CN115074544A - Method for recovering noble metal rhodium in rhodium-containing working solution - Google Patents
Method for recovering noble metal rhodium in rhodium-containing working solution Download PDFInfo
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- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 84
- 239000010948 rhodium Substances 0.000 title claims abstract description 84
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012224 working solution Substances 0.000 title claims abstract description 23
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 229920002261 Corn starch Polymers 0.000 claims description 8
- 239000008120 corn starch Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims 3
- 230000000630 rising effect Effects 0.000 claims 2
- 239000010970 precious metal Substances 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000013589 supplement Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- -1 Platinum group metals Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- KZKIPJHCUMSQEK-UHFFFAOYSA-N O=[O+][O-].Cl Chemical compound O=[O+][O-].Cl KZKIPJHCUMSQEK-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
- C22B11/021—Recovery of noble metals from waste materials
- C22B11/026—Recovery of noble metals from waste materials from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- 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
Abstract
The invention belongs to the technical field of precious metal recovery, and particularly relates to a method for recovering precious metal rhodium in rhodium-containing working solution. The method is realized by the following steps: adding an adsorbent into the rhodium-containing working solution, and uniformly mixing to obtain a mixture; roasting the mixture to obtain rhodium ash, then uniformly mixing sodium bisulfate and sodium chloride, and putting the mixture into a furnace with oxygen for roasting to obtain a reaction product; dissolving the reaction product with water, filtering, adding NaOH solution into the filtrate, and adjusting the pH value to obtain rhodium hydroxide precipitate. According to the invention, the specific adsorbent is added into the working solution to adsorb the noble metal rhodium, and the organic matter is continuously carbonized in the process of slowly raising the temperature, so that the noble metal rhodium is removed from the system, the loss of the noble metal rhodium is effectively reduced, and the recovery rate of the rhodium can reach more than 94%.
Description
Technical Field
The invention belongs to the technical field of precious metal recovery, and particularly relates to a method for recovering precious metal rhodium in rhodium-containing working solution.
Background
Platinum group metals in China are rarely distributed, particularly the noble metal rhodium has unique physical and chemical characteristics, particularly high catalytic activity and high selectivity, so that the rhodium catalyst is widely applied to petroleum industry catalysts, automobile three-way catalysts, catalytic hydrogenation, methanol carbonylation, olefin hydroformylation and the like, and therefore the market demand is considerable. However, rhodium is rarely distributed in the earth crust, and domestic mineral resources are deficient, so that separation and purification are difficult, thereby greatly limiting the possibility of obtaining a rhodium-containing source by domestic production enterprises and seriously restricting the development of domestic chemical enterprises. In recent years, domestic researchers have continuously researched the recovery of noble metals containing rhodium catalysts, and a set of rhodium recovery method system is formed.
Methods for recovering rhodium from the deactivated spent catalyst are classified into wet methods and combustion methods. The wet recovery of rhodium includes extraction, precipitation, oxidation distillation, washing, adsorption separation, chemical activation, etc.
The extraction method disclosed in Japanese patent No. 56-2994 and the adsorption separation method disclosed in Japanese patent No. 49-121793 recover rhodium by separating the organic components and rhodium complex in the spent catalyst through extraction or adsorption, and because the noble metal rhodium has strong chemical binding capacity with the organic phosphine compound and the catalyst raffinate is viscous, the recovery rates of rhodium in these methods are low, respectively about 90% and 91%.
Chinese patent ZL200710177195 introduces a liquid destructive decomposition method for recovering waste rhodium catalyst raffinate, the method utilizes a mixed solution of inorganic acid and oxidant to carry out high-temperature digestion, carbonization and oxidation on the waste rhodium catalyst raffinate, and removes organic components in a gas form to recover rhodium, and the recovery rate of the method is higher than 97 percent, and the defect is that the efficiency is relatively low.
A basic compound of Ia or IIa group of the periodic table of elements is added into the residual liquid of the waste rhodium catalyst in the ZL patent 93117639 to burn and recover rhodium, the recovery rate of rhodium can reach more than 99 percent, and the method needs strict temperature control to reduce rhodium loss and prevent rhodium from overburning, thus being not very beneficial to industrial amplification.
According to the Chinese patent ZL201210437138.9, on the basis of temperature programming, silicon dioxide is added as a protective agent, so that rhodium loss and rhodium overburning control become more favorable, however, due to the consideration of rhodium overburning, part of organic matters cannot be removed through burning, further treatment is needed through hydrochloric acid ozone, and the treatment time is longer.
