CN107130114B - The separation and recovery method of palladium in a kind of palladium-containing waste liquid - Google Patents
The separation and recovery method of palladium in a kind of palladium-containing waste liquid Download PDFInfo
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- CN107130114B CN107130114B CN201710392009.5A CN201710392009A CN107130114B CN 107130114 B CN107130114 B CN 107130114B CN 201710392009 A CN201710392009 A CN 201710392009A CN 107130114 B CN107130114 B CN 107130114B
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- palladium
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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
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
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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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- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to liquid waste disposal technique fields, and in particular to the separation and recovery method of palladium, step are in a kind of palladium-containing waste liquid：Carboxymethylation reaction is carried out to chitosan, then further water-soluble chitosan derivative is prepared in modification；Chitosan derivatives are added in low concentration palladium-containing waste liquid, are stirred evenly, ionic palladium is made to interact to form stable chelate with chitosan derivatives；High molecular weight chitosan is dissolved in diluted acid, is added in the waste liquid after chelating by 0.1 times~5 times of chitosan derivatives dosage, under stirring, the Palladium Chelating in waste liquid, colloidal palladium and other form palladiums is made to cooperatively form solid palladium floccule body with chitosan；The separation of variform palladium and waste liquid is realized by filtering or settlement action.The present invention is obtained by modifying function to the selective water-solubility chitosan derivative of palladium, interacts to form palladium floccule body with unmodified chitosan, it is low to avoid chitosan derivatives molecular weight, it is difficult to form the defect of palladium floccule body.
Description
Technical field
The invention belongs to liquid waste disposal technique fields, and in particular to the separation and recovery method of palladium in a kind of palladium-containing waste liquid.
Background technology
The main source of palladium-containing waste liquid is the electroplating effluents such as activation, passivation in each electronics industry technique productions, the waste liquid
Weakly acidic, palladium content is~50ppm.Palladium containing~10ppm in the waste liquid of the noble metals such as porpezite, gold production.Printing electricity
Workpiece cleaning waste water after road plate hole metallization, plastic electroplating and the activation of various non-metal electroplatings also contains a certain amount of palladium,
Content is~1ppm.The study found that a large amount of palladium-containing waste liquids are as Normal wastewater processing discharge in electroplating industry, after not only increasing
The difficulty of continuous wastewater treatment, and cause the waste of resource.According to statistics, what China's plating and circuit-board industry generated every year contains
There is 3 tons or so of Metal Palladium that cannot effectively be recycled in palladium waste liquid.In addition, palladium is discharged and accumulated can endanger the mankind in environment
Health such as causes asthma, allergy and rhinitis and other disease.In order to improve the rate of recovery of palladium in printed circuit board waste liquid, grind both at home and abroad
The person of studying carefully successively has carried out the technologies such as extraction, ion-exchange and resin adsorption method different degrees of research.Although these
Research makes some progress in some aspects, but also all there is certain deficiency, and preferable treatment technology is also only capable of making palladium
Content is reduced to 3~4ppm.Palladium is the one of the major reasons for causing palladium recovery rate to reduce in the form of different in palladium-containing waste liquid.
Invention content
In order to overcome above-mentioned defect existing in the prior art, the present invention provides a kind of separation and recovery of palladium in palladium-containing waste liquid
Method；It is obtained to the selective water-solubility chitosan derivative of palladium by modifying function, it is mutual with unmodified chitosan
Effect forms palladium floccule body, it is low to avoid chitosan derivatives molecular weight, it is difficult to form the defect of palladium floccule body；The letter of its technique
Single, rate of recovery height, processing procedure environmental protection do not generate secondary pollution.
The separation and recovery method of palladium in a kind of palladium-containing waste liquid of the present invention, including:
(1) carboxymethylation reaction:Chitosan is reacted under certain condition with alkali and monoxone, makes chitosan molecule structure
It is upper that there is carboxyl functional group, carboxymethylated product is obtained, formula is:
(2) modified-reaction：By the carboxymethylated product and functional group reactions obtained by (1) step, chitosan derivatives are obtained；
(3) chelatropic reaction：Chitosan derivatives obtained by (2) step are added in palladium-containing waste liquid, stirs evenly, chitosan is made to spread out
Biology is fully reacted with palladium forms stable chelate；
(4) flocculation：It takes a certain amount of chitosan to be dissolved with diluted acid, it is useless that (3) step is then added under stirring
In liquid, palladium floccule body is formed, is filtered after standing several minutes, realizes the separation of palladium floccule body and waste liquid.
