CN100582019C - Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin - Google Patents
Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin Download PDFInfo
- Publication number
- CN100582019C CN100582019C CN200710060488A CN200710060488A CN100582019C CN 100582019 C CN100582019 C CN 100582019C CN 200710060488 A CN200710060488 A CN 200710060488A CN 200710060488 A CN200710060488 A CN 200710060488A CN 100582019 C CN100582019 C CN 100582019C
- Authority
- CN
- China
- Prior art keywords
- palladium
- exchange resin
- adsorption
- acrylic acid
- desorb
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a process for adsorbing and recycling palladium in waste liquor containing palladium by ion exchange resin, belonging to the technical field of the separation method utilizing the ion exchange resin as sorbent to treat liquid. The step of the process is to dispose weakly acidic acrylic acid type cation exchange resin as absorption bed layers and utilize the absorption bed layers to absorb the waste liquor containing palladium, absorption time is 40-60 minutes, and operation temperature is 25-85DEG C. Utilizing hydrochloric acid to desorb the waste liquor containing palladium, desorption time is 60-80 minutes, and the operation temperature is 25-85DEG C. Evaporating, concentrating and crystallizing the desorption liquor containing palladium after desorbing, and at last, recycled palladium compound PdCl2 is obtained. The process also can employ repeated cycle to absorb and desorb 2-8 times. The recovery rate of palladium can reach above 72% by employing the process of the invention. Recovery cost is low. The required equipment and technique is simple, and the operation is easy. Resin is easy to regenerate, and the resin after desorption can be used in repeated cycle.
Description
Technical field
It is the separation method of sorbent treatment liquid that technical scheme of the present invention relates to ion exchange resin, specifically, is that the method that contains palladium in the palladium waste liquid is reclaimed in spent ion exchange resin absorption.
Background technology
Great majority reclaim the method for palladium from spent catalyst, useless electronic instrument device and spent plating bath secondary resource all will extract the process that reclaims in the solution of associating.The method that reclaims palladium from solution common in the prior art has the precipitator method, active carbon adsorption and solvent extration.The precipitator method are Zn powder or Al powder to be added to contain in the palladium solution displace palladium, and the thick palladium that obtains obtains the high palladium powder of purity through the inferior palladium method of complicated dichloro two amminos treating process again after chlorination is boiled in acid, and this method complex process wastes time and energy, and is not suitable for the industrialization operation.Active carbon adsorption is to adsorb palladium from low palladium content solution, reaches the effect of high and low metal separation, but the reproduction ratio of gac is difficult.Solvent extration is to add specific organic solvent in containing palladium solution, palladium and its formation complex compound in the solution are enriched in the organic phase, organic phase after the separation is carried out back extraction with thiocarbamide or ammoniacal liquor etc., obtain being rich in the strip liquor of palladium, this back extraction process is difficulty, and used extraction agent price is all expensive partially, causes the extraction process cost higher.
The novel method that reclaims palladium is also among constantly researching and developing.CN1388256 discloses the method that reclaims palladium with the bacterium thalline from the palladium ion waste liquid of lower concentration, absorption after wherein filtering the thalline of palladium need at room temperature place 6-48 hour, after 550-800 ℃ calcination 1.5-3 hour, so this method operational cycle is long, and the bacterium thalline can not reuse.CN1400322 has disclosed a kind of method of separating platinum palladium iraurita, be to be stationary phase with weakly basic styrene type anion exchange resin, make moving phase with hydrochloric acid medium, realize that platinum, palladium, iridium, gold separate with base metal, used waste liquor PH＜7, resin after the absorption needs stepwise elution, uses 0.5mol/L-2mol/L NH
4CL+1mol/L-3mol/L NH
3H
2O desorb palladium, this method step is various, and certain limitation is arranged on experiment condition and operational condition; CN85100240 has disclosed with mercapto-amine-type chelating resin and has reclaimed gold and palladium in the electroplating effluent, pH value＜7 of waste liquid, the 900 ℃ of high-temperature roastings 2 hours in Ma Fulu of the saturated resin need of absorption palladium.In a word, above-mentioned existing method all exists the rate of recovery of palladium not high, and the complicated shortcoming of operational condition.
Summary of the invention
Technical problem to be solved by this invention is: provide spent ion exchange resin absorption to reclaim the method that contains palladium in the palladium waste liquid, this method has overcome existing not high with the rate of recovery of palladium in the class methods, and the complicated shortcoming of operational condition.
