This application is based upon and claims priority to Chinese Patent Application No. 202210430805.4, filed on Apr. 22, 2022, the entire contents of which are incorporated herein by reference.
The present disclosure belongs to the technical field of hydrometallurgy and relates to clean production technology for wet recovery of palladium and in particular to a method for clean recovery of palladium.
Palladium is a platinum-group element (PGE) with excellent plasticity, stability, and catalytic activity, which is widely used in fields of aerospace, nuclear energy, electronics, catalysts, and the like. Palladium is also regarded as a strategic reserve metal due to its uniqueness and scarcity. Platinum-group metals (PGMs) are scarce and expensive, and thus the recovery of PGMs is of great significance.
Palladium nitrate can be used as an analytical reagent and also as a raw material for the synthesis of various palladium compounds and catalysts. Palladium nitrate is currently prepared through simple dissolution with nitric acid. Due to the uncertainty of palladium raw materials, the direct dissolution with nitric acid has disadvantages such as long palladium dissolution time, low solubility, and low direct yield of palladium nitrate. In addition, the dissolution of palladium each time requires a large amount of nitric acid, and the repeated palladium dissolution process has disadvantages such as large energy consumption and NOx production that causes heavy environmental pollution.
CN109592722A discloses a method for preparing palladium nitrate. A high-purity palladium powder is added to a reactor, then an analytically-pure concentrated nitric acid solution with a mass percentage concentration of 65% to 68% is added at a mass 4 to 9 times the mass of the palladium powder. The temperature in the reactor is maintained at 10° C. to 70° C., and the resulting reaction solution is thoroughly stirred. Hydrochloric acid with a mass concentration of 37% is diluted to 1% to 2% and added to the resulting reaction solution until a mass of HCl is 0.005% to 0.25% of the mass of the palladium powder in the reactor. The resulting system is continuously stirred to allow a reaction for 0.5 h to 4 h to obtain a palladium nitrate solution with the palladium powder completely dissolved. The above method commonly has the following problems: (1) The reaction between nitric acid and palladium will produce a large amount of nitrogen oxide gas. (2) During the reaction process, nitric acid, aqua regia, a NOx tail gas absorber, and the like are used, which increases the cost, leads to a large amount of waste liquor, and causes heavy environmental pollution.
CN105671304A discloses a method for recovering rare earth and platinum-group metals (PGMs) from a failed catalyst for purifying an automobile exhaust gas, including the following steps: (1) fine grinding; (2) sulfation roasting; (3) dilute acid leaching: the roasting product obtained in step (2) is subjected to leaching with dilute sulfuric acid, and the resulting mixture is filtered to obtain a rare earth sulfate solution and an insoluble PGM-containing residue; (4) recovery of rare earth: sodium sulfate is added to the rare earth sulfate solution obtained in step (3) to produce a complex sulfate precipitate, and a lanthanum cerium rare earth oxide (REO) is prepared with the precipitate; and (5) recovery of PGMs: PGMs are leached from the insoluble residue obtained in step (3) with hydrochloric acid and chlorine, and a leaching liquor is treated by the existing separation, purification, and refining process to obtain the PGMs of platinum, palladium, and rhodium, separately. In the above method, PGMs cannot be dissolved by sulfation roasting and are enriched in the insoluble residue. The leaching of PGMs with hydrochloric acid and chlorine is a traditional technology, and the use of highly-toxic chlorine has a safety risk.
CN103834808A discloses a method for recovering rare and precious metals from a scrapped automotive electronic device, where a mixed solution of hydrochloric acid and sodium hypochlorite is used to leach rare and precious metals. The use of sodium hypochlorite as an oxidizing agent will also produce a large amount of highly-toxic chlorine. The above method includes the following steps: (1) disassembly of a scrapped automotive component; (2) crushing of the scrapped automotive component that includes rare and precious metals; (3) mixing and roasting of a crushed powder and sodium hydroxide; (4) washing with hot water; (5) filtering the resulting mixture, wherein aluminum and molybdenum are recovered from the resulting filtrate, and the resulting filter residue is dissolved with an acid and then filtered to obtain a rare earth and iron ion-containing solution and a precious metal-containing filter residue; (6) preparing an REO with the rare earth and iron ion-containing solution obtained after the filtration in step (5); (7) leaching the precious metal-containing filter residue obtained in step (5) with a mixed solution of hydrochloric acid and sodium hypochlorite to obtain a solution containing gold, palladium, platinum, and rhodium, and extracting gold by electrowinning; (8) platinum extraction; and (9) using the filtrate with platinum removed in step (8) to prepare a crude palladium powder. In the above method, formic acid is used to extract crude palladium under vigorous stirring, which leads to low purity and efficiency; an acid solution such as hydrochloric acid in the pre-process results in poor safety.
