CN101045959A - Method for recovering rh - Google Patents
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- CN101045959A CN101045959A CNA2006101603463A CN200610160346A CN101045959A CN 101045959 A CN101045959 A CN 101045959A CN A2006101603463 A CNA2006101603463 A CN A2006101603463A CN 200610160346 A CN200610160346 A CN 200610160346A CN 101045959 A CN101045959 A CN 101045959A
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Abstract
To provide a method for refining an Rh solution containing Ag and one or more impurities selected from heavy metals and alkaline earth metals. The method for refining the Rh solution comprises steps of: adding an alkali to an Rh-containing aqueous solution of hydrochloric acid also containing Ag and one or more impurities selected from heavy metals and alkaline earth metals to adjust pH to 7 to 12; filtrating and separating the resulting neutralized precipitates containing Rh and other components; regulating the additive amount of hydrochloric acid in such a way that the mole ratio of Cl to Rh, Cl/Rh, at redissolution with hydrochloric acid ranges from 3 to 4; filtering the resulting solution to remove Ag as precipitate; and extracting the solution with DEHPA.
Description
Technical field
The present invention relates to the method for purification of the solution of a kind of Rh of containing, for example, contain processing from the intermediates residue of the precious metal recovery process of cupric electrolysis mud (slime) and the method for purification of the Rh hydrochloric acid soln that contains heavy metal, alkaline-earth metal, Ag that obtains.
Background technology
As above-mentioned, the technology that reclaims Rh from the solution of the precious metal that contains Rh etc. expeditiously is disclosed few.
Yet, for example in the spy opens 2005-97695 number " process for mutual separation of platinum group metal element " (patent documentation 1), disclose the process for mutual separation of the platinum group metal element of Pd, Pt, Ir, Rh etc.
The unexposed situation that comprises Ag in this treatment solution.Therefore when reclaiming Rh, do not demonstrate the trouble when extracting by extraction agent.
Discoveries such as present inventor when reclaiming Rh from the solution that contains Ag, divide phasic property poor, can not reclaim Rh expeditiously.The impurity of Fe, Pb etc. remains in the liquid after the extraction, can not reclaim Rh effectively.
[patent documentation 1] spy opens " process for mutual separation of platinum group metal element " 2005-97695 number
Summary of the invention
The invention provides a kind of method that reclaims highly purified Rh, do not have the defective of above-mentioned prior art, residual such as the impurity of the deterioration of minute phasic property and Fe, Pb etc. purified efficiently and contains the Rh solution of heavy metal and alkaline-earth metal, Ag.
Present inventors etc. carry out following invention in order to solve above-mentioned problem.
That is, the invention provides
(1) a kind of method of purification of Rh solution, wherein, to contain among heavy metal, the alkaline-earth metal any more than a kind impurity and the aqueous hydrochloric acid of the Rh of Ag, add alkali pH adjusted to 7～12, make the one-tenth fractional precipitation beyond the Rh, with this neutralization precipitation thing filtering separation, dissolve again with hydrochloric acid, make Cl at this moment become 3～4, with the liquid filtering of the hydrochloric acid addition so adjusted the mol ratio Cl/Rh of Rh, after Ag removed as throw out, extract with DEHPA.
(2) according to the method for purification of the Rh solution of above-mentioned (1), wherein, in the aqueous hydrochloric acid of Rh, add alkali, pH is adjusted to 7～12, make Rh one-tenth fractional precipitation in addition, after this neutralization precipitation thing filtering separation,, so that being 2.7～3.5 to the mol ratio Cl/Rh of Rh, the Rh solution that so obtains is filtered, after Ag is removed as throw out Cl by dissolving with hydrochloric acid, add hydrochloric acid so that Cl is 4～8 to the mol ratio Cl/Rh of Rh, resulting liquid is extracted with DEHPA.
(3) according to the method for purification of the Rh solution of above-mentioned (1), wherein, filtering separation make one-tenth fractional precipitation beyond the Rh the neutralization precipitation thing, adjust the hydrochloric acid addition when dissolving again so that Cl is 3～4 to the mol ratio Cl/Rh of Rh with hydrochloric acid, heating postcooling more than 90 ℃, after afterwards Ag being removed as throw out, extract with DEHPA.
(4) according to the method for purification of the Rh solution of above-mentioned (2), wherein, add hydrochloric acid so that Cl is 4～8 to the mol ratio Cl/Rh of Rh, extracting with DEHPA afterwards to room temperature with heating postcooling more than 90 ℃.
(5) according to the method for purification of each described Rh solution in above-mentioned (1)～(4), wherein, with hydrochloric acid with the Ru concentration in the lysed again liquid of Rh neutralization precipitation thing as below the 20mg/l, extract with DEHPA, both the rate of recovery of Rh can be highly guaranteed thus, heavy metal, alkaline-earth metal can be removed again to water.
According to above-mentioned (1), (2), be both can highly guarantee the rate of recovery of Rh to water, the method for the Rh that can purify again is when extracting with the lysed again liquid of hydrochloric acid Rh neutralization precipitation thing with DEHPA, Ru concentration in the solution as below the 20mg/l, is extracted with DEHPA again.
