CN114350971A - Method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag - Google Patents
Method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag Download PDFInfo
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 150
- 239000010948 rhodium Substances 0.000 title claims abstract description 150
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002893 slag Substances 0.000 title claims abstract description 21
- 238000001556 precipitation Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 239000002244 precipitate Substances 0.000 claims abstract description 43
- 238000001914 filtration Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 24
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 12
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 52
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 29
- 238000001704 evaporation Methods 0.000 claims description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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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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Abstract
The invention relates to a method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag, which comprises the steps of slurrying the rhodium-containing ammonium chloroplatinate precipitation slag with boiled deionized water, adjusting the pH of the solution to be = 10-12, adding a sodium borohydride solution for reduction, adding a small amount of sodium borohydride solution after complete reduction to ensure that the sodium borohydride in the solution is excessive, boiling, filtering, discarding supernatant, washing the precipitate to obtain platinum-rhodium powder, dissolving the platinum-rhodium powder with aqua regia, filtering to remove the precipitate to obtain feed liquid, concentrating nitrate removal, hydrolyzing with sodium hypochlorite to obtain rhodium precipitate, dissolving the rhodium precipitate to obtain exchange liquid through ion exchange, extracting the exchange liquid with TBP to obtain pure rhodium liquid, precipitating the pure rhodium liquid with tetramethylammonium chloride, precipitating, calcining, and introducing hydrogen to obtain rhodium powder. The method can extract rhodium powder from the ammonium chloroplatinate precipitation slag with low rhodium content, and has the advantages of simple operation, good repeatability, no special requirement on equipment, recovery rate of more than 90 percent, purity of the rhodium powder of 99.95-99.98 percent and the like.
Description
Technical Field
The invention belongs to the field of precious metal recovery and purification, and particularly relates to a method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag.
Background
In the separation and purification of platinum-rhodium alloy, after platinum is separated, in the refining process of rhodium, ammonia water is usually used for adjusting the pH of the solution to =1.5, so that platinum is precipitated in the form of ammonium chloroplatinate, rhodium is left in the solution in the form of chloro complex anion, and then the rhodium solution is primarily purified by filtration. In the actual production, the unit finds that the finally obtained ammonium chloroplatinate precipitation slag contains 2 to 6 percent of rhodium besides a large amount of platinum due to the fact that partial alkali concentration is too high when the pH is adjusted by ammonia water or the concentration of rhodium liquid is too high, so that part of rhodium is precipitated together with platinum, washing is insufficient during filtering, other operational factors are artificial, and the like. The price of the noble metal rhodium is high, and the price fluctuation in the market is large, particularly in the early year, the price rises to about 7000 yuan/gram. Therefore, the method has high economic benefit for timely recovering rhodium from the rhodium-containing ammonium chloroplatinate precipitation slag. Secondly, the recovery and utilization of the noble metal rhodium are changed, so that the damage to the environment caused by mining ores for refining the rhodium is reduced.
The difficult problem of recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag is that the dissolution of materials is extremely slow when aqua regia is directly used, which is not beneficial to industrial production. The literature reports that ammonium chloroplatinate precipitate is pulped by adding water, reduced by adding hydrazine hydrate, and then dissolved by aqua regia to extract platinum. However, direct addition of hydrazine hydrate makes it difficult to completely reduce the slurry, particularly rhodium, resulting in only refining of platinum in the subsequent recovery process, and even if very little rhodium is reduced, recovery of rhodium from rhodium-containing ammonium chloroplatinate has been ignored in reports of recovery of rhodium-containing ammonium chloroplatinate. Secondly, the difficult problem is the refining of rhodium, and because the content of rhodium in slag is low and the content of impurities is high, the rhodium slag is difficult to purify and meets the industrial use requirement. Therefore, a method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag is urgently needed.
Disclosure of Invention
The invention aims to provide a method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag, which has the advantages of simple operation, good repeatability, no special requirement on equipment and the like.
