Palladium catalyst recycling technology 1. Wen-hai 2. Huangdeng Jiang (1. Liuzhou environmental monitoring detachment, Liuzhou 545001; 2.

Liuzhou environmental protection monitoring station, Liuzhou 545001) Abstract Palladium catalysts are widely used in chemical industry, and its inactivation to be significant, the recovery of palladium has a greater economic value. Describes the different types of palladium catalyst recycling waste carrier purification methods. Key words Pd; catalyst; recovery Key Words TQ426.83 Document code A Article ID 1003-2673 (2008) 11-20-02 1. Introduction palladium is a metal, hydrogen and oxygen on the adsorption capacity with a special, widely used in the catalyst industry. Many different types of palladium catalysts, most used in the petrochemical industry and catalytic hydrogenation and oxidation reactions, such as the preparation of acetaldehyde, pyridine derivatives, vinyl acetate and a variety of chemical reaction products [1]. Mass content of palladium in the catalyst is generally the very few to a few percent. Expensive and limited resources, palladium, palladium catalyst deactivation is mainly the growth of palladium to catalytic activity of the grain size decreases, the coverage and poisoning of impurities and other reasons. And palladium are good corrosion resistance, high temperature performance and stable electrical properties, the loss of palladium during the reaction was not great, the waste palladium catalyst Pd content compared with the difference between the fresh catalyst is not, therefore, spent catalysts Palladium for a more complete recovery to be possible. So far, palladium catalyst preparation methods are impregnation, vapor deposition of metal ions, solvated metal atom impregnation, ion exchange, sol - gel method. Palladium catalyst dispersed in suitable carrier to use, for different reactions, the largest carrier for the present study, activated carbon, aluminum oxide, zeolite and zeolite, ceramics, silicone and so on. Under the palladium catalyst preparation methods and

different carriers, but also by the corresponding method of recycling. Activated carbon supported palladium catalyst 2 Pd catalysts are widely used in pharmaceutical and chemical industries. **** for example, **** diisocyanate synthesis and purification of caprolactam, acid hydrogenation reactions are used palladium / activated carbon catalyst. After a long use, the palladium catalyst contaminated by impurities loss of activity, a waste catalyst. From spent Pd / activated carbon catalyst for the recovery of palladium is currently the most widely incineration. Will air at 800-1500 volatile coal combustion into CO2 removed. Palladium in the form of ash left behind to be enriched, according to the composition of ash, using the appropriate treatment process, characterized by using less chemicals, technology is relatively simple. Usually by reducing agents such as combustion residues (hydrazine hydrate, formic acid) reduction, the reduction of oxidized palladium into palladium metal, palladium recovery rate of increase. Dissolved with hydrochloric acid, after which iron, titanium and other impurities, oxidizing agents (aqua regia, ****, etc.) dissolved palladium, follow-up procedure is slightly different, but generally will be dissolved palladium complex with ammonia to form a precipitate drying, roasting to purification. Palladium carbon catalyst to improve the recovery rate of waste, reduce resource waste, Lin Yimin et al [2] for related experiments, the results show that the recovery rate of waste palladium carbon catalyst is the burning of the most important aspects of palladium in the solution, the process of reduction and purification loss is minimal. Palladium particles in the incineration process is easy with the burning of the gas out of the incinerator, resulting in the loss of palladium, so incineration is the most important steps in the process of burning, burning device design will become a research priority. Domestic Wuguan Min et al [3] palladium recovery incinerator designed system, the burning furnace, blast equipment, scrubbers, filters, chimney structure, effectively

inhibited the loss of palladium, the palladium recovery rate of 95% or more. Wuguan Min et al [3] from the failure of the recovery of Pd-C catalyst Pd way. That of an alkali metal or alkaline earth metal carbonate as additive in the 700 ~ 800 , the waste incineration Pd-C catalyst for oxidation of carbon removal, fine residue obtained after refining with alkali metal acid sulphate react to produce soluble Pd salt , and then separated by electrolysis Pd. Pd recovery rate of up to one-way more than 97% purity of 99.95%. In addition to burning solution method but also have a soda leaching, there are fire method (gas volatility), pressure acid leaching, chloride (fluoride) volatilization, adsorption and other recovery techniques. 3Al2O3 catalyst such palladium catalysts is mainly Al2O3 as the carrier, mainly for the hydrogenation of ethylene, including removal of crude acetylene, propylene hydrogenation of crude off the propargyl and pyrolysis gasoline hydrogenation. Palladium content of active component in the very few with a few per thousand, and the value of recycling of these catalysts is also relatively large. Surface of the catalyst metal particles increases and the sintering hydrocarbons catalytic activity covered, so that the catalytic activity greatly reduced the loss of catalytic activity. This process, almost no loss of active components, so there is still recovery value. Al2O3 supported catalyst for recycling of the most widely used technology at home and abroad are roasting leaching method and sublimation. 3.1 The first roasting leaching palladium catalyst waste sometime in the high temperature baking to remove impurities and volatile organic compounds which, and then leaching recovery. Leaching of the catalyst there are many ways Pd can be used aqua regia digestion method, hydrochloric acid dissolution method added oxidants, sulfuric acid dissolving carrier and so on, respectively, after filtering processing of the filtrate and the residue, commonly