The method of purification of Rh hydrochloric acid soln of the present invention,
(1) make the Cl in the hydrochloric acid soln that contains the Rh of any impurity more than a kind etc. among heavy metal, the alkaline-earth metal become 3～4 to the mol ratio Cl/Rh of Rh, adjust in this way, it is extracted with DEHPA, the low loss of Rh can either be guaranteed thus, heavy metal and alkaline-earth metal can be removed fully again.
(2) interpolation with hydrochloric acid is divided into twice, and Ag dissolves as chloro-complex, can further reduce the Rh loss that brings because of the DEHPA extraction by this control.
(3) the Ru concentration in the liquid before the DP extraction is made as below the 20mg/l,, can either guarantees the low loss of Rh thus, can remove heavy metal and alkaline-earth metal fully again with the DEHPA extraction.
Description of drawings
Fig. 1 represents a form of schema of the present invention.
Fig. 2 represents the neutralizing treatment pH of Rh hydrochloric acid soln and the relation of Rh loss.
The relation of the Rh loss when the pairing DP-8R of the Cl/Rh mol ratio of liquid extracted before Fig. 3 represented to extract.
Cl/Rh mol ratio when Fig. 4 represents the dissolving of Rh corrective and the Ag concentration in the lysate and Rh be the relation of solution loss not.
Fig. 5 is a form of schema of the present invention, represents the form different with form shown in Figure 1.
Cl/Rh mol ratio when Fig. 6 represents the dissolving of Rh corrective and Ag concentration and Rh be the relation of solution loss not.
The relation of the Rh loss when the Cl/Rh mol ratio of liquid and DP-8R extracted before Fig. 7 represented to extract.
The relation of the Rh loss when Fig. 8 represents with respect to the DP-8R extraction of the Ru concentration of liquid before the extraction.
Embodiment
Below the present invention is explained detailedly.
Process object liquid of the present invention is in the processing of the solution that takes place when the cupric electrolysis mud reclaims precious metal or contain the solution of Ag when reclaiming precious metal from spent catalyst etc. in the processing of the solution of generation.
For example, be following liquid: contain Pt from 50mg/L to 1g/L, contain Pd from 50 to 400mg/L, contain Ru from 1 to 30mg/L, contain Ir from 15mg/L to 3g/L, contain Rh from 100mg/L to 40g/L, contain Ag from 0.5 to 1.5g/L, contain Fe from 0.5 to 2g/L, contain Pb from 50mg/L to 2g/L etc.
Object handles liquid of the present invention is hydrochloric acid acidity.The concentration of hydrochloric acid does not limit especially, can be from 0.1 to 8.0mol/L.
Contain at the Rh of process object and to add alkaline agent in the hydrochloric acid soln.Alkaline agent is a caustic soda etc.
The interpolation of alkaline agent is in order to make the pH value the when composition beyond the Rh reclaimed as corrective be in 7～12.Thus, can solution loss in the liquid of Rh after neutralization, can reclaim as the corrective filtering separation.Also have the part of Ag this moment separated in filtrate.
(1 additive process of hydrochloric acid)
When dissolving the corrective that contains Rh and other compositions again, be adjusted into Cl is become about 3～4 the mol ratio Cl/Rh of Rh with hydrochloric acid.
And if find this mol ratio, then the loss of Rh is few.
When the Cl/Rh mol ratio is lower than 3, have intermediate phase to generate when extracting with DEHPA, Rh loses increase, and the heavy metal concentration that residues in the liquid of extraction back uprises.
When the Cl/Rh mol ratio is higher than 4, from the problem of Rh loss aspect, still do not rise as the solubleness of the Ag of impurity with respect to Rh, Ag concentration uprises.
In addition, temperature and heat-up time when dissolving the corrective that contains Rh and other composition again with hydrochloric acid, if with more than 90 ℃ the heating then serve as abundant more than 1 hour.Heating temperature and heat-up time, can easily adjust according to the method for the change in color of Rh solution.For example, if be heated to more than 90 ℃, then obviously red increasing, solution becomes sorrel.
When being heated to 100 ℃, the solution of blackish green begins slightly redly near 80 ℃, as above-mentioned if then red increasing when becoming more than 90 ℃.
This colour-change is presumably because Cl carries out the coordination to Rh, by adding hydrochloric acid so that the Cl/Rh mol ratio becomes more than 3, is believed to generate [RhCl
3(H
2O)
3] the Rh chloro-complex that waits.
Cl is to the ligancy of Rh, is considered to and to change heat-up time according to Cl solution in the solution and Heating temperature, still, if the Cl concentration in the solution is suitable, thinks that then Heating temperature is high more, and it is short more that Cl fully carries out the needed time to the coordination of Rh.
Warmed-up Rh solution is cooled to the room temperature postprecipitation, filtering separation AgCl, can make the Ag concentration in the filtrate thus is 45～80mg/l.Also have,,,, it can be removed fully by filtering with 0.1 μ m membrane filter (membranefilter) so preferably filter with the tiny as far as possible strainer of mesh because the sedimentary granularity of AgCl is little.
(2 additive processs of hydrochloric acid)
With the neutralization precipitation thing of dissolving with hydrochloric acid Rh the time, be divided into 2 times by interpolation hydrochloric acid, can either suppress Ag and dissolve as chloro-complex, can further reduce the Rh loss in the DEHPA extraction again.
When dissolving the corrective that contains Rh composition in addition again with hydrochloric acid, adjust the addition of hydrochloric acid so that Cl becomes 2.7～3.5 to the mole number of Rh, filter dissolved Rh hydrochloric acid soln, Ag is removed as throw out, the not solution loss that can occur Rh thus hardly can make the Ag concentration in the filtrate be in below the 80mg/l.
