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2003 (87) International publication number: WO 2004/106563 (09. Ross Timothy New Delhi 110 001 (IN) Bromhead Johnson 19 Buckingham Street (72) Inventors: London • JASRA.05. any person may give notice to the European Patent Office of opposition to that patent.01) C22B 7/00 (2006. AL LT LV MK Bhavnagar Gujarat 364 002 (IN) (43) Date of publication of application: • BORICHA. Gujarat 364 002 (IN) (56) References cited: GB-A. in accordance with the Implementing Regulations.: of the grant of the patent: C22B 11/00 (2006.6 455 018 EP 1 636 393 B1 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin. Raksh V.6 PCT/IN2003/000202 (22) Date of filing: 30. WC2N 6EF (GB) Bhavnagar. 22.2012 Bulletin 2012/32 (86) International application number: (21) Application number: 03817072.12.2006 Bulletin 2006/12 Bhavnagar Gujarat 364 002 (IN) (73) Proprietor: Council of Scientific and Industrial Research (74) Representative: Manaton. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid.01) 08. Arvindkumar B. 99(1) European Patent Convention). Pushpito K.08. AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Bhavnagar HU IE IT LI LU MC NL PT RO SE SI SK TR Gujarat 364 002 (IN) Designated Extension States: • BAJAJ.798 712 US-A. Hari C.5 783 062 US-B1. 75001 PARIS (FR) . Printed by Jouve. (Art.03. (11) EP 1 636 393 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.2004 Gazette 2004/50) (54) PROCESS FOR RECOVERY OF PALLADIUM FROM SPENT CATALYST VERFAHREN ZUR RÜCKGEWINNUNG VON PALLADIUM AUS VERBRAUCHTEM KATALYSATOR PROCEDE DE RECUPERATION DE PALLADIUM A PARTIR D’UN CATALYSEUR USE (84) Designated Contracting States: • GHOSH.4 072 508 US-A.

followed by treating the acidified solution with ulated restrictions on disposal of metal containing waste. Pt 20 oximes employed for the extraction of palladium are hy- and Rh are used in a variety of industrial applications as droxyoxime and derivatives. such as palladium and platinum. discloses the separation and purification of palla- from side reaction and leaching of the effective catalyst dium present in a aqueous solution with at least one other for the solid support are common in some cases of het.. precious zeolite. the cals industries. hydrogenation and dehydrogen.g. In view of the environmentally stip. The process required washing out of acid from the or- aration of metal complexes from product mixtures. the problem related to degradation of 50 [0008] U. 1984 to Hunter polymeric or inorganic solid support like silica. who have dis- Background of the invention 15 closed the extractants for the recovery of palladium using ortho alkoxy substituted phenyl oxime compounds which [0002] Precious transition metal ions and their coordi. contaminants arise et al. the presence of excessive ligand must have high affinity for precious metals to be contaminants reduces the efficacy of recycling of the cat. genation reactions. modified silica. which are expensive con- catalysts for oxidation. gold. Commercially. owing to difficulties in sep. is anchored on carbon and is used as catalyst for the typically with aqua regia or hydrochloric acid /chlorine hydrogenation of nitro aromatics or as a catalyst for many gas followed by solvent extraction. discloses a process for recovering.. and can be recycled. carbon. coordination metal complexes of Pd. Pd. 25 ticularly gold and the platinum group metals. from stripping / precipitation. in particular alkyl substituted 8-hydroxyquinoline. ganic phase is not degraded providing acid is washed mogeneous conditions for hydroformylation and hydro.250 (1986) to Dimmit.705. The process comprises the adsorption of one precious [0003] In certain situations. 55 an ortho alkoxy substituted phenyl oxime by using solvent effective recovery of the residual precious metals from extractions techniques. Au. The loaded fibrous body is and the reaction effluent may comprise of various rem. In many cases. the use of solvent extraction to separate the precious metals [0001] The present invention relates to an improved 5 from one another and from base metals that may also be process for the recovery of palladium from spent catalyst. isomerization and dimeriza. where coordination metal complexes are supported on [0007] G. sidering the industrial application. pal- spent catalysts or inorganic waste and more specifically ladium and rhodium). aliphatic and cyclo-aliphatic hydrocarbons process to be environmentally acceptable and econom.145 (1987) to Demopou- used in catalyzing such