Preferably, the deacetylation of chitosan used in (1) step is >=70%.
Preferably, the carboxymethylation reaction, the carboxyl grafting on the positions C6 of chitosan.
Preferably, a concentration of 0.1~100ppm of palladium, pH value of solution=1~6 in the palladium-containing waste liquid.
Preferably, the form of palladium is ionic state, glue in the palladium-containing waste liquid and simple substance is any or combination form.
Preferably, the functional group is thiohydroxy-containing group；The modified-reaction formula of the thiohydroxy-containing group is：
Preferably, the thiohydroxy-containing group is CS2With thiocarbamide it is any or combination.
Preferably, the chitosan derivatives are water solubility.
Preferably, (3) step chitosan derivatives dosage be (3) step palladium-containing waste liquid in palladium theoretical content mole be worth 0.1 times
~5 times；(4) step chitosan dosage be (3) step chitosan derivatives dosage mole value 0.1 times~5 times.
Compared with the prior art, the advantages of the present invention are as follows：Operating procedure is simple, wide adaptation range, and the rate of recovery is high, palladium
The rate of recovery reaches 95% or more；And processing procedure environmental protection, secondary pollution is not generated, residual waste solution can carry out returning for other materials
It receives, it is cost-effective.
Description of the drawings
Fig. 1 is the process flow chart of the separation and recovery method of palladium in a kind of palladium-containing waste liquid of the present invention.
Specific implementation mode
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto.
Embodiment 1
The separation and recovery method of palladium in a kind of palladium-containing waste liquid, as shown in Figure 1, including the following steps:
(1) chitosan that deacetylation is 80% is reacted under certain condition with alkali and monoxone, makes chitosan C6
Set the dissolubility that chitosan is improved with carboxyl functional group；
(2) modified-reaction：By the carboxymethylated product and CS obtained by (1) step2Reaction obtains water-soluble chitosan derivative
Object；
(3) chitosan derivatives obtained by (2) step are added in palladium-containing waste liquid, stir evenly, can be fully reacted with palladium
Forming stable chelate, (a concentration of 20ppm of palladium, pH value of solution 2.23, chitosan derivatives dosage are managed for palladium wherein in waste liquid
By 2 times of content mole value)；
(4) it takes a certain amount of chitosan to be dissolved with 1% glacial acetic acid, is added in (3) step waste liquid under agitation, form palladium
Floccule body filters after standing a few minutes, realizes the separation of palladium floccule body and waste liquid.
Wherein (4) step chitosan dosage be (3) step chitosan derivatives dosage mole value 2 times.
After being separated by filtration, a concentration of 0.56ppm of remaining palladium, palladium recovery rate are in filtrate：97.20%.
Embodiment 2
The separation and recovery method of palladium, includes the following steps in a kind of palladium-containing waste liquid:
(1) chitosan that deacetylation is 85% is reacted under certain condition with alkali and monoxone, makes chitosan C6
Set the dissolubility that chitosan is improved with carboxyl functional group；
(2) modified-reaction：Carboxymethylated product obtained by (1) step is reacted with thiocarbamide, water-soluble chitosan is obtained and spreads out
Biology；
(3) chitosan derivatives obtained by (2) step are added in palladium-containing waste liquid, stir evenly, can be fully reacted with palladium
Forming stable chelate, (a concentration of 1ppm of palladium, pH value of solution 2.52, chitosan derivatives dosage are that palladium is theoretical wherein in waste liquid
1.5 times of content mole value)；
(4) it takes a certain amount of chitosan to be dissolved with 1% glacial acetic acid, is added in (3) step waste liquid under agitation, form palladium
Floccule body filters after standing a few minutes, realizes the separation of palladium floccule body and waste liquid.
Wherein (4) step chitosan dosage be (3) step chitosan derivatives dosage mole value 3 times.
After being separated by filtration, a concentration of 0.02ppm of remaining palladium, palladium recovery rate are in filtrate：98.00%.
Embodiment 3
The separation and recovery method of palladium, includes the following steps in a kind of palladium-containing waste liquid:
(1) chitosan that deacetylation is 85% is reacted under certain condition with alkali and monoxone, makes chitosan C6
Set the dissolubility that chitosan is improved with carboxyl functional group；
(2) modified-reaction：Carboxymethylated product obtained by (1) step is reacted with thiocarbamide, water-soluble chitosan is obtained and spreads out
Biology；
(3) chitosan derivatives obtained by (2) step are added in palladium-containing waste liquid, stir evenly, can be fully reacted with palladium
Forming stable chelate, (a concentration of 20ppm of palladium, pH value of solution 3.52, chitosan derivatives dosage are managed for palladium wherein in waste liquid
By 2 times of content mole value)；
(4) it takes a certain amount of chitosan to be dissolved with 1% glacial acetic acid, is added in (3) step waste liquid under agitation, form palladium
Floccule body filters after standing a few minutes, realizes the separation of palladium floccule body and waste liquid.
