSO
45H
2o and saturated sodium-chloride take mass volume ratio as 1:4.8 – 6(g:ml) ratio mix, obtain reaction solution, then the metal-powder obtained in step (1) joined in reaction solution, control copper and CuSO in metal powder
45H
2copper mol ratio ([Cu]/[Cu in O
2+]) be greater than 1.4, stirring reaction 20-30min under 30-60 DEG C of condition, make copper be converted into cuprous chloride, palladium is enrichment in residue;
(3) palladium is without acidifying liquid making operation: be separated by the residue of enriched palladium in step (2), according to the method preparation feedback liquid in (2), join in reaction solution by rich palladium residue, controls [Cu]/[Cu in solution
2+] mol ratio is less than 0.9, under 60-80 DEG C of condition, stirring reaction 30-60min, makes palladium dissolve in the solution;
(4) palladium and base metal separation circuit: mixed with isoamyl sulfide by the solution of step gained in (3), concussion extraction 2-5 minute, after solution layering, gets upper strata and carries palladium organic phase, with the NH of 0.1-0.5mol/L
3h
2o carries out back extraction, and palladium is with Pd (NH3)
4cl
2form enter solution, be separated with base metal;
(5) palladium reduction operation: the formic acid solution of dropping 98% concentration that blows slowly in the solution obtained in (4), add-on is pressed 1g palladium 2-3ml formic acid and is calculated, dropping limit, limit is stirred, until the palladium Restore All precipitation in solution, then suction filtration, with pure water throw out 2-3 time, under 105 DEG C of conditions, after dry 8-12h, obtain palladium sponge.
2. reclaim the technique of palladium in discarded circuit board according to the non-acidizing described in right 1, it is characterized in that: in step (4) palladium and base metal separation circuit, the extraction of isoamyl sulfide is in a ratio of O/A=1:5, NH
3h
2the back extraction of O is in a ratio of O/A=1:1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410133646.7A CN104975178B (en) | 2014-04-04 | 2014-04-04 | The technique that non-acidizing reclaims palladium in discarded circuit board |
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| CN201410133646.7A CN104975178B (en) | 2014-04-04 | 2014-04-04 | The technique that non-acidizing reclaims palladium in discarded circuit board |
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| CN104975178A true CN104975178A (en) | 2015-10-14 |
| CN104975178B CN104975178B (en) | 2017-06-27 |
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| CN201410133646.7A Expired - Fee Related CN104975178B (en) | 2014-04-04 | 2014-04-04 | The technique that non-acidizing reclaims palladium in discarded circuit board |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114717420A (en) * | 2022-03-15 | 2022-07-08 | 中国科学院生态环境研究中心 | Method for recycling copper, silver and gold step by utilizing waste printed circuit boards |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO90071A2 (en) * | 1984-09-07 | 1986-08-30 | Institutul De Chimie,Ro | PROCESS FOR RECOVERING PALLADIUM FROM SILVER AND COPPER FROM ALLOY WASTE |
| JPH07145427A (en) * | 1993-11-24 | 1995-06-06 | Tanaka Kikinzoku Kogyo Kk | Method for recovering and recycling palladium or palladium alloy from contact material |
| CN102181644A (en) * | 2011-04-13 | 2011-09-14 | 深圳市格林美高新技术股份有限公司 | Method for reclaiming rare noble metals from waste circuit board |
| CN102190327A (en) * | 2010-03-08 | 2011-09-21 | 沈祖达 | Cuprous oxide preparation method |
| CN103397186A (en) * | 2013-07-12 | 2013-11-20 | 湖南省同力电子废弃物回收拆解利用有限公司 | Regenerating method and process for recycling rare precious metals from electronic wastes |
-
2014
- 2014-04-04 CN CN201410133646.7A patent/CN104975178B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO90071A2 (en) * | 1984-09-07 | 1986-08-30 | Institutul De Chimie,Ro | PROCESS FOR RECOVERING PALLADIUM FROM SILVER AND COPPER FROM ALLOY WASTE |
| JPH07145427A (en) * | 1993-11-24 | 1995-06-06 | Tanaka Kikinzoku Kogyo Kk | Method for recovering and recycling palladium or palladium alloy from contact material |
| CN102190327A (en) * | 2010-03-08 | 2011-09-21 | 沈祖达 | Cuprous oxide preparation method |
| CN102181644A (en) * | 2011-04-13 | 2011-09-14 | 深圳市格林美高新技术股份有限公司 | Method for reclaiming rare noble metals from waste circuit board |
| CN103397186A (en) * | 2013-07-12 | 2013-11-20 | 湖南省同力电子废弃物回收拆解利用有限公司 | Regenerating method and process for recycling rare precious metals from electronic wastes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114717420A (en) * | 2022-03-15 | 2022-07-08 | 中国科学院生态环境研究中心 | Method for recycling copper, silver and gold step by utilizing waste printed circuit boards |
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Granted publication date: 20170627 Termination date: 20180404 |