The present invention solves this technical problem the technical scheme that is adopted: the method that contains palladium in the palladium waste liquid is reclaimed in spent ion exchange resin absorption, and its operation steps is:
The first step, the pre-treatment of ion exchange resin and the setting of adsorption bed
Macropore acidulous acrylic acid cation exchange resin is used soaked in absolute ethyl alcohol 24 hours, be washed till no ethanol with distilled water again, be 2% salt acid soak 24 hours with mass percent concentration then, be washed till neutrality with distilled water again, pack into after air-dry in the glass column, form 6～8 centimetres high macropore acidulous acrylic acid cation exchange resin bed, load the absorbent cotton of 3～5 centimetres of thickness above the resin bed at this, below this resin bed, load the low-pressure high-density polyethylene silk of 2～4 centimetres of thickness, be set to adsorption bed;
Second step, adsorption operations
To contain the palladium waste liquid with constant flow pump and pump into the described glass column of the first step, make contain the palladium waste liquid with 3mL/ minute flow velocity by set adsorption bed in the first step, carry out adsorption operations by macropore acidulous acrylic acid cation exchange resin, adsorption time is 40～60 minutes, and service temperature is 25～85 ℃;
The 3rd step, the desorb operation
With mass percent concentration 3%～5% hydrochloric acid, with 3mL/ minute flow velocity by having adsorbed the macropore acidulous acrylic acid cation exchange resin of palladium in second step, it is carried out desorb, desorption time is 60～80 minutes, the desorb service temperature is identical with the temperature of the second step adsorption operations, obtains containing the palladium stripping liquid;
The 4th step, condensing crystal
The palladium stripping liquid that contains that obtains after the desorb operation of the 3rd step is carried out evaporating, concentrating and crystallizing, finally obtain the palladium compound PdCl that reclaims
2
The method that contains palladium in the palladium waste liquid is reclaimed in the absorption of above-mentioned spent ion exchange resin, and its second step adsorption operations and the desorb operation of the 3rd step adopt recirculation to carry out the operation 2～8 times of absorption-desorption.
Contain in the method for palladium in the palladium waste liquid the preferred homemade D113 macropore acidulous acrylic acid cation exchange resin of used macropore acidulous acrylic acid cation exchange resin in above-mentioned spent ion exchange resin absorption recovery.
The method that contains palladium in the palladium waste liquid is reclaimed in above-mentioned spent ion exchange resin absorption, and the evaporating, concentrating and crystallizing operation in its 4th step is general known chemical industry operation technology.
The invention has the beneficial effects as follows: adopt the technology of the present invention to reclaim the palladium that contains in the palladium waste liquid, the rate of recovery of palladium can reach more than 72%; Reclaim 1 milligram of PdCl
2The just concentration that is consumed is 4% hydrochloric acid 10-11 milliliter, and visible recovery cost is very low; Required equipment and technology are simple, and is easy and simple to handle; Resin is easily regenerated, the resin after the desorb can the recirculation utilization.
Embodiment
Embodiment 1
The handled palladium concentration that contains the palladium waste liquid is 112mg/L, contains [PdEDTA]
2+, [PdNH
3]
2+, Pd
2+, H
+And Cl
-, the pH value is 9.5～10.5.
The first step, the pre-treatment of ion exchange resin and the setting of adsorption bed
4g D113 macropore acidulous acrylic acid cation exchange resin is used soaked in absolute ethyl alcohol 24 hours, be washed till no ethanol with distilled water again, be 2% salt acid soak 24 hours with mass percent concentration then, be washed till neutrality with distilled water again, the diameter of packing into after air-dry is 16mm, in the glass column of high 35cm, form 7 centimetres high D113 macropore acidulous acrylic acid cation exchange resin bed, load the absorbent cotton of 4 centimetres of thickness above the resin bed at this, the low-pressure high-density polyethylene silk of 3 centimetres of thickness of filling is set to adsorption bed below this resin bed;
Second step, adsorption operations
With constant flow pump the above-mentioned palladium waste liquid that contains is pumped into the described glass column of the first step, make contain the palladium waste liquid with 3mL/ minute flow velocity by set adsorption bed in the first step, carry out adsorption operations by D113 macropore acidulous acrylic acid cation exchange resin, adsorption time is 50 minutes, service temperature is 65 ℃, and adsorption rate reaches 91%;
The 3rd step, the desorb operation
With mass percent concentration 4% hydrochloric acid, with 3mL/ minute flow velocity by having adsorbed the D113 macropore acidulous acrylic acid cation exchange resin of palladium in second step, it is carried out desorb, desorption time is 70 minutes, the desorb service temperature is identical with the temperature of the second step adsorption operations, obtain containing the palladium stripping liquid, desorption efficiency is 80%;
The 4th step, condensing crystal
The palladium stripping liquid that contains that obtains after the desorb operation of the 3rd step is carried out evaporating, concentrating and crystallizing, finally obtain the palladium compound PbCl that reclaims
2, palladium recovery rate is 72.8%.
