CN105039717A - Method for recycling palladium from alkaline palladium activation section waste water - Google Patents
Method for recycling palladium from alkaline palladium activation section waste water Download PDFInfo
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- CN105039717A CN105039717A CN201510572897.XA CN201510572897A CN105039717A CN 105039717 A CN105039717 A CN 105039717A CN 201510572897 A CN201510572897 A CN 201510572897A CN 105039717 A CN105039717 A CN 105039717A
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Abstract
The invention provides a method for recycling palladium from alkaline palladium activation section waste water. The method includes the following steps that 1, reduction is conducted; obtained raw palladium is dissolved with aqua regia, undissolved substance is filtered out, and the volume mass ratio of the aqua regia and the raw palladium is 5-6 to 1 L/kg; 3, filtering and dilution are conducted; 4, ion column adsorption is conducted; 5, ion columns are cleaned; 6, ion columns are regenerated; 7, palladium is recycled through regenerated liquid. According to the method, anion resins are used to selectively adsorb [PdCl4] <2->, base metals of copper, nickel and the like are effectively separated, the method is simple and easy to operate and control, the recycling rate is larger than 96%, and the product purity is larger than 99.98%.
Description
Technical field
The present invention relates to a kind of method of Recover palladium from alkaline palladium activation workshop section waste water.
Background technology
Electroless plating improves Surface Wear Resistance of Materials and corrosion proof a kind of surface reinforcing methods such as metal, along with its continuous development and improvement, the fields such as petrochemical complex, electronic technology, aerospace, machinofacture, precision instrument and chemical industry are widely used at present.The life tens of aircraft components part particularly effectively can be made doubly to hundred times, and effectively promote the development of aerospace cause.Along with the expansion of electroless plating range of application, the matrix variety of chemical plating gets more and more, and the catalytic activity of matrix etc. vary.Usually, need to implement the process of plating front activating to matrix, to obtain high autocatalytic activity, for suitable condition is created in the further enforcement of electroless plating.Therefore, the quality and effect plating front activating process directly decides the success or failure of electroless plating.
And to adopt more in activation treatment be ionic palladium activation liquid, ionic palladium is that West Germany and Japan release again on the basis of colloidal palladium, and more stable than colloidal palladium, coating adhesion is better.Ionic palladium activation solution can life-time service and not settlement separate, long service life, good stability.In ionic palladium activation solution, the content of precious metal palladium is minimum is 150 ~ 300mg/L.Ionic palladium activation solution is after activation workshop section completes activation, namely palladium activation waste water is become, but, because palladium is precious metal, it is expensive, if no matter ignore palladium activation waste water, the sharply rising of production cost will certainly be caused, therefore, Recover palladium from palladium activation waste water is the technology that each manufacturer is very valued.
The recovery of current Domestic Palladium is purified to produce and is mostly adopted traditional Chen Dian ﹑ Luo He ﹑ Suanization ﹑ to calcine and Process of Hydrogen Reduction, dosage is large and program is complicated, also have and adopt wet purification palladium technique, leaching process is generally: acid-soluble → desilver → purification → ammonia precipitation process → hcl acidifying → hydrazine hydrate reduction → palladium, but, the palladium though its technique can effectively be purified, but it can not the base-metal ion such as copper, nickel effectively in separation solution, cause the purity reclaiming gained palladium not reach 99.9%, affect its commercial value.
Summary of the invention
For solving above-mentioned Problems existing, the object of the present invention is to provide a kind of method of Recover palladium from alkaline palladium activation workshop section waste water, described method utilizes negative resin adsorption selection [PdCl
4]
2-, the base metals such as effective separating copper, nickel, and method is simple, hold easy operation control, the rate of recovery is greater than 96%, and product purity is all greater than 99.98%.