reactions as oxidation. dehydro. (e. [0004] Furthermore. The active extractant used was.B. In this patent. treated with aqueous cyanide solution to recover the met- nants. The hydrometal- The present invention particularly relates to a suitable lurgical processes employed for the separation and re- method of catalyst recovery of precious metals from covery of the platinum group metals. S. taining palladium and other metals. et al. par- genation. Palladium salt catalysts are also widely [0006] U.. The efficient recovery and purification of platinum chloride solutions. metals viz. or by hydrogen after a for complete recovery of such metals from spent catalysts 30 cold water wash. there ganic phase before solvent can be recover and reuse is growing need to developed heterogenized catalysts which is a multi step process. The main limitation of the process is that cyanide metal ions.. For example metals like Ag. from metal tion. platinum group metal by adjusting the pH of the solution erogeneous catalysis. be recovered by hydrogen reduction in stages. the catalysts are deacti. metal on the activated carbon. complexes of various valence states for the al ion. Platinum stripped into aqueous solution can metals. However. wherein said activated vated during the reaction cycle or subsequent work-up 45 carbon is in the form fibers. The or- Pt.654. [0005] Reference is made to the U. cipitated either by hydrogen reduction or is stripped with zeolite and/or clay materials are used as support for these mineral acid. 4. by solvent extraction and selective group metals. Various polymeric materials. Ru and Rh are used as commercial catalysts in ho.578. e. recover. S. catalysts over the repeated cycles. 40 William. Gold is lots of research efforts are directed to develop processes precipitated either by hot water. hydrogenation. discloses the recovery of precious metals. Palladium in the organic phase is pre- worldwide. However. present is becoming more widespread. of at least one dissolved compound of that precious met- mum extent possible once the catalyst is deactivated. chlorinated hy- 2 .896 (1987) to Van Der Puy et al. it is important to re. typically involve dissolving the met- the process concerns with the recovery of palladium that 10 al ions by some type of oxidative acidic chloride leach. from 0 to 5. 1 EP 1 636 393 B1 2 Description ically viable. palladium and platinum from a solution cover the precious metals from the support to the maxi.g. Patents No A-2127001. ation reactions. during the recovery of precious Field of the invention metals from ore or scrap including spent catalysts. los. platinum. ladium from aqueous compositions and mixtures con- ed catalysts and performance chemicals in fine chemi. 4. S. xylenes. Consequently. Illustrative of useful solvents are the reaction effluent is of paramount importance for a aromatic. spent catalyst is economically desired. alyst. 35 out before any hydrogen reduction.. and alumina. al. 4. Patent No. are useful for selectively separating and recovering pal- nation complexes find industrial applications as support. other organic transformations. cyclohexane. such as toluene. Similarly. Patent No. Patent No.

K. pretreated with an alkali metal salt of Eth. 5 due is then acid treated to obtain corresponding palladi- The drawback of the process is that it involves multistage um salt.331. (Industrial Engineering Chemistry-Research. Inoue. not suitable for industrial application. (b) heating the bath to a temperature and for a the extraction process. 3 EP 1 636 393 B1 4 drocarbons and kerosene.g.105. and Grant. recovery of metals from supported catalysts also makes et al. [0020] Yet another object of the present invention is to covery of palladium from wastewater by sorption on ac. obtained from a catalytic process performed in homoge- ganic phase. be reused ylenediaminetetraacetic acid (EDTA).. Moreover recovery of solvent for further re. In this patent. generation and recovery of palladium from spent residue.435. the extractant soluble in water-immiscible sol. followed by stripping of palladium from the neous conditions. acids as the organic moiety. e. ladium from spent catalyst with more than 99% purity. perchloric or nitric acid ploying a nickel anode and a nickel or copper cathode. rocomplexes thereof together with other platinum group metals and/or base metals in 0. for the process for the separation of platinum and/or use of mineral acids and invariably destroyed the support palladium from acid starting solutions containing the chlo.634 (1982) to Shanton. Patent No. electroless catalytic baths by dissolving the palladium to Kenneth J. solution of sulphuric. octanal oxime and hexanol oxime for the extrac- [0010] It has been found that with continued use. 35 structure. the tion of palladium metal. The resi- phase by extraction with an aqueous ammonia solution. hydrochloric. tain an anionic phase transfer material or catalyst to aid oxide. sawa.5 before treating with Summary of the invention activated carbon with EDTA solution to recover precious metals. 