Embodiment 2
Press step adsorption operations of second among the embodiment 1 and the desorb operation of the 3rd step, D113 macropore acidulous acrylic acid cation exchange resin recirculation is carried out the second step adsorption operations and the 3rd go on foot desorb operation 2 times, the accumulative total adsorption rate is 90.6%, the accumulative total desorption efficiency is 80.4%, and palladium recovery rate reaches 72.9%.
Embodiment 3
Press step adsorption operations of second among the embodiment 1 and the desorb operation of the 3rd step, D113 macropore acidulous acrylic acid cation exchange resin recirculation is carried out the second step adsorption operations and the 3rd go on foot desorb operation 4 times, the accumulative total adsorption rate is 90%, the accumulative total desorption efficiency is 90.5%, and palladium recovery rate reaches 81%.
Embodiment 4
Press step adsorption operations of second among the embodiment 1 and the desorb operation of the 3rd step, D113 macropore acidulous acrylic acid cation exchange resin is repeated the operation 8 times of absorption-desorption, the accumulative total adsorption rate is 90%, and the accumulative total desorption efficiency is 99.8%, and palladium recovery rate reaches 90%.
Embodiment 5
The handled palladium concentration that contains the palladium waste liquid is 95mg/L, contains [PdEDTA]
2+, [PdNH
3]
2+, Pd
2+, H
+And Cl
-, the pH value is 9.5～10.5.
The first step, the pre-treatment of ion exchange resin and the setting of adsorption bed
3.4g D113 macropore acidulous acrylic acid cation exchange resin is used soaked in absolute ethyl alcohol 24 hours, be washed till no ethanol with distilled water again, be 2% salt acid soak 24 hours with mass percent concentration then, be washed till neutrality with distilled water again, the diameter of packing into after air-dry is 16mm, in the glass column of high 35cm, form 6 centimetres high D113 macropore acidulous acrylic acid cation exchange resin bed, load the absorbent cotton of 3 centimetres of thickness above the resin bed at this, the low-pressure high-density polyethylene silk of 2 centimetres of thickness of filling is set to adsorption bed below this resin bed;
Second step, adsorption operations
With constant flow pump the above-mentioned palladium waste liquid that contains is pumped into the described glass column of the first step, make contain the palladium waste liquid with 3mL/ minute flow velocity by set adsorption bed in the first step, carry out adsorption operations by D113 macropore acidulous acrylic acid cation exchange resin, adsorption time is 40 minutes, service temperature is 25 ℃, and adsorption rate reaches 87.5%;
The 3rd step, the desorb operation
With mass percent concentration 4% hydrochloric acid, with 3mL/ minute flow velocity by having adsorbed the D113 macropore acidulous acrylic acid cation exchange resin of palladium in second step, it is carried out desorb, desorption time is 60 minutes, the desorb service temperature is identical with the temperature of the second step adsorption operations, obtain containing the palladium stripping liquid, desorption efficiency is 83.2%;
The 4th step, condensing crystal
The palladium stripping liquid that contains that obtains after the desorb operation of the 3rd step is carried out evaporating, concentrating and crystallizing, finally obtain the palladium compound PbCl that reclaims
2, palladium recovery rate is 72.8%.
Embodiment 6
The handled palladium concentration that contains the palladium waste liquid is 155mg/L, contains [PdEDTA]
2+, [PdNH
3]
2+, Pd
2+, H
+And Cl
-, the pH value is 9.5～10.5.