Therefore, a brand-new, clean, and economical method for recovering palladium is needed.
In view of the problems such as high waste acid and waste gas emissions, low palladium recovery rate, and high treatment cost of the existing recovery technology, the present disclosure provides a method for clean recovery of palladium, where a palladium-containing material is subjected to solution leaching with Ce4+ under the action of an additive, and then a leaching liquor obtained after a leaching reaction is completed is subjected to electrolysis to achieve Ce4+ regeneration and palladium preparation, which eliminates the generation of pollutants such as nitrogen oxides from the source and realizes the clean extraction of palladium.
In order to achieve the above objective, the present disclosure adopts the following technical solutions:
The present disclosure provides a method for clean recovery of palladium, including mixing a palladium-containing material, a Ce4+-containing acidic solution, and an additive and conducting a leaching reaction to obtain a Pd2+-containing solution.
Preferably, the method further includes: subjecting the Pd2+-containing solution to electrolysis, such that palladium is produced at a cathode and a Ce4+-containing acidic solution reusable for leaching is produced at an anode.
In the present disclosure, Ce4+ is used as a leaching agent and an oxidizing agent to conduct leaching under the action of an additive, during which the following leaching reaction occurs: 2Ce4++Pd=2Ce3++Pd2+. In the present disclosure, Ce4+ is used instead of the traditional nitric acid or aqua regia for leaching of a palladium-containing material. When a palladium-containing material is subjected to leaching with Ce4+ as an oxidative leaching agent and chlorine as an additive, almost no waste gas is produced during the leaching process. Therefore, the present disclosure provides a safe green palladium recovery process without waste gas emission.
In the present disclosure, the leaching is achieved by mixing a palladium-containing material, a Ce4+-containing acidic solution, and an additive to allow a reaction.
Preferably, the Ce4+-containing acidic solution includes sulfuric acid and/or nitric acid.
Preferably, the additive includes chlorine, including, but not limited to, an inorganic chloride and a chlorine-containing organic matter. For example, the additive may be chlorine, sodium chloride, potassium chloride, potassium chlorate, hydrochloric acid, chlorobenzene, monochloromethane, or the like, but is not limited to the listed compounds. Other chlorine-containing substances are also suitable for the method.
Preferably, a concentration of Ce4+ in the Ce4+-containing acidic solution is higher than or equal to 0.05 mol/L, such as 0.05 mol/L, 0.08 mol/L, 0.1 mol/L, 0.2 mol/L, 0.5 mol/L, or 1 mol/L, but the concentration is not limited to the listed values, and any other values in the range that are not listed are also applicable.
Preferably, a concentration of chlorine in a mixed solution obtained after the mixing is 0.01 mol/L to 0.5 mol/L, such as 0.01 mol/L, 0.02 mol/L, 0.08 mol/L, 0.1 mol/L, 0.2 mol/L, or 0.5 mol/L, but the concentration is not limited to the listed values, and any other values in the range that are not listed are also applicable.
The present disclosure has no special limitations on a liquid-to-solid ratio of the Ce4+-containing acidic solution to the palladium-containing material during the leaching reaction, which can be a conventional liquid-to-solid ratio or can be adjusted according to an actual process. During an actual process, tubular continuous leaching can also be adopted, where the Ce4+-containing acidic solution is allowed to flow through a pipeline, and the liquid-to-solid ratio is not specifically restricted.
Preferably, the method may further include the following step: subjecting the Pd2+-containing solution to electrolysis, such that palladium is produced at a cathode and a Ce4+-containing acidic solution reusable for leaching is produced at an anode.
In the present disclosure, the solution with Pd2+ and Ce3+ obtained after the leaching reaction is subjected to electrolysis, such that palladium is produced at a cathode and the regeneration of Ce4+ is achieved at an anode, where the following reaction occurs during the electrolysis: 2Ce3++Pd2+=2Ce4++Pd, that is, a reverse reaction of the leaching reaction. An electrolytic solution can be recycled and no waste liquid is produced, which ensures the overall economy and environmental friendliness of the method.
As a preferred technical solution for the present disclosure, the method includes the following steps:
Compared with the prior art, the present disclosure has the following beneficial effects.
(1) The present disclosure provides a method for clean recovery of palladium, where Ce4+ is used instead of nitric acid to leach palladium based on the leaching reaction of 2Ce4++Pd=2Ce3++Pd2+, and no NOx is produced during the leaching reaction, which avoids the environmental pollution caused by NOx during the traditional nitric acid leaching process.
(2) The present disclosure provides a method for clean recovery of palladium, where a leaching liquor is subjected to electrolysis, such that Ce4+ is regenerated and palladium is precipitated with a palladium leaching rate of higher than or equal to 99%, which achieves the recycling of the mother liquor and the near-zero emission of waste liquid and gas. The reaction process does not consume other chemical reagents, which reduces the environmental impact and production cost.
