CN104975178B - The technique that non-acidizing reclaims palladium in discarded circuit board - Google Patents
The technique that non-acidizing reclaims palladium in discarded circuit board Download PDFInfo
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- CN104975178B CN104975178B CN201410133646.7A CN201410133646A CN104975178B CN 104975178 B CN104975178 B CN 104975178B CN 201410133646 A CN201410133646 A CN 201410133646A CN 104975178 B CN104975178 B CN 104975178B
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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
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Abstract
The present invention is for the rare present situation of effective recovery method of palladium in current discarded circuit board, the technique that a set of non-acidizing reclaims palladium in discarded circuit board is provided, pretreatment process, enrichment operation is specifically included, without acidifying liquid making operation, base metal separation circuit and reduction operation.It is characterized in that：The metal part that will be sorted out in discarded circuit board is dissolved in the mixed solution that mantoquita and villaumite are prepared, enter solution after copper dissolution, it is enriched with palladium, the palladium after enrichment is dissolved after separation with excessive above-mentioned mixed solution again, palladium is taken with extractant, the palladium sponge that purity is 96 98% is obtained by precipitate reduction.The process costs are low, efficiency high, easily operated, and reaction condition is gentle, and whole process does not use strong acid and strong oxidizer, is a kind of recovery method of palladium in discarded circuit board of environmental protection.
Description
Technical field
The present invention relates to a kind of cleaning and reclaiming method of the palladium in utilization discarded circuit board, belong to environmental protection comprehensive with resource
Close using the solid waste treatment new technology in field, be particularly suitable for all kinds of environmentally friendly resource profits containing palladium waste material
With.
Background technology
The Main Economic power of discarded circuit board treatment comes from the recovery of wherein valuable metal, and wherein copper is discarded circuit
The most metal of content in plate, content accounts for the 20% of discarded circuit board, and with high recovery value, silver and gold are mainly used in
Electronic component and contact, palladium are the necessary raw material of wiring board hole metallization.Copper and noble metal（Mainly gold, silver and palladium）
More than the 95% of wiring board total value is accounted for, for the wiring board bare board for removing component, palladium accounts for 50% or so of its value.Cause
This, the recovery of palladium has great importance for wiring board resource.
In recent years, the study hotspot that wiring board is reclaimed is hydrometallurgy.But it is existing research be concentrated mainly on copper, gold,
The recovery of silver and other common metals.Seldom, the method that in addition, there will be can not overcome hydrometallurgy for research in terms of Palladium recovery
Shortcoming, for example, time-consuming, financial cost it is high cause in practice it is inoperable, use substantial amounts of acid and strong oxidizer etc..Wiring board
The committed step of middle Palladium recovery is that palladium is separated with other metals, and particularly palladium is separated with copper.In assist side, copper content pole
Height, copper is closer to the property of palladium.The method of existing selective dissolution copper is less efficient, and the part of copper can be caused to flow
Lose.Therefore, a committed step of Palladium recovery is the selective dissolution of the enrichment with copper of palladium.It is molten in noble metal recovery process
Agent extraction is the effective ways for reclaiming low content of noble metal.It has a series of advantage, for example, preferably selectivity, gained
Metal purity is high, and the rate of recovery higher can be realized using multitple extraction.There is dialkyl group using the extractant of more palladium at present
Thioether, dialkyl sulphoxide, ketoxime, the hydroxy derivatives of quinoline, organophosphorous extractant.Wherein dialkyl sulfide has best choosing
Selecting property and extraction efficiency high, have obtained more concerns.The present invention is with printed substrate in waste and old electric electric product as former
Material, by enrichment, without operations such as acidifying liquid making, base metal separation, extract and separates, realizes that the cleaning of palladium is reclaimed, and establishes one
Plant easy to operate, efficiency high, the new method of environmental protection.