If hydrochloric acid addition at this moment is many, then Ag solubleness rises, and the Ag concentration in the filtrate uprises.If the hydrochloric acid addition is few, then not all dissolvings of the Rh in the corrective make to become filter residue when filtering, and the not solution loss of Rh takes place.
In addition, for filtrate, add hydrochloric acid so that the Cl/Rh mol ratio becomes 4～8, in heating liquids more than 90 ℃, with the DEHPA extraction, the Rh of aqueous phase just has loss slightly thus, can reach the level of making the Rh about 4N, removes heavy metal and alkaline-earth metal.
If do not carry out adding, heating of hydrochloric acid with DEHPA extraction, then because Cl to the coordination deficiency of Rh, intermediate phase generates, and increases from the loss of the Rh of water.
Also have, when in above-mentioned neutralization precipitation thing, comprising NaCl, Cl concentration when calling dissolving with hydrochloric acid neutralization precipitation thing down, be easy to precipitation and remove Ag, saltout when preventing extracting operation simultaneously, with pure water neutralization precipitation thing repulp is cleaned after-filtration, in filtrate,, use dissolving with hydrochloric acid the NaCl after separating.
(removing the method for Ru in advance)
In addition, if comprise Ru when extract with DEHPA in the Rh hydrochloric acid soln, greasy and the intermediate phase generation that viscosity is high of useless buttery is arranged when extraction then, Rh loses increase.Though reason it be unclear that, be considered to owing to Ru when extracting operation can not stably be present in aqueous phase, thereby generate sludge (sludge).
Therefore, before extracting operation, need method, remove Ru in advance up to about 20mg/l by for example distillation etc.
[embodiment]
(1 additive process of hydrochloric acid)
To 1 additive process of hydrochloric acid, be illustrated along schema shown in Figure 1.Also have, the following embodiment and the analysis of comparative example all utilize ICP emission spectroanalysis device to carry out.
(embodiment 1)
Use the Rh hydrochloric acid soln shown in the table 1 as raw material.
Table 1
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| The Rh hydrochloric acid soln | 218 | 140 | 0 | 20708 | 865 | 5 | 30 | 10 | 486 | 31 | 184 | 67 | 819 |
| HCl dissolves (before filtering) again | 180 | 84 | 23 | 38735 | 2685 | 11 | 73 | 37 | 1856 | 88 | 303 | 176 | 4346 |
| HCl dissolves (filtering the back) again | 234 | 0 | 0 | 35830 | 1229 | 11 | 66 | 36 | 1718 | 88 | 521 | 168 | 37 |
| DP-8R extraction back liquid | 403 | 45 | 0 | 36418 | 2209 | 0 | 0 | 0 | 9 | 0 | 0 | 4 | 32 |
In this solution 250ml, add the NaOH aqueous solution, 90 ℃ pH is adjusted to 7 after, put cold 1 evening.With 5C filter paper vacuum filtration neutralization precipitation thing, a part of in filtrate, removing Ag.After the neutralization precipitation thing is washed with the pure water repulp, repeat to remove NaCl fully with the straight empty filtering operation of filter paper 2 times.
To in and throw out add hydrochloric acid so that the Cl/Rh mol ratio is 3.1, be heated to 60 ℃ of dissolvings.Add pure water so that the Rh concentration of solution be about 40g/l after, with 90 ℃ of heating 1 hour, to promote the coordination reaction of Cl to Rh.The color of solution is varied to sorrel from blackish green.After putting cold 1 evening, filter with 0.1 μ m membrane filter, filtering separation is the throw out of principal constituent with AgCl.
Ag in the filtrate filtered, the 37mg/L that becomes as shown in table 1, the 4346mg/L preceding with filtration compares reduction greatly.
Solvent extraction uses DP-8R (big eight chemistry systems) with kerosene (kerosine) it to be diluted to 20% as extraction agent DEHPA.Press O/A=2: 1 adds 20% DP-8R in the lysate again to hydrochloric acid, adds NaOH while stir, and pH is adjusted to 3.8.After stirring in 30 minutes, move to separating funnel and leave standstill, separate organic phase and water.
To repeat water after this operation 2 times as DP-8R extraction back liquid.Divide phasic property all good in 2 stages of extraction.Table 1 display analysis value.Heavy metal, the alkaline-earth metal of removing Ag can be removed to below the 10mg/l, Fe is removed to 9mg/L, and Pb is removed to 4mg/L.
The Rh loss that this extracting operation brings is 0.1%.
Also have Rh loss in the extracting operation, calculate according to following calculation formula.
Rh loss (%)=(C-D) ÷ C * 100 during extraction
C: the Rh amount (g) before the extraction in the liquid
Liquid Rh concentration analysis value (mg/L) ÷ 1000 before liquid measure (L) before=extraction * extraction
D: the Rh amount (g) in the liquid of extraction back
=extraction back liquid measure (L) * extraction back liquid Rh concentration analysis value (mg/L) ÷ 1000
Dissolution conditions is suitable again for hydrochloric acid by making corrective, can reduce the Rh loss that extracting operation brings, however, because some Rh is assigned in the organic phase, so the loss to the Rh of organic phase can take place.