The technical scheme of the invention is as follows:
a method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag comprises the steps of slurrying the rhodium-containing ammonium chloroplatinate precipitation slag with boiled deionized water, adjusting the pH = 10-12 of a solution, adding a sodium borohydride solution for reduction, adding a small amount of sodium borohydride solution after complete reduction, boiling, filtering, discarding supernatant, washing the precipitate to obtain platinum-rhodium powder, dissolving the platinum-rhodium powder with aqua regia, filtering to remove the precipitate to obtain a feed liquid, concentrating and removing nitrate, hydrolyzing with sodium hypochlorite to obtain rhodium precipitate, performing ion exchange to obtain an exchange liquid after the rhodium precipitate is dissolved, extracting the exchange liquid with TBP to obtain pure rhodium liquid, precipitating the pure rhodium liquid with tetramethylammonium chloride, calcining the obtained precipitate, and introducing hydrogen to obtain rhodium powder.
The concentration of the sodium borohydride is 20 g/L.
The small amount means that the sodium borohydride solution in the solution is made to be excessive.
The pH value of the solution is adjusted by using sodium hydroxide solution with the concentration of 20 g/L.
The hydrolysis method comprises the following steps: concentrating the feed liquid 1, removing nitrate until liquid film appears,
A. adding deionized water for dissolution, controlling the total concentration of platinum and rhodium to be 40-60 g/L, after boiling, adjusting the pH value of the solution to be = 8-10 by using sodium hypochlorite with the concentration of 2.5mol/L, standing for 12-24 h, and filtering to obtain rhodium precipitate 1;
B. and (3) dissolving the rhodium precipitate 1 with hydrochloric acid, evaporating to dryness, repeating the step A, standing for 8-24 h, filtering, and washing a filter cake for several times with a saturated sodium chloride solution to obtain the rhodium precipitate.
The ion exchange: dissolving the rhodium precipitate with hydrochloric acid, evaporating to dryness, dissolving with deionized water, diluting until the rhodium concentration is 30-50 g/L, adjusting the pH value to be = 1.5-2.0 with ammonia water, filtering, exchanging the filtrate with cation resin to obtain an exchange solution 1, concentrating and evaporating the exchange solution 1 to dryness to obtain crystals, adding water for dissolving, and repeating the steps for the second exchange to obtain the exchange solution.
The cation exchange resin is 732 type strong acid type cation exchange resin.
The TBP extraction method comprises the following steps: concentrating and evaporating the exchange solution to dryness, dissolving the exchange solution by using a saturated acidic sodium chloride solution, controlling the concentration of rhodium in the solution to be 30-50 g/L, pouring the rhodium into a TBP solution, introducing chlorine, stirring, standing for layering, taking a rhodium solution, and repeating the steps to perform secondary extraction to obtain a pure rhodium solution.
The preparation method of the saturated acidic sodium chloride solution comprises the following steps: preparing 4mol/L hydrochloric acid solution, and adding sodium chloride solid into the hydrochloric acid solution until the sodium chloride solid is not dissolved.
The method for precipitating the pure rhodium solution by tetramethylammonium chloride comprises the following steps: evaporating the pure rhodium solution to dryness, adding water to dissolve the pure rhodium solution, controlling the concentration of rhodium to be 40-60 g/L, boiling, adding tetramethylammonium chloride solid with the weight of rhodium being 3.5-4.0 times of that of the rhodium, and concentrating to obtain tetramethylammonium chlororhodate precipitate.
The precipitate calcination is to calcine the precipitate at 550 ℃ for 2h to obtain sponge rhodium; and the hydrogen is introduced, namely the sponge rhodium is introduced with hydrogen at 800 ℃ for reduction for 2h, the hydrogen is continuously introduced until the furnace temperature is reduced to 100 ℃, and then the sponge rhodium is naturally cooled to the room temperature.
According to the method, sodium borohydride is adopted to reduce the rhodium-containing chloroplatinic acid ammonium slurrying solution, and the sodium borohydride has stronger reducibility than hydrazine hydrate, so that the slurrying solution is reduced more thoroughly, particularly, rhodium is reduced, and the subsequent recovery of rhodium is facilitated
The method adopts the steps of reducing the rhodium-containing ammonium chloroplatinate, and immediately dissolving the platinum-rhodium powder with high activity by using aqua regia, so that the material dissolving time can be greatly shortened.