The Beijing chemical research institute recovers rhodium by a combustion method, and incinerates waste liquid containing rhodium catalyst by adopting a specific temperature-raising program to obtain rhodium ash. The rhodium loss in the incineration and ashing process is less, and the rhodium recovery rate is greatly improved. The method for recovering the rhodium by vacuum distillation, evaporation and incineration is also provided for the low-concentration rhodium waste liquid, the equipment is simple, the operation is easy, the recovery rate of the rhodium is relatively high, but a large amount of bubbles are generated in the combustion process, and organic matters contained in the rhodium are easy to catch fire, so that the loss of the rhodium is caused.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for recovering noble metal rhodium in rhodium-containing working solution, which can prepare rhodium trichloride, overcomes the defects of a wet method and a combustion method in the prior art, and recovers the noble metal rhodium in the working solution by a simple recovery process and high yield.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention provides a method for recovering noble metal rhodium in rhodium-containing working solution, which comprises the following steps:
(1) adding an adsorbent into the rhodium-containing working solution, and uniformly mixing to obtain a mixture;
(2) roasting the mixture in a temperature programming mode to obtain rhodium ash;
(3) adding sodium bisulfate and sodium chloride into the roasted rhodium ash, uniformly mixing, and putting the mixture into a furnace with oxygen for roasting to obtain a reaction product;
(4) dissolving the reaction product with water, filtering, adding NaOH solution into the filtrate, and adjusting the pH value to obtain rhodium hydroxide precipitate.
Further, in the step (1), the mass ratio of the rhodium-containing working solution to the adsorbent is 1:0.5-1: 5.
Further, in the step (1), the adsorbent is one or two of corn starch and activated carbon.
The temperature raising program used in the invention is as follows: keeping the temperature at the interval of 50 ℃ for 60-240min before 200-300 ℃, keeping the temperature at the rate of 0.5-2.5 ℃/min, keeping the temperature at the interval of 100 ℃ for 60-240min after 200-300 ℃, keeping the temperature at the rate of 0.5-2.5 ℃/min until the temperature rises to 600-800 ℃, and keeping the temperature for 60-240 min.
Further, in the step (3), the adding amount of the sodium bisulfate and the sodium chloride is 5-15 times of that of the rhodium ash.
Further, in the step (3), the mass ratio of the sodium bisulfate to the sodium chloride is 5-30: 1.
Further, in the step (3), before the roasting is carried out at 200-300 ℃, the temperature is kept for 60-240min every other 50 ℃, the heating rate is 0.5-2.5 ℃/min, after the roasting is carried out at 200-300 ℃, the temperature is kept for 60-240min every other 100 ℃, the heating rate is 0.5-2.5 ℃/min, and the temperature is raised to 600-800 ℃.
Further, in the step (4), the mass ratio of the reaction product to water is 1: 1-5; the concentration of the NaOH solution is 1-5 mol/L; the pH value is 7-9.
Compared with the prior art, the invention has the following effects:
according to the invention, the specific adsorbent is added into the working solution to adsorb the noble metal rhodium, and the organic matter is continuously carbonized in the process of slowly raising the temperature, so that the noble metal rhodium is removed from the system, the loss of the noble metal rhodium is effectively reduced, and the recovery rate of the rhodium can reach more than 94%.
Detailed Description
The present invention will be described in further detail with reference to specific examples and comparative examples.
The rhodium concentration in the rhodium-containing working solution to be treated in the following examples was 1135 mg/kg.
Example 1
Adding 1000g of corn starch into 500g of rhodium-containing working solution, and uniformly mixing. And (2) placing the mixture into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting according to a specific temperature rise program, wherein the temperature is kept for 120min at intervals of 50 ℃ before 300 ℃, the temperature rise rate is 0.5 ℃/min, the temperature is kept for 120min at intervals of 100 ℃ after 300 ℃, the temperature rise rate is 1 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 100 ℃, and the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 120 min. After completion of calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to 8, to obtain a rhodium hydroxide precipitate, the results of which are shown in Table 1.
TABLE 1
Example 2
1200g of corn starch is added into 500g of rhodium-containing working solution and mixed evenly. And (2) placing the mixture into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting according to a specific temperature rise program, wherein the temperature is kept for 120min at intervals of 50 ℃ before 300 ℃, the temperature rise rate is 0.5 ℃/min, the temperature is kept for 120min at intervals of 100 ℃ after 300 ℃, the temperature rise rate is 1 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 100 ℃, the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 80 min. After completion of the calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to about 8, to obtain a rhodium hydroxide precipitate, the results of which are shown in Table 2.
TABLE 2
Example 3
Adding 1500g of corn starch into 500g of rhodium-containing working solution, and uniformly mixing. And (2) placing the mixture into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting according to a specific temperature rise program, wherein the temperature is kept for 120min at intervals of 50 ℃ before 300 ℃, the temperature rise rate is 0.5 ℃/min, the temperature is kept for 120min at intervals of 100 ℃ after 300 ℃, the temperature rise rate is 1 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 100 ℃, and the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 100 min. After completion of the calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to about 8, to obtain a rhodium hydroxide precipitate, the results of which are shown in Table 3.
TABLE 3
Example 4
1200g of corn starch is added into 500g of rhodium-containing working solution and mixed evenly. And (2) placing the mixture into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting according to a specific temperature rise program, wherein the temperature is kept for 240min at intervals of 50 ℃ before 300 ℃, the temperature rise rate is 0.5 ℃/min, and after 300 ℃, the temperature is kept for 240min at intervals of 100 ℃, the temperature rise rate is 1 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 240min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 240min at intervals of 100 ℃, and the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 240 min. After completion of the calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to about 8, to obtain a rhodium hydroxide precipitate, the results of which are shown in Table 4.