In order to facilitate the understanding of the present disclosure, some examples of the present disclosure are listed below. Those skilled in the art should understand that these examples only help explain the present disclosure and should not be regarded as specific limitations to the present disclosure.
The technical solutions of the present disclosure will be further described below through specific embodiments.
In a specific embodiment, the present disclosure provides a method of clean recovery of palladium, including the following steps:
(2) The Pd2+-containing solution obtained in step (1) is subjected to electrolysis, such that palladium is produced at a cathode and a Ce4+-containing acidic solution reusable for leaching is produced at an anode.
It should be noted that the process provided in the examples of the present disclosure or a replacement or change of conventional data are within the protection scope and disclosure scope of the present disclosure.
In this example, a method for clean recovery of palladium was provided, including the following steps:
0.1 g of palladium powder and a specified amount of sodium chloride solid were mixed and ground for 1 min. A Ce4+-containing sulfuric acid solution was added to make [Cl]=0.04 mol/L and [Ce4+]=0.05 mol/L in a resulting mixed solution, and a leaching reaction was conducted at 80° C. The resulting leaching solution was filtered to remove a residual solid and a suspended matter to obtain a clear palladium sulfate leaching liquor. As calculated, the palladium leaching rate in this example was 99.8%.
In this example, a method for clean recovery of palladium was provided, including the following steps:
0.2 g of palladium powder and a specified amount of lithium chloride solid were mixed and ground for 5 min. A Ce4+-containing sulfuric acid solution was added to make [Cl]=0.01 mol/L and [Ce4+]=0.05 mol/L in a resulting mixed solution, and a leaching reaction was conducted at 60° C. The resulting leaching solution was filtered to remove a residual solid and a suspended matter to obtain a clear palladium sulfate leaching liquor. As calculated, the palladium leaching rate in this example was 99.6%.
In this example, a method for clean recovery of palladium was provided, including the following steps:
5 g of palladium powder and a specified amount of sodium chloride solid were mixed and ground for 30 min. A nitric acid solution of ceric ammonium nitrate was added to make [Cl]=0.05 mol/L and [Ce4+]=1 mol/L in a resulting mixed solution, and a leaching reaction was conducted at 40° C. The resulting leaching solution was filtered to remove a residual solid and a suspended matter to obtain a clear palladium nitrate leaching liquor. As calculated, the palladium leaching rate in this example was 99.7%.
In this example, a method for clean recovery of palladium was provided, including the following steps:
2.3 g of palladium powder was mixed with a Ce4+-containing sulfuric acid solution, then a specified amount of sodium chlorate solid was added to make [Cl]=0.05 mol/L and [Ce4+]=0.5 mol/L in a resulting mixed solution, and a leaching reaction was conducted at 80° C. The resulting leaching solution was filtered to remove a residual solid and a suspended matter to obtain a clear palladium sulfate leaching liquor. As calculated, the palladium leaching rate in this example was 99.8%.
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this example, a method for clean recovery of palladium was provided, including the following steps:
In this comparative example, a method for clean recovery of palladium was provided, which was the method in Example 1 in the detailed description of CN109592722A, and an extracted palladium nitrate solution was prepared by the method. A large amount of yellow smoke (NOx) was produced during the reaction. Because nitric acid, aqua regia, a NOx tail gas absorber, and the like were used during the reaction, a large amount of waste liquid was produced, causing heavy environmental pollution.
For the palladium solution or palladium obtained by the method in each of Examples 1 to 12, a leaching rate was calculated as follows:
leaching rate=1−[(palladium concentration in leaching liquor×volume of leaching liquor)/(palladium content in initial material×raw material mass)]×100%.
Results showed that, in each of Examples 1 to 12, a palladium leaching rate was higher than 99%, no toxic gas was used in the leaching process, and no NOx was produced. Through electrolysis, the mother liquor was recycled without the generation of wastewater.
In summary, the present disclosure provides a method for clean recovery of palladium, where palladium is leached with a low-cost acidic Ce4+ solution as an oxidizing agent and chlorine as an additive, which completely eliminates the generation of a nitrogen oxide tail gas in the traditional process and realizes the clean extraction of palladium. A leaching liquor is subjected to electrolysis to realize the regeneration of Ce4+ and the preparation of palladium. The method of the present disclosure has a high palladium recovery rate, a low production cost, and promising application prospects.
The above are merely specific implementations of the present disclosure, and the protection scope of the present disclosure is not limited thereto. Any modification or replacement easily conceived by those skilled in the art within the technical scope of the present disclosure should fall within the protection scope of the present disclosure.
Number | Date | Country | Kind |
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202210430805.4 | Apr 2022 | CN | national |