CN114107675A - Novel method and device for recovering metal palladium - Google Patents

Novel method and device for recovering metal palladium Download PDF

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Publication number
CN114107675A
CN114107675A CN202111435400.1A CN202111435400A CN114107675A CN 114107675 A CN114107675 A CN 114107675A CN 202111435400 A CN202111435400 A CN 202111435400A CN 114107675 A CN114107675 A CN 114107675A
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waste liquid
palladium
tank
sending
reaction
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CN202111435400.1A
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Inventor
王小广
陈祥衡
吴渤
石杨
李明军
王青龙
徐若飞
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Shenzhen Zhongke Outaihua Environmental Protection Technology Co ltd
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Shenzhen Zhongke Outaihua Environmental Protection Technology Co ltd
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Priority to CN202111435400.1A priority Critical patent/CN114107675A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a novel method for recovering metal palladium, which comprises the following steps: (A) sending the waste liquid into a waste liquid pool; (B) feeding the waste liquid into a reaction tank, and adding hydroxyl radicals on line to perform oxidation reaction; (C) sending the waste liquid into a precipitation filter tank, and adding alkali liquor or acid liquor; (D) and feeding the waste liquid into an electrolytic bath for electrolysis, recovering metal palladium, and feeding the electrolyzed waste liquid into a sewage plant for treatment. The new method of the invention thoroughly changes the defects of the original physical recovery method, and adopts a chemical method to carry out gel breaking on the colloid palladium and recover the ion palladium into the metal palladium.