Also have, each pH during above-mentioned neutralization operation is pairing to be shown in Fig. 2 to the Rh of the corrective rate of recovery.Be in 7～12 by the pH that makes neutralizing treatment as can be known, can make to the Rh of the corrective rate of recovery more than 99.9%.
In addition, the hydrochloric acid addition in the above-mentioned processing is that the Cl/Rh mol ratio when adding hydrochloric acid changes to 2.2～3.6, and after other operation went out processing same as described abovely, the same with the DEHPA extraction, Fig. 3 showed Rh loss at this moment.
The Cl/Rh mol ratio is adjusted at 3.1～3.6 o'clock, and the Rh loss in the extraction is lower than 10%, and heavy metal and the basic metal in the liquid of extraction back is lower than 10mg/l in addition.
When the Cl/Rh mol ratio is lower than 3, the phase-splitting during extraction worsens and the Rh loss uprises, and extreme case is not phase-splitting.
When the Cl/Rh mol ratio was big, it was no problem to utilize the Rh loss in DEHPA when extraction and impurity to remove the aspect, but because Cl concentration increases, the Ag concentration that is comprised in the solution uprises and for preferably.
Cl/Rh mol ratio during with dissolving with hydrochloric acid neutralization precipitation thing changes to 1.3～4.4, and is same as described above, dissolve the neutralization precipitation thing again with hydrochloric acid, and Fig. 4 shows not solution loss of the Ag concentration of the liquid that has filtered and Rh.
When dissolving corrective again with hydrochloric acid, if the solubleness of Ag descended and suppress the addition of hydrochloric acid, then the Rh in the corrective can all not dissolve, Rh enters in the filtration residue and loses when filter operation.
Cl/Rh mol ratio when making hydrochloric acid dissolve corrective again is 3～4 as can be known, can either guarantee that Rh is lost in below 0.5%, can make Ag concentration be low to moderate 45～80mg/l again.
Also have, the Rh loss the during dissolving with hydrochloric acid of corrective is calculated according to following formula.
Rh loss (%)=(A-B) ÷ A * 100 during the corrective dissolving
Rh amount (g) in the A:Rh hydrochloric acid soln (liquid before the neutralization)
=Rh hydrochloric acid soln amount (L) * Rh hydrochloric acid soln Rh concentration analysis value (mg/L) ÷ 1000
B: the Rh amount (g) in the corrective lysate
=dissolving liquid measure (L) * lysate Rh concentration analysis value (mg/L) ÷ 1000
With among the NaOH and the Rh hydrochloric acid soln, Rh is precipitated as corrective, be with the pure water repulp, filter after, by dissolving corrective again,, Rh is concentrated to 50～80g/l from 10g/l to remove NaCl by hydrochloric acid.
Here, owing to make neutrality condition suitable, Rh concentration is＜1mg/l in the liquid of neutralization back, so the Rh loss that neutralization operation is brought can be considered zero.In addition,, with the corrective repulp NaCl is removed in filtrate with pure water, Rh loss at this moment also can be considered as zero.
According to as can be known last, in the aqueous hydrochloric acid of Rh, add alkali pH is adjusted into 7～12, with make one-tenth fractional precipitation beyond the Rh the corrective filtering separation after, so that Cl is 3～4 to the mol ratio Cl/Rh of Rh, filter this Rh solution with dissolving with hydrochloric acid, Ag is removed as throw out, make Ag concentration in the filtrate below 80mg/l,, can make the Rh loss be lower than 10% thus by the DEHPA extraction, can remove heavy metal, alkaline-earth metal in the liquid of extraction back, and make its concentration be lower than 10mg/l.
(comparative example 1)
Use the Rh hydrochloric acid soln shown in the table 2 as raw material.
Table 2
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| The Rh hydrochloric acid soln | 218 | 140 | 0 | 20709 | 965 | 5 | 30 | 10 | 486 | 31 | 184 | 67 | 810 |
| HCl dissolves (before filtering) again | - | - | - | - | - | - | - | - | - | - | - | - | - |
| HCl dissolves (filtering the back) again | 137 | 136 | 0 | 46617 | 3205 | 11 | 55 | 28 | 1591 | 85 | 576 | 147 | 26 |
| DP-8R extraction back liquid | - | - | - | - | - | - | - | - | - | - | - | - | - |
When dissolving the neutralization precipitation thing again with hydrochloric acid, quantitatively add hydrochloric acid so that the Cl/Rh mol ratio is 2.2, the adjusted heating of concentration was carried out 1 hour with 90 ℃, with the hydrochloric acid that carries out same treatment with embodiment 1 in addition again lysate as extraction before liquid.
The color of solution be green in sorrel slightly.DP-8R with 20%, by O/A=2: while 1 mix to stir and add NaOH, adjusting to pH is 3.8 back restir 30 minutes, move to separating funnel and leave standstill 30 minutes, but organic phase and water hangs turbid seriously and not phase-splitting.
This is presumably because the addition deficiency of hydrochloric acid, so each composition of aqueous phase can not stably dissolve at aqueous phase when extracting operation, and some is separated out.
(comparative example 2)
Use the Rh hydrochloric acid soln shown in the table 3 as raw material.