The content of the invention
Effective recovery method that the purpose of the present invention is directed to palladium in discarded circuit board is rare, and conventional method organic efficiency is low
Under, and need to use strong acid to extract, while producing the present situation of secondary pollution, there is provided a kind of environment-friendly, efficiency high, low cost,
Easily operated Palladium recovery method, realizes that the clean and effective of palladium in discarded circuit board is reclaimed.It is characterized in that：Component will be removed
Discarded circuit board is heat-treated, by crushing, being separated into metal component and nonmetallic ingredient.Metal component is with shortage
Copper sulphate and sodium chloride solution treatment, elemental copper is dissolved and then enriched palladium, then use excessive copper sulphate and sodium chloride
Solution dissolves palladium, then uses isoamyl sulfide（S201）Extraction of palladium, sponge target is obtained finally by reduction.Concrete technology includes
Following procedures：
1. pretreatment process：Discarded circuit board is processed into 30min at a temperature of 270-330 DEG C, makes gold in discarded circuit board
Category and nonmetallic dissociation, metal component and nonmetallic ingredient are obtained through cracking and sorting, and metal part is used to extract palladium, nonmetallic group
Divide otherwise processed or sale.
2. palladium is enriched with operation：By CuSO4·5H2O and saturated sodium-chloride with mass volume ratio be 1:4.8–6(g:Ml ratio)
Example mixing, obtains reaction solution, and then the metal dust that 1 step is obtained is added in reaction solution, under the conditions of 30-60 DEG C, stirs
Reaction 20-30min is mixed, in the process, copper and CuSO in control metal powder4·5H2Copper mol ratio in O（[Cu]/[Cu2+]）
More than 1.4, copper is converted into stannous chloride, and palladium is enriched in undissolved residue.
3. palladium is without acidifying liquid making operation：Undissolved residue in step 2 is added in reaction solution again, in control solution
[Cu]/[Cu2+] mol ratio be less than 0.9, under the conditions of 60-80 DEG C, stirring reaction 30-60min, palladium is all dissolved in solution
In.
4. palladium and base metal separation circuit：Solution obtained by 3 steps is mixed with isoamyl sulfide solution（Extraction phase ratio
O/A=1:5）, concussion extraction 2-5 minutes.After after solution layering, take upper strata and carry palladium organic phase, with the NH of 0.1-0.5mol/L3·
H2O（O/A=1:1）, two grades of back extraction are carried out, palladium is with Pd (NH3)4Cl2Form enter solution, separated with base metal.
5. palladium reduces operation：Slowly the formic acid solution of 98% concentration is added dropwise in the solution obtained toward 4, addition presses 1g palladiums
2-3ml formic acid is calculated, and is stirred when being added dropwise, until the palladium Restore All precipitation in solution, is then filtered by suction, uses pure water
Sediment 2-3 times, palladium sponge is obtained after 8-12h is dried under the conditions of 105 DEG C.
The enrichment operation of above-mentioned palladium is in order to improve the rate of recovery of palladium, if the content of palladium is higher in wiring board（＞ 0.2g/
kg）, then being enriched with operation can omit.The present invention compared with conventional art, with clean environment firendly, mild condition, reaction time it is short,
The advantages of simple to operate, whole unused strong acid and strong oxidizer, be a kind of Palladium recovery method of environmental protection.
Present disclosure is expanded on further with reference to Figure of description and embodiment.
Brief description of the drawings
Fig. 1 is the process chart of discarded circuit board non-acidizing Recover palladium.
Specific embodiment
The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention
Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention
It is whole, still fall within protection scope of the present invention.