For achieving the above object, technical scheme of the present invention is:
From alkaline palladium activation workshop section waste water, a method for Recover palladium, comprises the steps:
1) reduce
In waste water, add hydrazine hydrate reduce, interpolation limit, limit is stirred to and no longer produces precipitation, then stirs 30 ~ 60 minutes, and by waste water pump to centrifuge, gained precipitation is thick palladium;
2) by thick for gained palladium aqua regia dissolution, elimination insolubles, chloroazotic acid is 5 ~ 6:1, L/ kilogram with the volume mass ratio of thick palladium;
Wherein, to be dissolved in the reaction formula of chloroazotic acid as follows for thick palladium:
3Pd+12HCl+2HNO
3=2NO↑+3H
2[PdCl
4]+4H
2O
From above formula, in the solution, palladium is with H
2pdCl
4form exists, PdCl
4 -2be negatively charged ion, the base metal impurities such as Rong liquid Zhong Tong ﹑ nickel are positively charged ion.
3) filter, dilute
Step 2) after gained solution filters elimination insolubles, solution ph is diluted to 2;
Because after aqua regia dissolution alkali palladium, acidity is too high, after needing dilution, just ion exchange column can be entered, therefore with tap water dilution pH to 2.
4) ion column absorption
Solution after dilution is pumped in ion column, adopts the palladium ion in strongly basic anionic resin adsorbent solution;
The base metal impurities such as the copper ﹑ nickel now in solution are not adsorbed by strongly basic anionic resin, stay in the solution.
5) ion column is cleaned
Ion column absorption terminate after, cleaning ion column, be washed till Inlet and outlet water color identical till;
6) ion column regeneration
Regenerate ion column with regenerated liquid, the consumption of regenerated liquid is 2-3 times of amount of resin, and the resin after regeneration recovers primary colors and is regeneration completely;
Wherein, described amount of resin is 60% of ion column volume.
The chemical transformation of regeneration: H
2[PdCl
4] → [Pd (NH
3)
4] Cl
2
7) regenerated liquid Recover palladium
A) hydrochloric acid adjusts pH
Regulate regenerated liquid pH value to 0.5 ~ 1 after ion column regeneration with concentrated hydrochloric acid, generate pale yellow precipitate (namely palladium is present in precipitation), filter, collect filtrate;
Reaction equation is: [Pd (NH
3)
4] Cl
2+ 2HCl → [Pd (NH
3)
2] Cl
2↓+2NH
4cl
B) hydrazine hydrate reduction
After above-mentioned yellow mercury oxide ammonia solvent, add hydrazine hydrate, stirring reaction is clarified to supernatant liquor, and soak for some time to sinking to bottom, described hydrazine hydrate is 400 ~ 500:1, mL/ kilogram with the volume mass ratio of yellow mercury oxide;
Reaction equation:
[Pd (NH
3)
2] Cl
2(precipitation)+2 (NH
2)
2h
2o → Pd ↓+2NH
3h
2o+2NH
4cl+N
2↑
C) filtering-depositing
Suction filtration limit, limit hot wash step b) gained precipitation, treat that the filtrate of suction filtration becomes neutrality can stop cleaning, the precipitation after cleaning is dried and can obtain high purity palladium.
Further, step 1) described in waste water palladium ion concentration be 50 ~ 200mg/L.
Separately, step 1) in the thick palladium of gained palladium content be greater than 70%.
Separately have, step 3) in tap water, solution ph is diluted to 2.
Again, step 5) in clean ion column with tap water.
Further, step 6) described regenerated liquid is the mixed solution of ammoniacal liquor and ammonium chloride, in regenerated liquid, the massfraction of ammoniacal liquor is 8%, and the massfraction of ammonium chloride is 40g/L.
And, step 7) described in hydrazine hydrate be 80% hydrazine hydrate, the volume mass of hydrazine hydrate and palladium powder is than being 0.5:1, mL/g.
Separately, gained high purity palladium purity > 99.98%.