According to the invention, sodium borohydride is adopted to reduce the rhodium-containing chloroplatinic acid ammonium slurrying solution, and an excessive sodium borohydride solution is added to ensure that platinum and rhodium in the solution are completely reduced. The method combines the steps of dissolving platinum and rhodium powder by aqua regia, hydrolyzing by sodium hypochlorite to primarily separate platinum and rhodium, removing base metals by ion exchange, extracting platinum by TBP, precipitating rhodium by tetramethylammonium chloride and the like, can extract rhodium powder which is industrially available from ammonium chloroplatinate precipitation slag with low rhodium content, and has the recovery rate of more than 90 percent and the purity of the rhodium powder of 99.95 to 99.98 percent.
The method adopts tetramethylammonium chloride to precipitate rhodium, and because the tetramethylammonium chloride has larger molecular weight than ammonium chloride, rhodium is more thoroughly precipitated, thereby being beneficial to improving the recovery rate of rhodium.
The invention continues to be cooled by introducing hydrogen to the furnace temperature of 100 ℃ after introducing hydrogen for 2h at 800 ℃, and other gas is not needed for protection cooling, thereby reducing the trouble in operation.
The method has the advantages of simple operation, good repeatability, no special requirement on equipment and the like.
Detailed Description
In the invention, sodium hydroxide, sodium chloride and tetramethylammonium chloride adopt commercially available superior pure reagents, and other chemicals adopt commercially available analytical pure reagents.
Example 1
1. Pretreatment of rhodium-containing ammonium chloroplatinate precipitate
2412.20g of rhodium-containing ammonium chloroplatinate precipitation slag is added into 20L of boiled deionized water for slurrying, the pH =10 of the solution is adjusted by a sodium hydroxide solution with the concentration of 20g/L, then a sodium borohydride solution with the concentration of 20g/L is slowly added for reduction, after the reduction is completed, 5ml of sodium borohydride solution is added to ensure that the sodium borohydride in the solution is excessive, the solution is boiled for 30min, the solution is filtered, the supernatant is discarded, the precipitate is washed, and the precipitate is dried to obtain 900.12g of crude platinum rhodium powder.
2. Aqua regia liquid preparation
Equally dividing the crude platinum rhodium powder into 6 5000ml beakers, respectively adding 2000ml of dilute aqua regia (the volume ratio of the dilute aqua regia is concentrated hydrochloric acid to concentrated nitric acid to water =5:1:1, the weight percentage concentration of the concentrated nitric acid is 86%, and the weight percentage concentration of the hydrochloric acid is 37%), heating for dissolving until the solution is completely dissolved, and filtering to remove insoluble substances to obtain feed liquid 1.
3. Hydrolysis
And 3.1, filtering the feed liquid 1 in the step 2, uniformly distributing the filtered feed liquid in 6 5000ml beakers, heating and concentrating to remove nitrate until no reddish brown gas appears, continuously concentrating until a liquid film appears, adding deionized water to dissolve, controlling the concentration of the feed liquid to be approximately equal to 40g/L, adjusting the pH of the solution to be =8 by using sodium hypochlorite with the concentration of 2.5mol/L after boiling, standing for 12h, and filtering to obtain rhodium precipitate 1 and filtrate 1.
3.2 rhodium deposition 1 using concentrated hydrochloric acid (the weight percentage concentration of concentrated hydrochloric acid is 37%, the same below) to dissolve, evaporating to dryness, adding water to dissolve, controlling the feed liquid concentration to be approximately equal to 40g/L, after boiling, using sodium hypochlorite with the concentration of 2.5mol/L to adjust the pH of the solution to be =8, standing for 12h, filtering, washing the filter cake with saturated sodium chloride solution for 3 times, obtaining rhodium deposition 2 and filtrate 2.
4. Ion exchange
Dissolving the rhodium precipitate 2 with hydrochloric acid, evaporating to dryness, dissolving with deionized water, controlling the concentration of the feed liquid to be approximately equal to 30g/L, adjusting the pH of the solution to be =1.5 with ammonia water, exchanging the filtrate with 732 strong acid type cation resin after filtering, and washing out residual rhodium liquid in the resin with hydrochloric acid solution with the pH of = 1.5. Concentrating the exchange solution 1, evaporating to dryness, and repeating the above steps to obtain the exchange solution.