used methods of extraction of palladium complex purification, electrolysis, ion exchange law. When the Carrier by the -Al2O3, can be calcined at high temperatures into acid insoluble -Al2O3, and then impregnated with aqua regia acid solvent such as recycling. Good solvents NaCN, NaOH NaCN, aqua regia, NH4C1 or NH4NO3 and HC1 oxidants (such as H2O2) and so on. After roasting waste palladium catalyst, sulfuric acid, aqua regia dissolution process, through ion exchange, ammonia complex purification palladium. Such technology has some limitations: aqua regia leaching solution is usually a large number of dissolved aluminum, iron and other ions in the ammonia complex will have a **** washing the hydroxide gel filtration and precipitation, will be adsorbed palladium, to increase the difficulty of separation, led to the recovery of palladium decreased. This process is suitable for processing materials with high content of palladium and aluminum materials, iron and other elements of content cannot be too high. Zhang Zheng-Hong et al [4,5] Treatment with aqua regia impregnation sodium sulfide, the reaction is: H2PdCl4 Na2S = PdS 2NaC1 2HC1, experimental results show that: Na2S small amount of precipitation that can achieve a high rate (almost 100%), without adding excess Na2S. Pd precipitation with sodium sulfide and residual nitric acid will reduce the harm, because when adding sodium sulfide reacts with sulfur nitrate, a nitrate effect in time. Pd sulfide precipitation has good selectivity, rapid response, easy to control conditions, without a single catch nitrate, low cost, reduced to elemental Pd and simple process. Moreover, the catalyst is dissolved oxidant and HCl, and then electrolysis to extract palladium are more commonly used. This method uses electrochemical principles, the concentrated solution into an electrolytic cell in the electrolytic refining. Cathode in electrolytic deposition of palladium on the cathode materials used are mainly two: the carbon cathode, iron cathode. The law and avoid the extensive use of aqua regia in a hurry the

process of nitrate pollution of the environment, but in the electrolytic cell to be complicated to operate. Aqua regia leaching method is commonly used methods, the process is simple, but the aqua regia corrosion, pollution of the environment, it is not suitable for industrialization. 3.2 sublimation method under high temperature and pressure, with the gasification agent treatment of waste catalyst, gasification agent concentration trapping agent to collect the reaction with palladium complexes [6]. At a certain temperature, the chlorine in the circular flow of waste by heating the palladium catalyst into the separation of volatile chlorides, the use of watersoluble capture agent after capturing PdCl2 recovery. PdCl2 trapping agent and the formation of complex salt, commonly used chelating agent has NH4C1, NaC1, NaF, KF and so on. In addition to chlorine as well outside the commonly used gasification agent CO, SO2, CaC12, NaC1 and so on. German experts Allen's patented two-step method reported in the recovery of precious metals, high temperature distillation of two-step method, the effect is better and high recovery rate. This method is unique technology, gasification agent and chelating agent are basically highly toxic substances, equipment requirements and therefore high. 3.3 Pretreatment of wet Fe Replacement: After crushing the spent catalyst with hydrochloric acid and sodium chlorate oxidation leaching, filtering the full reaction of the secondary leaching residue. Filtrate plus Fe replacement. Control of acidity, replacement fluid discharge. Coarse palladium powder obtained for washing, leaching with hydrochloric acid, and then were precipitated with **** palladium and palladium dichloride ammonia Purification Asian network, 99.95% purity palladium sponge. Waste palladium catalyst Pd content is 0.3%, Pd recovery rate of 99%. Low cost, effective [7,8]. This approach to a second leaching, complex operation, also recovered acid and chlorine sub-carrier of aluminum powder Pd difficult to separate, take a

long time filtering. Add oxidant dissolved 3.4 hydrochloric acid method of waste washed palladium catalyst and sodium hydroxide solution mixing, and then restore (or formaldehyde through hydrogen at 60 ), will be reduced to palladium metal palladium, add 8mol / L hydrochloric acid, in the Walter stirring chlorine gas, so that the form of palladium was dissolved in H2PdCl4 down, filter washing, the filtrate and the washing combined one, the aluminum (Al mass fraction 99.5%) immersion, palladium was precipitated, by rough palladium [8]. Recoveries above 92%, palladium 98% purity. Hydrochloric acid through chlorine method, because of the increase cannot be completely absorbed chlorine, chlorine gas from the exhaust emissions, the need to be addressed, complex operation. 4 multi-active components with palladium catalyst such catalysts generally contain the active component of other metals such as Pt, Ni, Ru, Re, Ce and so on. In the recovery process, the first of the deactivated catalyst pretreatment, and then the different precious metals refining process for separation and purification, the process is more complex. Active ingredient and carrier in accordance with their different use of appropriate methods, usually using aqua regia, acid pretreatment, and then through the metal reduction, or electrochemical methods of purification. 5 Conclusion palladium are precious metals, is an important chemical raw material, domestic reserves and production capacity has certain limits. Palladium catalyst is palladium waste valuable secondary resources, a very high recovery value. According to China's development status and outlook, in the petrochemical industry, polyester industry, automobile and environmental protection areas in the recovery of palladium catalysts for the production will have a huge economic benefit. Especially in the heavy oil resources that enhance and Pd tight prices in the future, strengthening the recovery of spent catalyst and the results for industrial production as soon as possible is an

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