Wherein (4) step chitosan dosage be (3) step chitosan derivatives dosage mole value 1 times.
After being separated by filtration, a concentration of 0.62ppm of remaining palladium, palladium recovery rate are in filtrate：96.90%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. the separation and recovery method of palladium in a kind of palladium-containing waste liquid, which is characterized in that including:
(1) carboxymethylation reaction:Chitosan is reacted under certain condition with alkali and monoxone, makes to have in chitosan molecule structure
There is carboxyl functional group, obtain carboxymethylated product, formula is:
(2) modified-reaction：By the carboxymethylated product and functional group reactions obtained by (1) step, chitosan derivatives are obtained；
(3) chelatropic reaction：Chitosan derivatives obtained by (2) step are added in palladium-containing waste liquid, stirs evenly, makes chitosan derivatives
It is fully reacted with palladium and forms stable chelate；
(4) flocculation：It takes a certain amount of chitosan to be dissolved with diluted acid, is then added under stirring in (3) step waste liquid,
Palladium floccule body is formed, is filtered after standing several minutes, realizes the separation of palladium floccule body and waste liquid.
2. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 1, which is characterized in that (1) used in step
The deacetylation of chitosan is >=70%.
3. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 1, which is characterized in that the carboxymethyl
Change reaction, the carboxyl grafting on the positions C6 of chitosan.
4. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 1, which is characterized in that described useless containing palladium
A concentration of 0.1~100ppm of palladium, pH value of solution=1~6 in liquid.
5. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 4, which is characterized in that described useless containing palladium
The form of palladium is ionic state, glue in liquid and simple substance is any or combination form.
6. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 1, which is characterized in that the functional group
For thiohydroxy-containing group；The modified-reaction formula of the thiohydroxy-containing group is：
7. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 6, which is characterized in that described to contain sulfydryl
Functional group is CS2With thiocarbamide it is any or combination.
8. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 1, which is characterized in that the chitosan
Derivative is water solubility.
9. the separation and recovery method of palladium in a kind of palladium-containing waste liquid according to claim 1, which is characterized in that (3) step shell is poly-
Sugar derivatives dosage is palladium theoretical content mole is worth in (3) step palladium-containing waste liquid 0.1 times~5 times；(4) step chitosan dosage is
(3) 0.1 times~5 times of step chitosan derivatives dosage mole value.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698711A (en) * | 2009-10-22 | 2010-04-28 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing chitosan resin for extracting noble metals from bittern |
| CN101701042A (en) * | 2009-03-28 | 2010-05-05 | 中国科学院海洋研究所 | Carboxymethyl chitosan thiourea resin and preparation method and application thereof |
| CN106430875A (en) * | 2016-10-26 | 2017-02-22 | 中国矿业大学(北京) | Preparation method and use method of urban sewage plant sludge heavy metal stabilizing agent |
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- 2017-05-27 CN CN201710392009.5A patent/CN107130114B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701042A (en) * | 2009-03-28 | 2010-05-05 | 中国科学院海洋研究所 | Carboxymethyl chitosan thiourea resin and preparation method and application thereof |
| CN101698711A (en) * | 2009-10-22 | 2010-04-28 | 国家海洋局天津海水淡化与综合利用研究所 | Method for preparing chitosan resin for extracting noble metals from bittern |
| CN106430875A (en) * | 2016-10-26 | 2017-02-22 | 中国矿业大学(北京) | Preparation method and use method of urban sewage plant sludge heavy metal stabilizing agent |
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Effective date of registration: 20220105 Address after: 518000 c717, 7th floor, Tsinghua University Research Institute, No. 019, Gaoxin South 7th Road, high tech Zone community, Yuehai street, Nanshan District, Shenzhen, Guangdong Patentee after: Shenzhen Xiaohe Environmental Protection Technology Co.,Ltd. Address before: 518057 Shenzhen Qinghua University Research Institute c717, Gaoxin South 7th Road, Nanshan Science Park, Shenzhen City, Guangdong Province Patentee before: RESEARCH INSTITUTE OF TSINGHUA University IN SHENZHEN |
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