5. TBP extraction
Concentrating and evaporating the exchange liquid to dryness, dissolving the exchange liquid by using a saturated acidic sodium chloride solution, controlling the concentration of rhodium in the feed liquid to be approximately equal to 30g/L, pouring the rhodium into a TBP extraction bottle with the volume of 1000ml, introducing chlorine for 10min, stirring for 10min, standing for layering, discharging lower-layer rhodium liquid, pouring the rhodium liquid into an extraction bottle with the volume of 1000ml of TBP solvent, repeating the steps and extracting once again to obtain pure rhodium liquid.
6. Precipitating tetramethylammonium chloride, calcining, introducing hydrogen
Evaporating a pure rhodium solution to dryness, adding water for dissolving, controlling the rhodium concentration in the feed liquid to be approximately 40g/L, boiling, adding 110g of tetramethylammonium chloride solid (more than or equal to 99.8%) under stirring, concentrating to obtain tetramethylchloroammonium rhodate crystal precipitate, filtering, washing a filter cake for 3 times by using a tetramethylammonium chloride solution with the weight percentage concentration of 20%, transferring the precipitate into a crucible, calcining for 2 hours at 550 ℃, naturally cooling to room temperature to obtain sponge rhodium, taking out, grinding the sponge rhodium, placing the sponge rhodium into a quartz tube, introducing hydrogen at 800 ℃ for reduction for 2 hours, continuously introducing hydrogen until the furnace temperature is reduced to 100 ℃, naturally cooling to room temperature, taking out, and detecting and analyzing by GDMS to obtain the rhodium powder with the purity of 99.95-99.98%.
Example 2
1. Pretreatment of rhodium-containing ammonium chloroplatinate precipitate
3200.11g of rhodium-containing ammonium chloroplatinate precipitation slag is added into 38L of boiled deionized water for slurrying, the pH =12 of the solution is adjusted by a sodium hydroxide solution with the concentration of 20g/L, then a sodium borohydride solution with the concentration of 20g/L is slowly added for reduction, after the reduction is completed, 5ml of sodium borohydride solution is added to ensure that the sodium borohydride in the solution is excessive, the solution is boiled for 30min, the supernatant is discarded, and the solution is filtered, washed and drained to obtain 1230.10g of crude platinum rhodium powder.
2. Aqua regia liquid preparation
Equally dividing the crude platinum rhodium powder into 8 5000ml beakers, respectively adding 2000ml of dilute aqua regia (the volume ratio of the dilute aqua regia is concentrated hydrochloric acid to concentrated nitric acid to water =5:1:1, the weight percentage concentration of the concentrated nitric acid is 86%, and the weight percentage concentration of the hydrochloric acid is 37%), heating for dissolving until the solution is completely dissolved, and filtering to remove insoluble substances to obtain feed liquid 1.
3. Hydrolysis
And 3.1, filtering the feed liquid 1 in the step 2, uniformly distributing the filtered feed liquid in 8 5000ml beakers, heating and concentrating to remove nitrate until no reddish brown gas appears, continuously concentrating until a liquid film appears, adding deionized water to dissolve, controlling the concentration of the feed liquid to be approximately equal to 60g/L, boiling, adjusting the pH of the solution to be =9 by using sodium hypochlorite with the concentration of 2.5mol/L, standing for 24h, and filtering to obtain rhodium precipitate 1 and filtrate 1.
3.2 rhodium deposition 1 using concentrated hydrochloric acid (the weight percentage concentration of concentrated hydrochloric acid is 37%, the same below) to dissolve, evaporating to dryness, adding water to dissolve, controlling the feed liquid concentration to be approximately equal to 60g/L, boiling, adjusting pH with sodium hypochlorite =9, standing for 24h, filtering, washing the filter cake with saturated sodium chloride solution for 4 times, getting rhodium deposition 2 and filtrate 2.
4. Ion exchange
Dissolving the rhodium precipitate 2 with hydrochloric acid, evaporating to dryness, dissolving with deionized water, controlling the concentration of the feed liquid to be approximately equal to 50g/L, adjusting the pH of the solution to be =2.0 with ammonia water, exchanging the filtrate with 732 strong acid type cation resin after filtering, and washing out residual rhodium liquid in the resin with hydrochloric acid solution with the pH = 2.0. Concentrating the exchange solution 1, evaporating to dryness, and repeating the above steps to obtain the exchange solution.