Beneficial effect of the present invention is:
Salkali waste palladium activation solution reduces by method provided by the present invention, be dissolved in chloroazotic acid, then use the palladium in anionite-exchange resin adsorbent solution, filter with after ammoniacal liquor, ammonium chloride solution regenerating resin, regenerated liquid acid adjustment, after filter cake ammonia solvent, obtain High Purity Palladium with hydrazine hydrate reduction.Wherein in ion column adsorption process, adopt the palladium ion in strongly basic anionic resin adsorbent solution, and make the base metal impurities such as copper nickel stay in solution, and then to make in the final palladium reclaimed the not base metal impurity such as cupric nickel, obviously promote the purity of palladium.
Method technique of the present invention is simple, the rate of recovery is high, production cost is low, can be widely used in the recovery of palladium in alkaline palladium activation workshop section washing water.Palladium recovery rate is greater than 96%, reclaims gained palladium purity and is all greater than 99.98%.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water provided by the present invention.
Embodiment
Following examples for illustration of the present invention, but can not be used for limiting the scope of the invention.The implementation condition adopted in embodiment can be for further adjustments according to the condition of producer, and unaccounted implementation condition is generally conventional laboratory conditions.
With reference to Fig. 1, the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water provided by the present invention, comprises the steps:
1) reduce
In waste water, add hydrazine hydrate reduce, interpolation limit, limit is stirred to and no longer produces precipitation, then stirs 30 ~ 60 minutes, and by waste water pump to centrifuge, gained precipitation is thick palladium;
2) by thick for gained palladium aqua regia dissolution, elimination insolubles, chloroazotic acid is 5 ~ 6:1, L/ kilogram with the volume mass ratio of thick palladium;
Wherein, to be dissolved in the reaction formula of chloroazotic acid as follows for thick palladium:
3Pd+12HCl+2HNO
3=2NO↑+3H
2[PdCl
4]+4H
2O
From above formula, in the solution, palladium is with H
2pdCl
4form exists, PdCl
4 -2be negatively charged ion, the base metal impurities such as Rong liquid Zhong Tong ﹑ nickel are positively charged ion.
3) filter, dilute
Step 2) after gained solution filters elimination insolubles, solution ph is diluted to 2;
Because after aqua regia dissolution alkali palladium, acidity is too high, after needing dilution, just ion exchange column can be entered, therefore with tap water dilution pH to 2.
4) ion column absorption
Solution after dilution is pumped in ion column, adopts the palladium ion in strongly basic anionic resin adsorbent solution;
The base metal impurities such as the copper ﹑ nickel now in solution are not adsorbed by strongly basic anionic resin, stay in the solution.
5) ion column is cleaned
Ion column absorption terminate after, cleaning ion column, be washed till Inlet and outlet water color identical till;
6) ion column regeneration
Regenerate ion column with regenerated liquid, the consumption of regenerated liquid is 2-3 times of amount of resin, and the resin after regeneration recovers primary colors and is regeneration completely;
The chemical transformation of regeneration: H
2[PdCl
4] → [Pd (NH
3)
4] Cl
2
7) regenerated liquid Recover palladium
A) hydrochloric acid adjusts pH
Regulate regenerated liquid pH value to 0.5 ~ 1 after ion column regeneration with concentrated hydrochloric acid, generate pale yellow precipitate (namely palladium is present in precipitation), filter, collect filtrate;
Reaction equation is: [Pd (NH
3)
4] Cl
2+ 2HCl → [Pd (NH
3)
2] Cl
2↓+2NH
4cl
B) hydrazine hydrate reduction
After above-mentioned yellow mercury oxide ammonia solvent, add hydrazine hydrate, stirring reaction is clarified to supernatant liquor, and soak for some time to sinking to bottom, described hydrazine hydrate is 400 ~ 500:1, mL/ kilogram with the volume mass ratio of yellow mercury oxide;
Reaction equation:
[Pd (NH
3)
2] Cl
2(precipitation)+2 (NH
2)
2h
2o → Pd ↓+2NH
3h
2o+2NH
4cl+N
2↑
C) filtering-depositing
Suction filtration limit, limit hot wash step b) gained precipitation, treat that the filtrate of suction filtration becomes neutrality can stop cleaning, the precipitation after cleaning is dried and can obtain high purity palladium.