30 recovery methods are applicable to the homogeneous and must then be discarded. (c) placing the solution in an electrolytic cell and derivatives. 40 provide an improved process for the recovery of palladi- tional groups of the formula R. S. the sense that it is only concerned with degradation of uses makes the process complicated. as waste hence may not be reaction mixtures and employ chelating agents for ex- suitable for commercial application.. and (ii) a cathode comprised 20 dustrial application. to Pauko Jan. S. Jr. decanal substantially reduce tin deposits. 4. page 2111) have described the use of the cathode at a voltage which tends to minimize and non-cheating oximes such as dodecanal oxime. 4. [0017] The main object of the present invention is to vent. Process known in the prior art for [0011] U. which are expensive considering the in- having (i) a nickel anode. (Chemical Abstract 109 (24): 213964) disclose the re. Vol- and (d) electrowinning palladium from the solution onto ume 29.. The aqueous phase was separated from the or. wherein strongly acidic form a true solution followed by electro-deposition em. However.. osene. 54 9597 (1978) discloses the re. this is useful for homogenous aqueous 55 [0021] The aim of the present invention is directed to catalyst waste and is not directly applicable to non-aque. This report also has drawback in catalytic bath becomes contaminated with copper from the sense that the oximes employed for the extraction the copper cladding. the oximes em- time sufficient to essentially remove excess hydrogen ployed for the extraction of palladium are hydroxyoxime peroxide. However. S. ladium from the organic acidic solution containing oxime loidal palladium in the bath so as to form a true solution 15 as extracting reagent.258 (1984) to Melka. [0016] According to above prior art. Richard A. most of the metal troless plating becomes less adherent than desirable. 550 association with the oxime compounds in the organic to 600°C to decompose the organic fragment. et al. discloses the recovery of palladium from spent 10 [0014] US Patent No. the two phases and recovering the extracted platinum or [0018] Another object of the present invention is to re- palladium or both from the loaded solvent extractant. 50 recover carbon black as a vatue added product that can tivated carbon. 25 oxime. Yoshizuka and T Furu- or easily separable from the palladium to be deposited. 251467 (1988). [0013] JP Patent No. The wastewater is required to be acidified to pH 3-7. Baba. 4. this invention has a limited scope in processes. The spent catalyst obtained from hydrogenation plant 3 . metal complex having lower aliphatic mono-carboxylic [0009] U. of a metal or metallic surface which is non-contaminating [0015] Y. The preferred solvent is ker.742 (1978) to Edwards.2N-CH2 -COOH wherein um from spent catalyst that obviates the drawbacks as R is a long-chain alkyl group and thereafter separating detailed above. [0019] Still another object of the present invention is [0012] C. provide an improved process for the recovery 100% pal- ous systems. carried in an organic phase and comprising func. The organic phase may also con- by the addition of an oxidizing agent. hydrogen per. Patent No. which is subjected to heating ca. cover palladium from the spent catalyst generated from These extractant are generally very expensive and use 45 the hydrogenation plant used for the hydrogenation of organic solvents that are not environment friendly. to recover 100% palladium with more then 99% purity. are nitro aromatic compounds. When contamination reaches an are expensive considering the industrial application extent such that the bath becomes ineffective or the elec. is used as stripping solvent for the extraction of the pal- The recovery includes the steps of (a) dissolving the col. tracting metal ions. Patent No.01 to 2M acid solutions Objects of the invention comprises contacting the starting solution with a suitable extractant. (1990). K.