5. TBP extraction
Concentrating and evaporating the exchange solution 2 to dryness, dissolving the exchange solution with saturated acidic sodium chloride solution, controlling the concentration of rhodium in the feed liquid to be approximately equal to 40g/L, pouring the rhodium into an extraction bottle filled with 1000ml of TBP, introducing chlorine for 10min, stirring for 10min, standing for layering, discharging the lower-layer rhodium solution, pouring the rhodium solution into the extraction bottle filled with 1000ml of TBP, and repeating the steps to extract once again to obtain pure rhodium solution.
6. Precipitating tetramethylammonium chloride, calcining, introducing hydrogen
Evaporating pure rhodium solution to dryness, adding water for dissolving, controlling the concentration of the feed liquid to be 60g/L, boiling, adding 150g of tetramethylammonium chloride solid (more than or equal to 99.8%) under stirring, concentrating to obtain tetramethylammonium chlororhodate crystal precipitate, filtering, washing a filter cake for 5 times by using tetramethylammonium chloride solution with the weight percentage concentration of 20%, transferring to a crucible, calcining at 550 ℃ for 2h, naturally cooling to room temperature to obtain sponge rhodium, taking out, grinding the sponge rhodium, filling hydrogen into a quartz tube for reduction for 2h at 800 ℃, continuously filling hydrogen until the furnace temperature is 100 ℃, naturally cooling to room temperature, taking out, and detecting and analyzing by GDMS (gas chromatography mass spectrometry) to obtain the rhodium powder with the purity of 99.95-99.98%.
Example 3
1. Pretreatment of rhodium-containing ammonium chloroplatinate precipitate
1840.70 ammonium chloroplatinate precipitation slag containing rhodium is added into 18L boiled deionized water for slurrying, the pH =10 of the solution is adjusted by a sodium hydroxide solution with the concentration of 20g/L, then a sodium borohydride solution with the concentration of 20g/L is slowly added for reduction, after the reduction is completed, 5ml of sodium borohydride solution is added to ensure that the sodium borohydride in the solution is excessive, the solution is boiled for 30min, the supernatant is discarded, the solution is filtered and washed, and the wet weight is 699.52g of crude platinum rhodium powder after the extraction.
2. Aqua regia liquid preparation
Equally dividing the crude platinum rhodium powder into 5 5000ml beakers, respectively adding 2000ml of dilute aqua regia (the volume ratio of the dilute aqua regia is concentrated hydrochloric acid to concentrated nitric acid: water =5:1:1, the weight percentage concentration of the concentrated nitric acid is 86%, and the weight percentage concentration of the hydrochloric acid is 37%), heating for dissolving until the solution is completely dissolved, and filtering to remove insoluble substances to obtain feed liquid 1.
3. Hydrolysis
And 3.1, filtering the feed liquid 1 in the step 2, uniformly distributing the filtered feed liquid in 5 5000ml beakers, heating and concentrating to remove nitrate until no reddish brown gas appears, continuously concentrating until a liquid film appears, adding deionized water to dissolve, controlling the concentration of the feed liquid to be approximately equal to 50g/L, boiling, adjusting the pH of the solution to be =10 by using sodium hypochlorite with the concentration of 2.5mol/L, standing for 24h, and filtering to obtain rhodium precipitate 1 and filtrate 1.
3.2 rhodium deposition 1 using concentrated hydrochloric acid (hydrochloric acid weight percentage concentration of 37%, the same below) dissolved, evaporation to dryness, water dissolution, control feed liquid concentration of approximately 50g/L, boiling, using 2.5mol/L sodium hypochlorite to adjust solution pH =10, standing 24h, filtering, filter cake using saturated sodium chloride solution washing 5 times, get rhodium deposition 2 and filtrate 2.
4. Ion exchange
Dissolving the rhodium precipitate 2 with concentrated hydrochloric acid, evaporating to dryness, dissolving with deionized water, controlling the concentration of feed liquid to be approximately equal to 50g/L, adjusting the pH of the solution to be =2.0 with ammonia water, filtering, exchanging filtrate with 732 type strong acid type cation resin, and washing residual rhodium solution in the resin with hydrochloric acid solution with the pH of =2.0 to obtain an exchange solution 1. Concentrating the exchange solution 1, evaporating to dryness, and repeating the above steps to obtain the exchange solution.