Further, step 1) described in waste water palladium ion concentration be 50 ~ 200mg/L.
Separately, step 1) in the thick palladium of gained palladium content be greater than 70%.
Separately have, step 3) in tap water, solution ph is diluted to 2.
Again, step 5) in clean ion column with tap water.
Further, step 6) described regenerated liquid is the mixed solution of ammoniacal liquor and ammonium chloride, in regenerated liquid, the massfraction of ammoniacal liquor is 8%, and the massfraction of ammonium chloride is 40g/L.
And, step 7) described in hydrazine hydrate be 80% hydrazine hydrate, the volume mass of hydrazine hydrate and palladium powder is than being 0.5:1, mL/g.
Separately, gained high purity palladium purity > 99.98%.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (8)
1. activate a method for Recover palladium workshop section's waste water from alkaline palladium, it is characterized in that, comprise the steps:
1) reduce
In waste water, add hydrazine hydrate reduce, interpolation limit, limit is stirred to and no longer produces precipitation, then stirs 30 ~ 60 minutes, and by waste water pump to centrifuge, gained precipitation is thick palladium;
2) by thick for gained palladium aqua regia dissolution, elimination insolubles, chloroazotic acid is 5 ~ 6:1, L/ kilogram with the volume mass ratio of thick palladium;
3) filter, dilute
Step 2) after gained solution filters elimination insolubles, solution ph is diluted to 2;
4) ion column absorption
Solution after dilution is pumped in ion column, adopts the palladium ion in strongly basic anionic resin adsorbent solution;
5) ion column is cleaned
Ion column absorption terminate after, cleaning ion column, be washed till Inlet and outlet water color identical till;
6) ion column regeneration
Regenerate ion column with regenerated liquid, the consumption of regenerated liquid is 2-3 times of amount of resin, and the resin after regeneration recovers primary colors and is regeneration completely;
7) regenerated liquid Recover palladium
A) hydrochloric acid adjusts pH
Regulate regenerated liquid pH value to 0.5 ~ 1 after ion column regeneration with concentrated hydrochloric acid, generate pale yellow precipitate, filter, collect filtrate;
B) hydrazine hydrate reduction
After above-mentioned yellow mercury oxide ammonia solvent, add hydrazine hydrate, stirring reaction is clarified to supernatant liquor, and soak for some time to sinking to bottom, described hydrazine hydrate is 400 ~ 500:1, mL/ kilogram with the volume mass ratio of yellow mercury oxide;
C) filtering-depositing
Suction filtration limit, limit hot wash step b) gained precipitation, treat that the filtrate of suction filtration becomes neutrality can stop cleaning, the precipitation after cleaning is dried and can obtain high purity palladium.
2. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, is characterized in that, step 1) described in waste water palladium ion concentration be 50 ~ 200mg/L.
3. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, is characterized in that, step 1) in the thick palladium of gained palladium content be greater than 70%.
4. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, is characterized in that, step 3) in tap water, solution ph is diluted to 2.
5. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, is characterized in that, step 5) in clean ion column with tap water.
6. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, it is characterized in that, step 6) described regenerated liquid is the mixed solution of ammoniacal liquor and ammonium chloride, in regenerated liquid, the massfraction of ammoniacal liquor is 8%, and the massfraction of ammonium chloride is 40g/L.
7. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, is characterized in that, step 7) described in hydrazine hydrate be 80% hydrazine hydrate, the volume mass of hydrazine hydrate and palladium powder is than being 0.5:1, mL/g.