Table 3
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| The Rh hydrochloric acid soln | 240 | 278 | 0 | 19996 | 1476 | 4 | 34 | 9 | 472 | 22 | 167 | 39 | 1432 |
| HCl dissolves (before filtering) again | 201 | 345 | 1 | 49697 | 3743 | 11 | 87 | 32 | 1522 | 49 | 467 | 128 | 2572 |
| HCl dissolves (filtering the back) again | 424 | 272 | 14 | 50687 | 3817 | 12 | 92 | 35 | 1545 | 55 | 528 | 123 | 76 |
| DP-8R extraction back liquid | 709 | 209 | 0 | 46422 | 3219 | 0 | 0 | 1 | 10 | 0 | 1 | 18 | 27 |
When dissolving the neutralization precipitation thing again with hydrochloric acid, quantitatively add hydrochloric acid so that the Cl/Rh mol ratio is 2.5, add pure water and carry out the adjusted heating of concentration and carried out 30 minutes with 60 ℃, with the hydrochloric acid that carries out same treatment with embodiment 1 in addition again lysate as extraction before liquid.
The color of solution is blackish green.DP-8R with 20%, by O/A=2: while 1 mix to stir and add NaOH, adjusting to pH is 3.8 back restir 30 minutes, moves to separating funnel and leaves standstill 30 minutes, separation organic phase and water.
To repeat water after this operation 2 times as DP-8R extraction back liquid.Divide phasic property all to generate outstanding turbid phase at the interface in 2 stages of extraction.The analytical value of the water before and after the extraction shows at table 3.The Fe concentration of extraction back liquid aqueous phase is 10mg/l, and Pb concentration is 18mg/l, and the removal of Fe, Pb is insufficient.
The Rh loss that this extracting operation causes is 19.7%.This is considered to because hydrochloric acid addition deficiency heats insufficient.
Condition and branch phasic property, impurity in the DP extraction about embodiment 1 and comparative example 1,2 is removed, the Rh loss is summarized in table 4.
Table 4
| Hydrochloric acid is dissolution conditions again | The DP-8R extraction results | Estimate | ||||||||
| Hydrochloric acid addition (Cl/Rh mol ratio) | Heat-up time | Heating temperature | The color of solution | Divide phasic property | Extraction back liquid impurity concentration (mg/L) | Rh loses (%) | ||||
| Fe | Cu | Pb | ||||||||
| Embodiment 1 | 3.1 | 1 hour | 90℃ | Sorrel | Well | 9 | ＜1 | 4 | 0.1 | Rh loss small impurities is removed well |
| Comparative example 1 | 2.2 | 1 hour | 90℃ | The greenbelt sorrel | The profit muddiness can not phase-splitting | - | - | - | - | Can not phase-splitting can't carry out extracting operation |
| Comparative example 2 | 2.5 | 30 | 60℃ | Blackish green | The water-oil interface muddiness generates mutually | 10 | 1 | 18 | 19.7 | Rh loses many impurity and removes insufficient |
As embodiment 1, by the Cl/Rh mol ratio being adjusted to 3～4 when the dissolving with hydrochloric acid of Rh corrective, heating more than 90 ℃ 1 hour, the Rh loss in DEHPA when extraction is in below 10%, and can remove heavy metal, alkaline-earth metal is lower than 10mg/l until it.
As comparative example 1,2, when the Cl/Rh mol ratio is lower than 3, though Heating temperature, when extracting with DEHPA, not phase-splitting and can not carry out extracting operation fully, even if can phase-splitting also generate intermediate phase, Rh loses increase, the extracting and separating of impurity worsens.
Also have, if the Cl/Rh mol ratio is more than 4, then the solubleness of AgCl rises, Rh hydrochloric acid again in the filtrate of solubleness Ag concentration rise, the Ag quality in the Rh end article rises and is not preferred.Cl/Rh mol ratio and Rh the hydrochloric acid relation of lysate Ag concentration are again represented by Fig. 4.
In Rh hydrochloric acid dissolves again, if be that condition 4 below, more than 60 ℃ is dissolved again, be cooled to after the room temperature with the Cl/Rh mol ratio, with the filtration of 0.1 μ m membrane filter, then can remove Ag and be lower than 80mg/l until its concentration.
The Cl/Rh mol ratio is 3～4, can make Ag concentration be in 45～80mg/l, and Rh at this moment not solution loss is below 0.5%.
Go up according to this as can be known, first according to the present invention, Rh just has loss slightly, can remove heavy metal and alkaline-earth metal effectively.
(embodiment 2)
(hydrochloric acid adds 2 methods)
Hydrochloric acid is added 2 methods, be illustrated according to schema shown in Figure 5.
Use the Rh hydrochloric acid soln shown in the table 5 as raw material.
Table 5
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Fb | Ag | |
| The Rh hydrochloric acid soln | 37 | 145 | 0 | 7521 | 104 | 2 | 9 | 5 | 111 | 7 | 186 | 60 | 381 |
| HCl dissolves (before filtering) again | 252 | 1207 | 0 | 61285 | 684 | 16 | 76 | 39 | 792 | 51 | 1411 | 407 | 51 |
| HCl dissolves (filtering the back) again | 216 | 1133 | 0 | 55531 | 628 | 15 | 71 | 36 | 736 | 48 | 1310 | 378 | 45 |
| Liquid before the DP-8R extraction | 236 | 1094 | 0 | 52056 | 614 | 15 | 65 | 36 | 731 | 48 | 1299 | 381 | 45 |
| DP-8R extraction back liquid | 206 | 1026 | 0 | 51773 | 607 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 42 |
In this solution 9L, add the NaOH aqueous solution, 90 ℃ pH adjusted to 7 after, put cold 1 evening.With 5C filter paper vacuum filtration neutralization precipitation thing, a part of in filtrate, removing Ag.After the neutralization precipitation thing is washed with the pure water repulp, repeat fully to remove NaCl with the straight empty filtering operation of filter paper 2 times.