5. TBP extraction
Concentrating and evaporating the exchange liquid to dryness, dissolving the exchange liquid by using a saturated acidic sodium chloride solution, controlling the concentration of rhodium in the feed liquid to be approximately equal to 50g/L, pouring the rhodium into an extraction bottle filled with 500ml of TBP, introducing chlorine for 10min, stirring for 10min, standing for layering, discharging the lower-layer rhodium liquid, pouring the rhodium liquid into the extraction bottle filled with 500ml of TBP, and repeating the steps to extract once again to obtain pure rhodium liquid.
6. Precipitating tetramethylammonium chloride, calcining, introducing hydrogen
Evaporating pure rhodium solution to dryness, adding water for dissolving, controlling the concentration of the feed liquid to be 50g/L, boiling, adding 96g of tetramethylammonium chloride solid (more than or equal to 99.8%) under stirring, concentrating to obtain tetramethylammonium chlororhodate crystal precipitate, filtering, washing a filter cake for 4 times by using tetramethylammonium chloride solution with the weight percentage concentration of 20%, transferring to a crucible, calcining at 550 ℃ for 2h, naturally cooling to room temperature to obtain sponge rhodium, taking out, grinding the sponge rhodium, filling hydrogen into a quartz tube for reduction for 2h at 800 ℃, continuously filling hydrogen until the furnace temperature is 100 ℃, naturally cooling to room temperature, taking out, and detecting and analyzing by GDMS (gas chromatography mass spectrometry) to obtain the rhodium powder with the purity of 99.95-99.98%.
Claims (10)
1. A method for recovering rhodium from rhodium-containing ammonium chloroplatinate precipitation slag is characterized by slurrying the rhodium-containing ammonium chloroplatinate precipitation slag with boiled deionized water, adjusting the pH = 10-12 of a solution, adding a sodium borohydride solution for reduction, adding a small amount of the sodium borohydride solution after complete reduction, boiling, filtering, discarding a supernatant, washing the precipitate to obtain platinum-rhodium powder, dissolving the platinum-rhodium powder with aqua regia, filtering to remove the precipitate to obtain a feed liquid, concentrating to remove nitrate, hydrolyzing with sodium hypochlorite to obtain rhodium precipitate, dissolving the rhodium precipitate to obtain an exchange liquid through ion exchange, extracting the exchange liquid with TBP to obtain a pure rhodium liquid, precipitating the pure rhodium liquid with tetramethylammonium chloride, calcining the obtained precipitate, and introducing hydrogen to obtain the rhodium powder.
2. The method of claim 1, wherein: the concentration of the sodium borohydride is 20 g/L.
3. The method of claim 1, wherein: the small amount means that the sodium borohydride solution in the solution is made to be excessive.
4. The method of claim 1, wherein: the pH value of the solution is adjusted by using sodium hydroxide solution with the concentration of 20 g/L.
5. The method according to claim 1, characterized in that the method of hydrolysis: concentrating the feed liquid 1, removing nitrate until liquid film appears,
A. adding deionized water for dissolution, controlling the total concentration of platinum and rhodium to be 40-60 g/L, after boiling, adjusting the pH value of the solution to be = 8-10 by using sodium hypochlorite with the concentration of 2.5mol/L, standing for 12-24 h, and filtering to obtain rhodium precipitate 1;
B. and (3) dissolving the rhodium precipitate 1 with hydrochloric acid, evaporating to dryness, repeating the step A, standing for 8-24 h, filtering, and washing a filter cake for several times with a saturated sodium chloride solution to obtain the rhodium precipitate.
6. The method of claim 1, wherein the ion exchange: dissolving rhodium precipitate with hydrochloric acid, evaporating to dryness, dissolving with deionized water, diluting until the rhodium concentration is 30-50 g/L, adjusting the pH value with ammonia water to be = 1.5-2.0, filtering, exchanging filtrate with cation resin to obtain an exchange solution 1, concentrating and evaporating the exchange solution 1 to dryness to obtain crystals, adding water for dissolving, and repeating the steps for exchanging once to obtain the exchange solution.