The first step, the pre-treatment of ion exchange resin and the setting of adsorption bed
4.60g D113 macropore acidulous acrylic acid cation exchange resin is used soaked in absolute ethyl alcohol 24 hours, be washed till no ethanol with distilled water again, be 2% salt acid soak 24 hours with mass percent concentration then, be washed till neutrality with distilled water again, the diameter of packing into after air-dry is 16mm, in the glass column of high 35cm, form 8 centimetres high D113 macropore acidulous acrylic acid cation exchange resin bed, load the absorbent cotton of 5 centimetres of thickness above the resin bed at this, the low-pressure high-density polyethylene silk of 4 centimetres of thickness of filling is set to adsorption bed below this resin bed;
Second step, adsorption operations
With constant flow pump the above-mentioned palladium waste liquid that contains is pumped into the described glass column of the first step, make contain the palladium waste liquid with 3mL/ minute flow velocity by set adsorption bed in the first step, carry out adsorption operations by D113 macropore acidulous acrylic acid cation exchange resin, adsorption time is 60 minutes, service temperature is 85 ℃, and adsorption rate reaches 93.8%;
The 3rd step, the desorb operation
With mass percent concentration 4% hydrochloric acid, with 3mL/ minute flow velocity by having adsorbed the D113 macropore acidulous acrylic acid cation exchange resin of palladium in second step, it is carried out desorb, desorption time is 80 minutes, the desorb service temperature is identical with the temperature of the second step adsorption operations, obtain containing the palladium stripping liquid, desorption efficiency is 85.1%;
The 4th step, condensing crystal
The palladium stripping liquid that contains that obtains after the desorb operation of the 3rd step is carried out evaporating, concentrating and crystallizing, finally obtain the palladium compound PbCl that reclaims
2, palladium recovery rate is 79.8.4%.
Claims (3)
1. the method that contains palladium in the palladium waste liquid is reclaimed in spent ion exchange resin absorption, it is characterized in that operation steps is:
The first step, the pre-treatment of ion exchange resin and the setting of adsorption bed
Macropore acidulous acrylic acid cation exchange resin is used soaked in absolute ethyl alcohol 24 hours, be washed till no ethanol with distilled water again, be 2% salt acid soak 24 hours with mass percent concentration then, be washed till neutrality with distilled water again, pack into after air-dry in the glass column, form 6～8 centimetres high macropore acidulous acrylic acid cation exchange resin bed, load the absorbent cotton of 3～5 centimetres of thickness above the resin bed at this, below this resin bed, load the low-pressure high-density polyethylene silk of 2～4 centimetres of thickness, be set to adsorption bed;
Second step, adsorption operations
To contain the palladium waste liquid with constant flow pump and pump into the described glass column of the first step, make contain the palladium waste liquid with 3mL/ minute flow velocity by set adsorption bed in the first step, carry out adsorption operations by macropore acidulous acrylic acid cation exchange resin, adsorption time is 40～60 minutes, and service temperature is 25～85 ℃;
The 3rd step, the desorb operation
With mass percent concentration 3%～5% hydrochloric acid, with 3mL/ minute flow velocity by having adsorbed the macropore acidulous acrylic acid cation exchange resin of palladium in second step, it is carried out desorb, desorption time is 60～80 minutes, the desorb service temperature is identical with the temperature of the second step adsorption operations, obtains containing the palladium stripping liquid;
The 4th step, condensing crystal
The palladium stripping liquid that contains that obtains after the desorb operation of the 3rd step is carried out evaporating, concentrating and crystallizing, finally obtain the palladium compound PdCl that reclaims
2
2. the method that contains palladium in the palladium waste liquid is reclaimed in absorption according to the described spent ion exchange resin of claim 1, it is characterized in that: its second step adsorption operations and the desorb operation of the 3rd step adopt recirculation to carry out the operation 2～8 times of absorption-desorption.