In the neutralization precipitation thing, add hydrochloric acid so that the Cl/Rh mol ratio is 3.5, add pure water with the Rh concentration of solution be about 50g/l after, with 80 ℃ of heating 30 minutes, dissolve corrective fully.The color of solution is a sorrel.
After putting cold 1 evening, filter with 0.1 μ m membrane filter, filtering separation is the throw out of principal constituent with AgCl.The Ag concentration of filtrate is 45mg/l, with the Ag concentration 37mg/l of embodiment 1 be value with degree.At this moment Rh not solution loss is 0.1%.
In above-mentioned filtrate, add hydrochloric acid so that the Cl/Rh mol ratio is 4.0, with 95 ℃ of heating 2 hours, promote the coordination of Cl to Rh.The color of solution further increases red from sorrel.With put the liquid that is chilled to room temperature as extraction before liquid
Solvent extraction uses DP-8R (big eight chemistry systems) with kerosene it to be diluted to 20%.Press O/A=1: 1 adds 20% DP-8R in the liquid before extraction, add NaOH while stir, and pH is adjusted to 3.8.
After stirring in 30 minutes, move to separating funnel and leave standstill, separate organic phase and water.To repeat water after this operation 2 times as DP-8R extraction back liquid.Divide phasic property all good in 2 stages of extraction.
Table 5 display analysis value.Heavy metal, the alkaline-earth metal of removing Ag can be removed below 10mg/l.The Rh loss that this extracting operation causes is 0.8%.
Also have, the Cl/Rh mol ratio with dissolving with hydrochloric acid neutralization precipitation thing the time changes to 1.3～4.4, similarly to Example 2, dissolves corrective again with hydrochloric acid, and Fig. 6 shows not solution loss of the Ag concentration of the liquid that has filtered and Rh.
Cl/Rh mol ratio when making hydrochloric acid dissolve corrective again is in 2.7～3.5 as can be known, can either guarantee that Rh is lost in below 0.5%, can make Ag concentration be lower than 80mg/l again.
In addition, in embodiment 2, the Cl/Rh mol ratio when adding hydrochloric acid changes to 3.1～7.1, after other operation and embodiment 1 do same processing, shows that by Fig. 7 the Rh when extract with DEHPA loses similarly to Example 1.
The Cl/Rh mol ratio is 4～7.1, and the Rh loss in the extraction is lower than 3%.Heavy metal and basic metal in the liquid of extraction back is lower than 10mg/l in addition.
When the Cl/Rh mol ratio was big, it was no problem to utilize Rh loss, the impurity of DEHPA extraction to remove the aspect, but because Cl concentration increases, in other operations that continue to implement, it is former thereby for preferred that it becomes that NaCl separates out when adding NaOH.
Therefore, preferred Cl/Rh mol ratio is below 8.
According to as can be known last, according to the present invention shown in second, in the aqueous hydrochloric acid of Rh, add alkali pH is adjusted into 7～12, with make one-tenth fractional precipitation beyond the Rh the corrective filtering separation after, 's 2.7～3.5 mode dissolving with hydrochloric acid with Cl to the mol ratio Cl/Rh of Rh, this Rh solution is filtered, Ag is removed as throw out, making Ag concentration in the filtrate below 80mg/l, in addition, is that 4～8 mode is added hydrochloric acid with Cl to the mol ratio Cl/Rh of Rh, warmed-up liquid is extracted by DEHPA, can make the Rh loss be lower than 4% thus, can remove the heavy metal in the liquid of extraction back, alkaline-earth metal, and make its concentration until being lower than 10mg/l.
(comparative example 3)
Use the Rh hydrochloric acid soln shown in the table 6 as raw material.
Table 6
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| The Rh hydrochloric acid soln | 218 | 140 | 0 | 20709 | 965 | 5 | 30 | 10 | 486 | 31 | 184 | 87 | 819 |
| HCl dissolves (before filtering) again | - | - | - | - | - | - | - | - | - | - | - | - | - |
| HCl dissolves (filtering the back) again | 298 | 83 | 0 | 31193 | 696 | 10 | 53 | 35 | 1833 | 86 | 485 | 116 | 62 |
| DP-8R extraction back liquid | 91 | 67 | 0 | 27522 | 1903 | 0 | 0 | 0 | 4 | 1 | 1 | 13 | 66 |
When dissolving the neutralization precipitation thing again, add hydrochloric acid, add pure water and carry out the adjusted heating of concentration and carried out 30 minutes with 60 ℃ so that the Cl/Rh mol ratio is 4.0 with hydrochloric acid, with the hydrochloric acid that carries out same treatment with embodiment 1 in addition again lysate as extraction before liquid.
The color of solution is sorrel.DP-8R with 20%, by O/A=2: while 1 mix to stir and add NaOH, adjusting to pH is that stirred 30 minutes 3.8 backs, moves to separating funnel and leaves standstill 30 minutes, separation organic phase and water.