Embodiment 1：
Non-acidizing reclaims the technique of palladium in discarded circuit board, specifically includes the following steps：
With reference to Fig. 1 technological processes, 5g CuSO45H2O are weighed, add 30mL saturated aqueous common salts, treat that CuSO45H2O is complete
After CL, the metal powder obtained by the enrichment of 1.87g old circuit boards is added, under the conditions of 60 DEG C after stirring reaction 30min, suction filtration enters
120mL deionized waters obtain stannous chloride, take filter residue standby.2.2g CuSO45H2O are weighed, 12.7mL saturated common salts are added
Water, after CuSO45H2O is completely dissolved, filter residue is added, suction filtration after stirring reaction 30min under the conditions of 60 DEG C.Suction filtration terminates,
By filtrate and isoamyl sulfide solution（S201 is dissolved in n-dodecane, concentration 10%）Mixing（O/A=1:5）, 2-5 points of concussion extraction
Clock.After after solution layering, the organic phase that upper strata carries palladium is taken, with the NH3H2O of 0.1-0.5mol/L（O/A=1:1）, carry out two grades
Back extraction.Palladium enters solution, is separated with base metal.Gained palladium solution concentration 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 includes the following steps：
With reference to Fig. 1 technological processes, 15g CuSO45H2O are weighed, add 90mL saturated aqueous common salts, treat CuSO45H2O
After being completely dissolved, the metal powder obtained by the enrichment of 3.4g old circuit boards is subsequently adding, under the conditions of 60 DEG C after stirring reaction 30min,
Suction filtration enters 350mL deionized waters and obtains stannous chloride.To be filtered containing cuprous chloride solution.Take filtrate standby.At this moment solution water
Solution will produce substantial amounts of white stannous chloride to precipitate, by solution in suction filtration after dark place hydrolysis 30min.Filtering terminates, by filtrate with
Isoamyl sulfide solution（S201 is dissolved in n-dodecane, concentration 10%）Mixing（O/A=1:5）, concussion extraction 2-5 minutes.Treat molten
After liquid layering, the organic phase of upper strata supported palladium is taken, with the NH3H2O of 0.1-0.5mol/L（O/A=1:1）, carry out two grades of back extraction.
Palladium enters solution, is separated with base metal.Gained palladium solution concentration is 42.4mg/L, and palladium recovery rate is 97.4%.
In examples detailed above, wiring board used is provided by one, Xiamen electronics offal treatment enterprise.The technique is applied to useless
Abandon the recovery of palladium in various waste materials containing palladium such as TV SKD, discarded computer main board, waste mobile telephone mainboard, program control mainboard.This
Invention is not limited to above-described embodiment, and the content of the invention can be implemented, and with good effect.
Claims (2)
1. non-acidizing reclaims the technique of palladium in discarded circuit board, specifically includes the following steps：
(1) pretreatment process：Discarded circuit board is processed into 30min at a temperature of 270-330 DEG C, make Metals of Discarded Printed Circuit Boards and
Nonmetallic dissociation, metal dust and nonmetallic ingredient are obtained through cracking and sorting；
(2) palladium enrichment operation：By CuSO4·5H2O is with saturated sodium-chloride with mass volume ratio as 1g:The ratio mixing of 4.8-6mL,
Obtain reaction solution, then the metal dust obtained in step (1) be added in reaction solution, control metal powder in copper with
CuSO4·5H2Copper mol ratio ([Cu]/[Cu in O2+]) it is more than 1.4, the stirring reaction 20-30min under the conditions of 30-60 DEG C, make
Copper is converted into stannous chloride, and palladium is enriched with residue；
(3) palladium is without acidifying liquid making operation：The residue of enriched palladium in step (2) is separated, reaction is prepared according to the method in (2)
Liquid, rich palladium residue is added in reaction solution, [Cu]/[Cu in control solution2+] mol ratio be less than 0.9, in 60-80 DEG C of condition
Under, stirring reaction 30-60min makes palladium dissolve in the solution；
(4) palladium and base metal separation circuit：Solution obtained by step in (3) is mixed with isoamyl sulfide, concussion extraction 2-5
Minute, after after solution layering, take upper strata and carry palladium organic phase, with the NH of 0.1-0.5mol/L3·H2O is stripped, and palladium is with Pd
(NH3)4Cl2Form enter solution, separated with base metal；
(5) palladium reduction operation：Slowly the formic acid solution of 98% concentration is added dropwise in the solution obtained toward (4), addition presses 1g palladiums
2-3mL formic acid is calculated, and is stirred when being added dropwise, until the palladium Restore All precipitation in solution, is then filtered by suction, uses pure water
Sediment 2-3 times, palladium sponge is obtained after 8-12h is dried under the conditions of 105 DEG C.
2. the technique that palladium in discarded circuit board is reclaimed according to the non-acidizing described in claim 1, it is characterized in that：Step (4) palladium
In base metal separation circuit, the extraction of isoamyl sulfide is in a ratio of O/A=1:5, NH3·H2The back extraction of O is in a ratio of O/A=
1:1。
Priority Applications (1)
| 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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| 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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| CN104975178A CN104975178A (en) | 2015-10-14 |
| CN104975178B true 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114717420B (en) * | 2022-03-15 | 2023-09-05 | 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 board |
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 |
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