8. the method for a kind of Recover palladium from alkaline palladium activation workshop section waste water according to claim 1, is characterized in that, gained high purity palladium purity > 99.98%.
Priority Applications (1)
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|---|---|---|---|
| CN201510572897.XA CN105039717A (en) | 2015-09-10 | 2015-09-10 | Method for recycling palladium from alkaline palladium activation section waste water |
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|---|---|---|---|
| CN201510572897.XA CN105039717A (en) | 2015-09-10 | 2015-09-10 | Method for recycling palladium from alkaline palladium activation section waste water |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707751A (en) * | 2018-06-20 | 2018-10-26 | 贵研资源（易门）有限公司 | A kind of restoring method of the low concentration platinum group metal in high alkalinity desiliconization liquid |
| CN112159898A (en) * | 2020-01-17 | 2021-01-01 | 倍永环保科技（上海）有限公司 | Palladium recovery method for printed circuit board factory |
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| JPH01111825A (en) * | 1987-10-23 | 1989-04-28 | Tanaka Kikinzoku Kogyo Kk | Method for recovering palladium from palladium-containing liquid |
| CN1400322A (en) * | 2002-09-05 | 2003-03-05 | 北京矿冶研究总院 | Method for separating platinum, palladium and iridium |
| CN1492062A (en) * | 2003-09-28 | 2004-04-28 | 河北沧州大化集团有限责任公司 | Process for recovering palladium from TDI hydro genation waste palladium carbon catalyst |
| CN104651615A (en) * | 2015-01-28 | 2015-05-27 | 昆山全亚冠环保科技有限公司 | Method for recovering silver and palladium from waste |
-
2015
- 2015-09-10 CN CN201510572897.XA patent/CN105039717A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01111825A (en) * | 1987-10-23 | 1989-04-28 | Tanaka Kikinzoku Kogyo Kk | Method for recovering palladium from palladium-containing liquid |
| CN1400322A (en) * | 2002-09-05 | 2003-03-05 | 北京矿冶研究总院 | Method for separating platinum, palladium and iridium |
| CN1492062A (en) * | 2003-09-28 | 2004-04-28 | 河北沧州大化集团有限责任公司 | Process for recovering palladium from TDI hydro genation waste palladium carbon catalyst |
| CN104651615A (en) * | 2015-01-28 | 2015-05-27 | 昆山全亚冠环保科技有限公司 | Method for recovering silver and palladium from waste |
Non-Patent Citations (3)
| Title |
|---|
| 郑雅杰等: "从废胶体钯中回收Pd工艺研究", 《贵金属》 * |
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| 项铁丽: "电子垃圾的回收与处理技术", 《2008中国环境科学学会学术年会优秀论文集（中卷）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707751A (en) * | 2018-06-20 | 2018-10-26 | 贵研资源（易门）有限公司 | A kind of restoring method of the low concentration platinum group metal in high alkalinity desiliconization liquid |
| CN112159898A (en) * | 2020-01-17 | 2021-01-01 | 倍永环保科技（上海）有限公司 | Palladium recovery method for printed circuit board factory |
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Effective date of registration: 20170310 Address after: 231300 Lu'an, Shucheng, Hangzhou Port Economic Development Zone, Magnolia Road Applicant after: Shucheng joint surface treatment Co., Ltd. Address before: 215111 Jiangsu city of Suzhou province Wuzhong District Jinting town tile Hill Building 3 Applicant before: SUZHOU LIANKE NANO PURIFICATION TECHNOLOGY CO., LTD. |
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Address after: 231300 Lu'an, Shucheng, Hangzhou Port Economic Development Zone, Magnolia Road Applicant after: Shucheng Union Environmental Technology Co., Ltd. Address before: 231300 Lu'an, Shucheng, Hangzhou Port Economic Development Zone, Magnolia Road Applicant before: Shucheng joint surface treatment Co., Ltd. |
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Application publication date: 20151111 |