To repeat water after this operation 2 times as DP-8R extraction back liquid.Divide phasic property all to generate outstanding turbid phase at the interface in 2 stages of extraction.The analytical value of the water before and after the extraction shows at table 4.The Pb concentration of extraction back liquid aqueous phase is 13mg/l, and the removal of Pb is insufficient.
The Rh loss that this extracting operation causes is 7.7%.This is considered to because the heating of hydrochloric acid after dissolving again is insufficient, so Cl becomes insufficient to the coordination of Rh, the part of Rh complex compound is separated out, or be collected into outstanding turbid mutually in, or a part is extracted to DP-8R.
With branch phasic property, impurity in the condition of embodiment 1,2 and comparative example 3 and the DP extraction remove, the Rh loss is summarized in table 7.
As comparative example 3, even the Cl/Rh mol ratio in 3～4 scope, low with respect to embodiment 1 Heating temperature, under the heat-up time short situation, also has intermediate phase to generate during the DEHPA extraction, the extracting and separating of impurity worsens, and the Rh loss increases to 7.7%.
On the other hand, as embodiment 1 and embodiment 2 as can be known, the Cl/Rh mol ratio is more than 3, if heating more than 90 ℃ 1 hour, because the Rh loss in the DEHPA extraction can be reduced to and be lower than 1%, so think that Cl fully carries out to the coordination of Rh, Heating temperature and heat-up time are abundant.
(embodiment 3)
(before extraction treatment, removing the method for Ru in advance)
By the following examples, the method for removing Ru in advance before extraction treatment is described in detail.
Use the Rh hydrochloric acid soln shown in table 8～12 as raw material.
The Ru concentration of Rh hydrochloric acid soln is about 0mg/l and 10～800mg/l, with the hydrochloric acid all handled equally with embodiment 2 in addition again lysate as extraction before liquid.The color of solution is a sorrel.
DP-8R with 20%, by O/A=1: while 1 mix to stir and add NaOH, adjusting to pH is 3.8 back restir 30 minutes, after moving to separating funnel and leaving standstill 30 minutes, separation organic phase and water.
To implement water after this operation 1 time as DP-8R extraction back liquid.
Make process object liquid (hydrochloric acid dissolve again (filter back)) the Ru change in concentration, table 7～11 show this liquid carried out the water after the extraction treatment and handle before analytical value.
Table 7
| Liquid heating condition before the DP-8R extraction | The DP-8R extraction results | Estimate | |||||||||
| Hydrochloric acid addition (Cl/Rh mol ratio) | Heat-up time | Heating temperature | The color of solution | Divide phasic property | Extraction back liquid impurity concentration (mg/L) | Rh loses (%) | |||||
| Fe | Cu | Pb | |||||||||
| Embodiment 1 | 3.1 | 1 hour | 90℃ | Sorrel | Well | 9 | 0 | 4 | 0.1 | Rh loss small impurities is removed well | |
| | 4.0 | 2 hours | 95 | Sorrel | Well | 0 | 0 | 0 | 0.8 | Rh loss small impurities is removed well | |
| Comparative example 3 | 4.0 | 30 | 60℃ | Sorrel | The water-oil interface muddiness generates mutually | 4 | 1 | 13 | 7.7 | Rh loses many impurity and removes insufficient | |
Table 8
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| HCl dissolves (filtering the back) again | 311 | 214 | 884 | 47551 | 3248 | 7 | 55 | 50 | 1300 | 44 | 265 | 91 | 33 |
| DP-8R extraction back liquid | 285 | 167 | 539 | 42096 | 2933 | 0 | 0 | 0 | 1 | 0 | 0 | 12 | 29 |
Table 9
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| HCl dissolves (filtering the back) again | 258 | 173 | 123 | 38464 | 2337 | 6 | 45 | 41 | 1101 | 36 | 219 | 76 | 25 |
| DP-8R extraction back liquid | 238 | 152 | 62 | 34120 | 2314 | 0 | 0 | 0 | 0 | 0 | 3 | 5 | 22 |
Table 10
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| HCl dissolves (filtering the back) again | 300 | 218 | 7 | 46808 | 3264 | 7 | 52 | 48 | 1304 | 42 | 254 | 89 | 32 |
| DP-8R extraction back liquid | 279 | 195 | 14 | 42560 | 2918 | 0 | 0 | 0 | 1 | 0 | 2 | 6 | 28 |
Table 11
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| HCl dissolves (filtering the back) again | 289 | 199 | 0 | 44530 | 2995 | 7 | 51 | 45 | 1221 | 40 | 245 | 85 | 30 |
| DP-8R extraction back liquid | 272 | 179 | 6 | 41599 | 2809 | 0 | 0 | 0 | 1 | 0 | 4 | 4 | 26 |
Table 12
| Concentration (mg/L) | |||||||||||||
| Pt | Pd | Ru | Rh | Ir | Mg | Ca | Mn | Fe | Al | Cu | Pb | Ag | |
| HCl dissolves (filtering the back) again | 258 | 258 | 0 | 51155 | 3587 | 8 | 61 | 55 | 1433 | 49 | 300 | 103 | 37 |
| DP-8R extraction back liquid | 234 | 249 | 0 | 47824 | 3334 | 0 | 0 | 0 | 4 | 0 | 4 | 8 | 33 |
About result, about Ru concentration and branch phasic property, the impurity in the DP extraction of liquid before extracting remove, Rh loses, in table 13 and Fig. 8, show.