Description

Novel method and device for recovering metal palladium
Technical Field
The invention relates to the field of PCBs, in particular to a method for recycling metal palladium and a special device.
Background
In national economic construction, the PCB is a basic industry for industrialization and informatization development, and along with the continuous development of economic construction, the PCB industry is rapidly developed. Both electroless copper plating and electroless gold plating in normal circuit board production produce palladium and are present in the waste liquor in the form of substantially colloidal palladium, so recovery of palladium is undertaken starting from colloidal palladium. At present, although the colloidal palladium can be effectively recovered by a physical method, the cost is too high, the recovery benefit is directly influenced, the colloidal palladium becomes a difficult point of a technical method for recovering the colloidal palladium, and the colloidal palladium is also a key problem which is always required to be solved by enterprises.
Because the economic value of palladium is very high, the usage amount of palladium in the production process is huge, and meanwhile, the usage amount of colloidal palladium is generally more than 10 times of that of ionic palladium, therefore, for the recovery technology of metal palladium, various enterprises actively research new technical methods so as to achieve low-cost recovery and create more economic benefits. However, to date, there has been no practical recovery technique.
Aiming at the current situation of recovering metallic palladium, a new technical method is needed to be researched at present to make up for the defects of the existing recovery of metallic palladium, so that the recovery of metallic palladium can be realized, the recovery benefit can be effectively improved, the problem of high-cost recovery can be better solved, and a better new path is found for the palladium recovery technology in chemical copper plating and chemical gold plating of the circuit board production process.
Disclosure of Invention
The technology of the invention provides an effective new chemical method recovery technology according to the defects of the existing physical method recovery technology of metal palladium, and can better solve the defects of the existing recovery technology of palladium. The new technical method is carried out by recovering both colloidal palladium and ionic palladium into metal palladium, and is characterized by solving the problem of converting the colloidal palladium into the ionic palladium, effectively controlling the precipitation of ionic tin and finally recovering the metal palladium through electrolysis. The technology utilizes a new chemical method and a new process, and firstly, gel breaking reaction is carried out on colloidal palladium in waste liquid.
The reaction principle is as follows:
[PdSn2]Cl6→Pd+2+Sn+2
gel breaking is carried out through reaction, colloid palladium in the waste liquid can be rapidly converted into ionic palladium and ionic tin through oxidation, then the ionic tin in the waste liquid can be precipitated through controlling according to the pH value of the waste liquid, and after the ionic tin is filtered and separated out, the palladium-containing waste liquid is sent to electrolysis for recycling metal palladium.
A novel process for recovering metallic palladium comprising the steps of:
(A) sending the waste liquid containing the colloidal palladium of the circuit board production line into a waste liquid pool for concentration;
(B) sending the waste liquid in the waste liquid tank into a reaction tank, adding an oxidant hydroxyl radical on line, carrying out oxidation reaction under stirring, and carrying out gel breaking on the colloidal palladium; the step utilizes the strong oxidizing property of hydroxyl free radicals to destroy the particle structure of the colloidal palladium so as to form ionic palladium and ionic tin in the waste liquid;
(C) sending the waste liquid of the reaction tank into a precipitation filter tank, and controlling and adding alkali liquor or acid liquor (firstly detecting the pH value, adding the alkali liquor into the slightly alkaline waste liquid and adding the acid liquor into the slightly acidic waste liquid) on line according to the pH value of the waste liquid to ensure that the ionic tin is almost completely precipitated, and then separating the ionic tin through filtration;
(D) and (3) sending the waste liquid of the precipitation filter tank into an electrolytic tank through a delivery pump, electrolyzing, recovering metal palladium, and sending the electrolyzed waste liquid to a sewage plant for treatment.
In the step (B), the hydroxyl radical is uniformly added by adopting a hydroxyl radical generator, the adding amount is 21-27 g/t of the waste liquid, and the reaction stirring time after the hydroxyl radical is added is 1.5-2 hours.
The novel method for recovering metal palladium, provided by the invention, comprises the following steps of (C), controlling the adding amount of the alkali liquor by controlling the pH value to be more than or equal to 8 when the concentrations of the acid liquor and the alkali liquor are 10% in step (C); when the acid liquor is required to be added, the adding amount of the acid liquor is controlled by the pH value being less than or equal to 3, so that the requirement that the ionic tin is almost completely precipitated can be met.
The device adopted by the novel method for recovering the metal palladium comprises a waste liquid pool, a reaction pool, a precipitation filter pool, a delivery pump and an electrolytic bath which are connected in sequence; the reaction tank is connected with a hydroxyl radical generator, and the precipitation filter tank is respectively connected with a lye tank and an acid tank.
The device comprises a reaction tank, a first waste liquid inlet, a second waste liquid inlet, a first oxidant feeding port, a second oxidant feeding port and a second oxidant feeding port, wherein the first waste liquid inlet and the second oxidant feeding port are arranged on the reaction tank; a second waste liquid inlet, an alkali liquid feeding port and an acid liquid feeding port are formed in the sedimentation filter tank; and a third waste liquid inlet and a waste liquid discharge outlet are arranged on the electrolytic cell.
The device of the invention is characterized in that a stirrer is arranged in the reaction tank.
The new method for recovering the metal palladium is different from the prior art in that:
the new method for recovering the metallic palladium thoroughly changes the defects of the original physical recovery method, and adopts a chemical method to carry out gel breaking on the colloidal palladium and recover the ionic palladium into the metallic palladium. Although the existing recovery method of colloidal palladium can effectively recover colloidal palladium by a physical method, the recovery benefit is influenced due to overhigh cost, and a feasible recovery technology does not exist so far. The research of the invention is carried out by adopting a novel chemical method, the colloidal palladium is quickly and effectively converted into ionic palladium and ionic tin by strong oxidation, and the ionic palladium and the ionic tin are filtered and separated, so that the recovery of metal palladium by electrolysis can be realized, the recovery benefit can be improved, the electrode plate structure is not influenced during electrolysis, and the problem of high-cost recovery of metal palladium can be better solved.
The invention can become a new method for recovering metal palladium, and most importantly, the originally adopted physical recovery technical method is changed, a new chemical method is adopted, particularly, colloidal palladium can be quickly and effectively converted into ionic palladium through a strong oxidation technology, a very key step is played for the process technology for recovering metal palladium, meanwhile, according to the performance of tin, a method for respectively controlling the pH value is adopted, so that ionic tin can be almost completely precipitated and can be filtered and separated, and the key second step is the new process method for recovering palladium provided by the invention, so that the recovery rate of palladium can be close to 95%, the recovery cost is reduced, the adverse effect on electrode plate hardening construction during electrolysis is avoided, and the whole process can be safely and stably carried out. Under the circumstance of no precedent, the method is an innovative attempt to recover the metal palladium, and a better new path is found for the palladium recovery technology in the electroless copper plating and the electroless gold plating of the circuit board production process.
The invention relates to a novel method for recovering metal palladium, which aims at the defect that the original colloidal palladium is recovered into the metal palladium, selects a novel chemical method through analysis and research, and finds a better new path for low-cost recovery. More importantly, the economic value of the palladium is high, and the amount of the palladium used in the production process is large. Meanwhile, the usage amount of the colloidal palladium is generally more than 10 times of that of ionic palladium, so that more economic benefits can be effectively created while the method for recovering metal palladium is solved.
The novel method and apparatus for recovering metallic palladium of the present invention will be further described with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus used in the novel method for recovering metallic palladium of the present invention.
Detailed Description
Example 1
As shown in fig. 1, the device adopted by the novel method for recovering metal palladium of the present invention comprises a waste liquid tank 1, a reaction tank 2, a precipitation filtration tank 3, a delivery pump 4 and an electrolytic bath 5 which are connected in sequence; the reaction tank 2 is connected with a hydroxyl radical generator 6, and the precipitation filter tank 3 is respectively connected with a lye tank 7 and an acid tank 8.
Wherein, a first waste liquid inlet and an oxidant feeding port are arranged on the reaction tank 2; a second waste liquid inlet, an alkali liquid feeding port and an acid liquid feeding port are formed in the sedimentation filter tank 3; a third waste liquid inlet and a waste liquid discharge outlet are arranged on the electrolytic cell 5; a stirrer 9 is provided in the reaction tank 2.
Example 2
A novel method for recovering metal palladium adopts the device of embodiment 1 for treatment, and specifically comprises the following steps:
(A) sending the waste liquid containing the colloidal palladium of the circuit board production line into a waste liquid pool 1 for concentration;
(B) sending the waste liquid in the waste liquid tank 1 into a reaction tank 2, adding an oxidant on line by adopting a hydroxyl radical generator 6, carrying out oxidation reaction under stirring, and destroying the particle structure of colloidal palladium to form ionic palladium and ionic tin; the oxidant is hydroxyl free radical, the adding amount is 21g/t of waste liquid, and the reaction stirring time after the hydroxyl free radical is added is 2 hours.
(C) Sending the waste liquid in the reaction tank 2 into a precipitation filtering tank 3, adding 10% alkali liquor on line, controlling the pH value of the waste liquid to be more than or equal to 8, realizing almost complete precipitation of the ionic tin, and removing the ionic tin through filtering separation;
(D) sending the waste liquid of the precipitation filter tank 3 into an electrolytic tank 5 through a delivery pump 4, and electrolyzing in the electrolytic tank 5 to recover metal palladium; and the waste liquid after electrolysis is sent to a sewage plant for treatment.
And (3) performing suction testing on the waste liquid after electrolysis: the recovery of palladium was 94.6%.
Example 3
The difference from example 2 is: in the step (B), the adding amount of the hydroxyl free radicals is 22g/t of the waste liquid, and the reaction stirring time after the hydroxyl free radicals are added is 1.9 hours. The rest is the same as in example 2.
And (3) performing suction testing on the waste liquid after electrolysis: the recovery of palladium was 94.5%.
Example 4
The difference from example 2 is: in the step (B), the adding amount of the hydroxyl free radicals is 24g/t of the waste liquid, and the reaction stirring time after the hydroxyl free radicals are added is 1.8 hours. The rest is the same as in example 2.
And (3) performing suction testing on the waste liquid after electrolysis: the recovery of palladium was 94.6%.
Example 5
The difference from example 2 is: in the step (B), the adding amount of the hydroxyl free radicals is 26g/t of the waste liquid, and the reaction stirring time after the hydroxyl free radicals are added is 1.6 hours. And (C) adding 10% acid liquor on line, and controlling the pH value of the waste liquor to be less than or equal to 3. The rest is the same as in example 2.
And (3) performing suction testing on the waste liquid after electrolysis: the recovery of palladium was 94.7%.
Example 6
The difference from example 2 is: in the step (B), the adding amount of the hydroxyl free radicals is 27g/t of the waste liquid, and the reaction stirring time after the hydroxyl free radicals are added is 1.5 hours. And (C) adding 10% acid liquor on line, and controlling the pH value of the waste liquor to be less than or equal to 3. The rest is the same as in example 2.
And (3) performing suction testing on the waste liquid after electrolysis: the recovery of palladium was 94.8%.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.