7. The method of claim 1, wherein the TBP extraction method comprises: concentrating and evaporating the exchange solution to dryness, dissolving the exchange solution by using a saturated acidic sodium chloride solution, controlling the concentration of rhodium in the solution to be 30-50 g/L, pouring the rhodium into a TBP solution, introducing chlorine, stirring, standing for layering, taking a rhodium solution, and repeating the steps to perform secondary extraction to obtain a pure rhodium solution.
8. The method according to claim 7, wherein the saturated acidic sodium chloride solution is prepared by the following method: preparing 4mol/L hydrochloric acid solution, and adding sodium chloride solid into the hydrochloric acid solution until the sodium chloride solid is not dissolved.
9. The method of claim 1, wherein the pure rhodium solution is precipitated by tetramethylammonium chloride: evaporating the pure rhodium solution to dryness, adding water to dissolve the pure rhodium solution, controlling the concentration of rhodium to be 40-60 g/L, boiling, adding tetramethylammonium chloride solid with the weight of rhodium being 3.5-4.0 times of that of the rhodium, and concentrating to obtain tetramethylammonium chlororhodate precipitate.
10. The method as claimed in claim 1, wherein the precipitation calcination is to calcine the precipitate at 550 ℃ for 2h to obtain sponge rhodium; and the hydrogen is introduced, namely the sponge rhodium is introduced with hydrogen at 800 ℃ for reduction for 2h, the hydrogen is continuously introduced until the furnace temperature is reduced to 100 ℃, and then the sponge rhodium is naturally cooled to the room temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114134335A (en) * | 2021-10-18 | 2022-03-04 | 英特派铂业股份有限公司 | Method for recovering rhodium in rhodium-containing nitrite wastewater |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260469A (en) * | 2008-04-21 | 2008-09-10 | 上海大学 | Method for reclaiming and purifying platinum and rhodium from waste material containing platinum and rhodium |
| CN103131857A (en) * | 2011-11-29 | 2013-06-05 | 沈阳有色金属研究院 | Method for purifying platinum group metal from waste three-way catalyst |
| CN104860358A (en) * | 2015-04-23 | 2015-08-26 | 金川集团股份有限公司 | High purity rhodium recovery purification method |
| WO2017143499A1 (en) * | 2016-02-22 | 2017-08-31 | Entegris, Inc. | Recovery of palladium from palladium-containing components |
| RU2693285C1 (en) * | 2018-11-06 | 2019-07-02 | Игорь Владимирович Федосеев | METHOD OF SEPARATING METALS FROM PLATINUM, PALLADIUM, RHODIUM Pt-Pd-Rh |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
-
2021
- 2021-11-29 CN CN202111433052.4A patent/CN114350971B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260469A (en) * | 2008-04-21 | 2008-09-10 | 上海大学 | Method for reclaiming and purifying platinum and rhodium from waste material containing platinum and rhodium |
| CN103131857A (en) * | 2011-11-29 | 2013-06-05 | 沈阳有色金属研究院 | Method for purifying platinum group metal from waste three-way catalyst |
| CN104860358A (en) * | 2015-04-23 | 2015-08-26 | 金川集团股份有限公司 | High purity rhodium recovery purification method |
| WO2017143499A1 (en) * | 2016-02-22 | 2017-08-31 | Entegris, Inc. | Recovery of palladium from palladium-containing components |
| RU2693285C1 (en) * | 2018-11-06 | 2019-07-02 | Игорь Владимирович Федосеев | METHOD OF SEPARATING METALS FROM PLATINUM, PALLADIUM, RHODIUM Pt-Pd-Rh |
| CN111054933A (en) * | 2019-12-09 | 2020-04-24 | 重庆材料研究院有限公司 | Method for preparing high-purity rhodium powder from platinum-rhodium waste |
Non-Patent Citations (1)
| Title |
|---|
| 张健,徐颖,张骥: "新型高强还原剂在铂族金属提取上的应用" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114134335A (en) * | 2021-10-18 | 2022-03-04 | 英特派铂业股份有限公司 | Method for recovering rhodium in rhodium-containing nitrite wastewater |
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