3. the method that contains palladium in the palladium waste liquid is reclaimed in described spent ion exchange resin absorption according to claim 1, and it is characterized in that: used macropore acidulous acrylic acid cation exchange resin is homemade D113 macropore acidulous acrylic acid cation exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710060488A CN100582019C (en) | 2007-12-28 | 2007-12-28 | Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710060488A CN100582019C (en) | 2007-12-28 | 2007-12-28 | Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101215012A CN101215012A (en) | 2008-07-09 |
| CN100582019C true CN100582019C (en) | 2010-01-20 |
Family
ID=39621533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710060488A Expired - Fee Related CN100582019C (en) | 2007-12-28 | 2007-12-28 | Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100582019C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101200807B1 (en) * | 2011-03-09 | 2012-11-14 | (주)알티아이엔지니어링 | Method for the recovery of precious metals from polyketone |
| CN102212702B (en) * | 2011-05-31 | 2012-12-05 | 长春一汽富维高新汽车饰件有限公司 | Device and method for recovering electroplating colloidal palladium |
| CN102329959B (en) * | 2011-09-05 | 2012-12-26 | 中南大学 | Separation method of palladium from silver electrolyte |
| CN102872808B (en) * | 2012-09-17 | 2014-02-19 | 工信华鑫科技有限公司 | Method for separating, enriching and purifying copper and nickel by using heavy metal adsorption material |
| CN102872807B (en) * | 2012-09-17 | 2014-02-19 | 工信华鑫科技有限公司 | Method for separating, enriching and purifying nickel and ferrous iron through heavy metal absorbing material |
| CN111500872A (en) * | 2019-01-30 | 2020-08-07 | 鹏鼎控股(深圳)股份有限公司 | Recovery treatment method of low-concentration palladium-containing waste liquid |
-
2007
- 2007-12-28 CN CN200710060488A patent/CN100582019C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 树脂吸附聚酮反应含钯废液及其重复利用的研究. 郭锦棠等.离子交换与吸附，第17卷第1期. 2001 |
| 树脂吸附聚酮反应含钯废液及其重复利用的研究. 郭锦棠等.离子交换与吸附，第17卷第1期. 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101215012A (en) | 2008-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100582019C (en) | Method for absorbing and reclaiming palladium from palladium-containing waste liquid by ion exchange resin | |
| CN101066824B (en) | Process of treating and reusing effluent from 1-amino-8-naphthol-3, 6-disulfonic acid production | |
| CN102826627B (en) | Method for removing pyrazine derivatives in waste water by resin adsorption method | |
| CN101560044B (en) | Treatment method of waste water in hydroxybenzoic acid production | |
| CN101928828A (en) | Method for extracting lithium from salt lake brine by adsorption method | |
| CN107265548B (en) | Method for deeply adsorbing and removing phosphorus by using hydrated iron oxide loaded attapulgite | |
| CN101139152A (en) | Printing and dyeing wastewater advanced treatment and recycling method by using resin | |
| CN103073086B (en) | Method for adsorbing glycerol contained in wastewater by using resin treated by boric acid | |
| CN111392946A (en) | Method for recovering 1,3 cyclohexanedione from wastewater containing 1,3 cyclohexanedione | |
| CN103449623A (en) | Method for preparing metal nanometer material by recovering from industrial waste water | |
| CN101781035B (en) | Method for recovering terramycin from terramycin production wastewater. | |
| Li et al. | The enrichment of rare earth from magnesium salt leaching solution of ion-adsorbed type deposit: A waste-free process for removing impurities | |
| CN104628587B (en) | A kind of amoxicillin of reclaiming produces the method for D-pHPG in waste liquid | |
| CN107805712A (en) | A kind of method for removing organic matter in uranium-bearing alkaline leaching liquid | |
| CN103949206B (en) | A kind of metal salt molecular sieve type deep dehydration adsorbent and preparation method | |
| CN104128067A (en) | Method for recycling organic solvent and processing residual liquid | |
| CN101591083A (en) | Para hydroxybenzene glycolylurea building-up process treatment of phenolic waste water | |
| CN101928048B (en) | Method for purifying humic acid pollutants in water by utilizing polyaniline | |
| CN114249451B (en) | Novel method for treating high-temperature gas cooled reactor element core preparation process wastewater | |
| CN101759268A (en) | Technology for treating phenol-contained wastewater in synthetic process of L-(+)-D-p-hydroxyphenylglycine | |
| CN101260020B (en) | Method for treating benzene-containing waste water and reclaiming benzene | |
| CN101298441B (en) | Method for reclaiming 1,2- benzoisothiazoline-3-ketone from mother liquor | |
| CN106390963A (en) | Desorption and regeneration method for composite bentonite materials for adsorbing ammonia nitrogen wastewater | |
| CN101380567B (en) | Regeneration and activation technique of iodine pollution solid adsorbent | |
| CN102816047B (en) | Technology for removing ammonia in ammoniacal smell ethanol in tetramethylpiperidinol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100120 Termination date: 20101228 |