Claims (6)

1. A novel method for recovering metal palladium is characterized in that: the method comprises the following steps:
(A) sending the waste liquid containing the colloidal palladium of the circuit board production line into a waste liquid pool for concentration;
(B) sending the waste liquid in the waste liquid tank into a reaction tank, adding an oxidant hydroxyl radical on line, carrying out oxidation reaction under stirring, and carrying out gel breaking on the colloidal palladium;
(C) sending the waste liquid of the reaction tank into a precipitation filtering tank, controlling and adding alkali liquor or acid liquor on line according to the pH value of the waste liquid to ensure that the ionic tin is almost completely precipitated, and then separating the ionic tin through filtering;
(D) and (3) sending the waste liquid of the precipitation filter tank into an electrolytic tank through a delivery pump, electrolyzing, recovering metal palladium, and sending the electrolyzed waste liquid to a sewage plant for treatment.
2. The novel process for recovering metallic palladium according to claim 1, characterized in that: in the step (B), hydroxyl radicals are uniformly added by a hydroxyl radical generator, the adding amount is 21-27 g/t of waste liquid, and the reaction stirring time after the hydroxyl radicals are added is 1.5-2 hours.
3. The novel process for recovering metallic palladium according to claim 2, characterized in that: in the step (C), the concentrations of the acid liquor and the alkali liquor are both 10%, and when the alkali liquor needs to be added, the adding amount of the alkali liquor is controlled according to the pH value of more than or equal to 8; when the acid liquor needs to be added, the adding amount of the acid liquor is controlled by the pH value being less than or equal to 3.
4. The device adopted by the novel method for recovering metal palladium in any one of claims 1 to 3 is characterized in that: comprises a waste liquid pool (1), a reaction pool (2), a precipitation filter pool (3), a delivery pump (4) and an electrolytic tank (5) which are connected in sequence; the reaction tank (2) is connected with a hydroxyl radical generator (6), and the precipitation filter tank (3) is respectively connected with a lye tank (7) and an acid tank (8).
5. The apparatus of claim 4, wherein: a first waste liquid inlet and an oxidant feeding port are formed in the reaction tank (2); a second waste liquid inlet, an alkali liquid feeding port and an acid liquid feeding port are formed in the sedimentation filter tank (3); and a third waste liquid inlet and a waste liquid discharge outlet are arranged on the electrolytic cell (5).
6. The apparatus of claim 5, wherein: a stirrer (9) is arranged in the reaction tank (2).
CN202111435400.1A 2021-11-29 2021-11-29 Novel method and device for recovering metal palladium Pending CN114107675A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4435258A (en) * 1982-09-28 1984-03-06 Western Electric Co., Inc. Method and apparatus for the recovery of palladium from spent electroless catalytic baths
CN105132693A (en) * 2015-10-13 2015-12-09 苏州联科纳米净化科技有限公司 Technology for recycling palladium from acid palladium waste solution obtained after activation of colloid activating palladium
CN111424280A (en) * 2020-03-31 2020-07-17 遂宁市瑞思科环保科技有限公司 Regeneration system and method for tin stripping waste liquid
CN112520894A (en) * 2020-11-30 2021-03-19 深圳中科欧泰华环保科技有限公司 Method and device for treating mixed wastewater containing cyanogen, nickel and total phosphorus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4435258A (en) * 1982-09-28 1984-03-06 Western Electric Co., Inc. Method and apparatus for the recovery of palladium from spent electroless catalytic baths
CN105132693A (en) * 2015-10-13 2015-12-09 苏州联科纳米净化科技有限公司 Technology for recycling palladium from acid palladium waste solution obtained after activation of colloid activating palladium
CN111424280A (en) * 2020-03-31 2020-07-17 遂宁市瑞思科环保科技有限公司 Regeneration system and method for tin stripping waste liquid
CN112520894A (en) * 2020-11-30 2021-03-19 深圳中科欧泰华环保科技有限公司 Method and device for treating mixed wastewater containing cyanogen, nickel and total phosphorus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
全国勘察设计注册工程师环保专业管理委员会: "《注册环保工程师专业考试复习教材 水污染防治工程技术与实践 上 第4版》", vol. 1, 北京冶金工业出版社, pages: 1494 - 65 *

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