TABLE 4
Example 5
1200g of corn starch is added into 500g of rhodium-containing working solution and mixed evenly. And (2) placing the mixture into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting according to a specific temperature rise program, wherein the temperature is kept for 60min at intervals of 50 ℃ before 300 ℃, the temperature rise rate is 0.5 ℃/min, the temperature is kept for 60min at intervals of 100 ℃ after 300 ℃, the temperature rise rate is 1 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 60min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 60min at intervals of 100 ℃, and the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 60 min. After completion of the calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to about 8, to obtain a rhodium hydroxide precipitate, the results of which are shown in Table 5.
TABLE 5
Comparative example 1
500g of rhodium-containing working solution is put into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting is carried out according to a specific temperature rise program, wherein the temperature is kept at constant intervals of 50 ℃ for 120min before 300 ℃, the temperature rise rate is 0.5 ℃/min, the temperature is kept at constant intervals of 100 ℃ for 120min after 300 ℃, the temperature rise rate is 1 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 100 ℃, and the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 120 min. After completion of the calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to about 8, to obtain a rhodium hydroxide precipitate, and the results are shown in Table 6.
TABLE 6
Comparative example 2
1200g of corn starch is added into 500g of rhodium-containing working solution and mixed evenly. And (2) placing the mixture into a furnace which has a tail gas treatment function and can supplement oxygen, and roasting according to a specific temperature rise program, wherein the temperature is kept for 120min at intervals of 50 ℃ before 300 ℃, the temperature rise rate is 15 ℃/min, the temperature is kept for 120min at intervals of 100 ℃ after 300 ℃, the temperature rise rate is 15 ℃/min, and the temperature is raised to 600 ℃. Uniformly mixing the roasted rhodium ash with 10 times of sodium bisulfate and sodium chloride by mass, putting the mixture into a furnace with oxygen for roasting, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 50 ℃, wherein the heating rate is 0.5 ℃/min, keeping the temperature at the temperature of 300 ℃ for 120min at intervals of 100 ℃, and the heating rate is 1 ℃/min until the temperature is raised to 600 ℃, and keeping the temperature for 120 min. After completion of the calcination, the reaction product was dissolved in water, filtered, and added with 1mol/L NaOH solution to adjust the pH to about 8, to obtain a rhodium hydroxide precipitate, the results of which are shown in Table 7.
TABLE 7
Although the foregoing description describes embodiments of the present invention, it is not intended to limit the scope of the present invention, and those skilled in the art will appreciate that various modifications and variations can be made without inventive faculty, and without departing from the scope of the present invention.
Claims (8)
1. A method for recovering noble metal rhodium in rhodium-containing working solution is characterized by comprising the following steps:
(1) adding an adsorbent into the rhodium-containing working solution, and uniformly mixing to obtain a mixture;
(2) roasting the mixture in a temperature programming mode to obtain rhodium ash;
(3) adding sodium bisulfate and sodium chloride into the roasted rhodium ash, uniformly mixing, and putting the mixture into a furnace with oxygen for roasting to obtain a reaction product;
(4) dissolving the reaction product with water, filtering, adding NaOH solution into the filtrate, and adjusting the pH value to obtain rhodium hydroxide precipitate.
2. The recovery method according to claim 1, wherein in the step (1), the mass ratio of the rhodium-containing working solution to the adsorbent is 1:0.5 to 1: 5.
3. The recycling method according to claim 2, wherein in the step (1), the adsorbent is one or two of corn starch and activated carbon.
4. The recycling method according to claim 1, wherein in the step (2), the temperature raising is performed by: keeping the temperature at the interval of 50 ℃ for 60-240min before 200-300 ℃, keeping the temperature at the rate of 0.5-2.5 ℃/min, keeping the temperature at the interval of 100 ℃ for 60-240min after 200-300 ℃, keeping the temperature at the rate of 0.5-2.5 ℃/min until the temperature rises to 600-800 ℃, and keeping the temperature for 60-240 min.
5. The recovery method according to claim 1 or 4, wherein in the step (3), the sodium bisulfate and the sodium chloride are added in an amount of 5 to 15 times as much as the rhodium ash.
6. The recovery method according to claim 5, wherein in the step (3), the mass ratio of the sodium bisulfate to the sodium chloride is 5-30: 1.
7. The recycling method according to claim 1, 5 or 6, wherein in the step (3), the roasting is performed at a constant temperature of 60-240min every 50 ℃ before the roasting is performed at 200-300 ℃, the temperature rising rate is 0.5-2.5 ℃/min, and is performed at a constant temperature of 60-240min every 100 ℃ after the roasting is performed at 200-300 ℃, the temperature rising rate is 0.5-2.5 ℃/min until the temperature rises to 600-800 ℃.
8. The recovery method according to claim 1 or 7, wherein in the step (4), the mass ratio of the reaction product to water is 1: 1-5; the concentration of the NaOH solution is 1-5 mol/L; the pH value is 7-9.
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