Table 13
| Hydrochloric acid is lysate again | Extraction back liquid Pb concentration | The Rh loss | Divide phasic property | ||
| Rh g/l | Ru mg/l | Pb mg/l | Extraction fs mg/L | Extraction fs % | The extraction fs |
| 47.6 | 884 | 91 | 24 | 75.9 | All muddy |
| 38.5 | 123 | 76 | 5 | 16.8 | Intermediate phase generates |
| 60.6 | 37 | 250 | 14 | 7.7 | Intermediate phase generates |
| 46.8 | 20 | 89 | 6 | 3.8 | Well |
| 44.5 | 10 | 85 | 4 | 2.4 | Well |
| 51.2 | 0 | 103 | 8 | 0.0 | Well |
15
If before the extraction in the liquid Ru concentration be 20mg/l, then as can be known in the DP extraction, divide phasic property good, can remove heavy metal such as Pb and alkaline-earth metal and be lower than 10mg/l, and can make the Rh loss be lower than 6% until it.
Though reason is also indeterminate, but be considered to, thereby generate sludge because when extracting operation, Ru can not stably be present in aqueous phase.
In order before extracting operation, to carry out removing of Ru, can implement by for example distillation procedure.
As from the foregoing,, in the DP extraction, divide phasic property good, can remove heavy metal, alkaline-earth metal, and the Rh loss is also few according to embodiment 1,2,3.
Claims (5)
1. the method for purification of a Rh solution, it is characterized in that, in containing heavy metal and alkaline-earth metal any more than a kind impurity and the aqueous hydrochloric acid of the Rh of Ag in add alkali, pH is adjusted to 7～12, filtering separation makes the sedimentary neutralization precipitation thing of composition beyond the Rh, and the Cl when adjustment hydrochloric acid addition dissolves to use hydrochloric acid again is 3～4 to the mol ratio Cl/Rh of Rh, with adjusted liquid filtering like this, after Ag removed as throw out, extract with DEHPA.
2. the method for purification of Rh solution according to claim 1, it is characterized in that, in the aqueous hydrochloric acid of Rh, add alkali, pH is adjusted to 7～12, make Rh one-tenth fractional precipitation in addition, after this neutralization precipitation thing filtering separation,, so that being 2.7～3.5 to the mol ratio Cl/Rh of Rh, the Rh solution that so obtains is filtered, after Ag is removed as throw out Cl by dissolving with hydrochloric acid, add hydrochloric acid so that Cl is 4～8 to the mol ratio Cl/Rh of Rh, resulting liquid is extracted with DEHPA.
3. the method for purification of Rh solution according to claim 1, it is characterized in that, filtering separation makes the sedimentary neutralization precipitation thing of composition beyond the Rh, Cl when adjustment hydrochloric acid addition dissolves to use hydrochloric acid again is 3～4 o'clock to the mol ratio Cl/Rh of Rh, heating postcooling more than 90 ℃, after afterwards Ag being removed as throw out, extract with DEHPA.
4. the method for purification of Rh solution according to claim 2 is characterized in that, is adding hydrochloric acid so that Cl is to the mol ratio Cl/Rh of Rh at 4～8 o'clock, is extracting with DEHPA afterwards to room temperature with heating postcooling more than 90 ℃.
5. according to the method for purification of each described Rh solution in the claim 1～4, it is characterized in that, with hydrochloric acid with Rh neutralization precipitation thing again the Ru concentration in the dissolved liquid be made as below the 20mg/l, extract with DEHPA, both the rate of recovery of Rh can be highly guaranteed thus, heavy metal, alkaline-earth metal can be removed again water.
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|---|---|---|---|---|
| CN103343239A (en) * | 2013-07-25 | 2013-10-09 | 贵研资源（易门）有限公司 | Method for separating and purifying rhodium |
| CN114453589A (en) * | 2022-02-18 | 2022-05-10 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AP2010005222A0 (en) | 2007-09-14 | 2010-04-30 | Barrick Gold Corp | Process for recovering platinum group metals usingreductants |
| CN115074537A (en) * | 2022-07-06 | 2022-09-20 | 山东海科创新研究院有限公司 | Ruthenium ion recovery method |
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| JPS61183420A (en) * | 1985-02-08 | 1986-08-16 | Sumitomo Metal Mining Co Ltd | Separation of rhodium from acidic aqueous solution of hydrochloric acid |
| JPH0649555A (en) * | 1992-08-04 | 1994-02-22 | N E Chemcat Corp | Method for recovering rhodium |
| JPH10226828A (en) * | 1997-02-18 | 1998-08-25 | Sumitomo Metal Mining Co Ltd | Method for refining rhodium from rhodium-containing precipitate |
| JP3741117B2 (en) * | 2003-09-26 | 2006-02-01 | 住友金属鉱山株式会社 | Mutual separation of platinum group elements |
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| CN103343239A (en) * | 2013-07-25 | 2013-10-09 | 贵研资源（易门）有限公司 | Method for separating and purifying rhodium |
| CN103343239B (en) * | 2013-07-25 | 2014-08-20 | 贵研资源（易门）有限公司 | Method for separating and purifying rhodium |
| CN114453589A (en) * | 2022-02-18 | 2022-05-10 | 贵研铂业股份有限公司 | Preparation method of high-purity gold |
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