the process com. the 55 6 molar. The digestion of the spent catalyst in acid is preferably [0028] In a further embodiment of the invention. ture in the range 60 to 80% and v) 3 to 6 % tar of dinitro. 6 to 11 to precipitate palladium as a metal salt such as [0030] In yet another embodiment of the invention.e. (i) thermally treating finaly divided spent catalyst 20 (ii) maintaining an inert atmosphere during heat generated from a hydrogenation plant. carbon treatment at ca. hydrochloric acid consisting of nitric acid.1 to 0. helium (ii) cooling the spent catalyst obtained from step (i) and the like gases. like nitrogen. the [0036] The finely divided spent catalyst may be sub- heat treatment is carried out in inert atmosphere or in air. particles from the liquid. above to room temperature ranging between 20 to (iii) cooling the spent catalyst to room temperature 40°C in air. The acid concentra- tained between 50 to 90°C and 4 to 6 hours respectively. (i) thermal treatment of finally divided spent catalyst prising in the temperature range of 350 to 450°C for a period selected from 4 to 6 hours.2. 4 .1 to 0. 45 jected to heat treatment in the temperature range [0026] In yet another embodiment of the invention. argon and helium. treatment using gases like nitrogen. iii) Carbon in the range 15 to 25%. Palladium recovered as palladium salt can be used for loading /anchoring on support materials [0034] The present invention provide an improve proc- which finds application as catalyst or catalyst support. (iv) reacting the acid with the spent catalyst under (v) allowing the acid to react with the spent catalyst continuous stirring. dissolve the palladium metal as corresponding salt and [0033] In yet another embodiment of the invention. the separate the carbon particles by filtration. (vii) drying the metal salt (vii) precipitating the palladium as metal salt in the 35 pH range 6 to 11. The spent catalyst was subjected to heat 5 [0032] In a further embodiment of the invention.1 to 0. in the range of 90 -110°C. [0035] The catalyst generated from the hydrogenation [0024] In another embodiment of the invention. palladium is precipitated as a metal salt at a pH in the [0037] The pH of the filtrate can be varied in the range range of 6 to 11. 0.1 to 0. the 350-450°C for a period of 4 to 6 hours.20 to 40°C) in air. hydrochloric acid or sulfuric acid and like acids. (iii) digesting the thermally treated and cooled spent 25 (iv) digesting the calcined spent catalyst in the min- catalyst in a mineral acid selected from the group eral acids selected from nitric acid. argon. particles from the liquid by known techniques.2. chloride with high purity was obtained by adjusting the 10 pH of filtrate. ladium salt. ess for the recovery of palladium from spent catalyst gen- [0022] Accordingly the present invention provides a 15 erated from hydrogenation plant by the steps of process for the recovery of palladium from spent catalyst generated from hydrogenation plant. 40 plant contains i) Pd in the range 0. the Pal. ii) Fe in the range metal salt is dried in an air dried oven at a temperature 0. the palladium chloride. iv) Mois. This product does not require any further Detailed description of the invention purification steps. The heat treatment inert atmosphere is obtained using a gas selected from is preferably carried out in inert atmosphere using gases the group consisting of nitrogen. Carbon and moisture content in the spent range 0. [0031] In yet another embodiment of the invention the toluene was used to recover precious palladium as pal. 5 EP 1 636 393 B1 6 contains i) Pd in the range 0. (vi) filtering the reaction mixture to separate carbon (vi) precipitating palladium as metal salt. [0025] In yet another embodiment of the invention. ii) Fe in the ladium. a period selected from 4 to 6 hours. The cal- [0027] In another embodiment of the invention. between to 2 to 6 molar. 30 under continuous stirring at a temperature in the (v) filtering the reaction mixture to separate carbon range of 50 to 90°C and for a period of 4 to 6 hours. 500°C to decompose organic moiety and particles are recovered as by product in the form of car- then digested in mineral acid for a stipulated period to bon black. [0023] In one embodiment of the invention.2%. iv) catalyst is maintained between 0. recovery of palladium as metal salt is 100%. Iron. argon or helium and like gases.1 to 0. 15 Moisture in the range 60 to 80% and v) 3 to 6 % tar of to 25% and 60 to 80% respectively. the thermal (viii) drying the metal salt in air dried oven in the treatment of the spent catalyst in step (i) is carried out at temperature range 90 to110°C a temperature in the range of 350 to 450°C and for a period selected from 4 to 6 hours.2%.1 to 0. Solid palladium metal salt is palladium chloride. dinitrotoluene may be used to recover palladium metal. tion used for the digestion can vary in the range of 2 to [0029] In yet another embodiment of the invention. hydrochloric acid and sulfuric or sulfuric acid at a concentration in the range 2 to acid.2%. the cined catalyst is preferably digested in mineral acids like concentration of mineral acid for digestion is maintained 50 nitric acid.2%. iii) Carbon in the range 15 to 25%. 6 molar. the carried out at temperature in the range of 50 to 90°C for temperature and time needed for acid digestion is main. (i.

The pH of the second filtrate was again raised to ii) oxidation of carbonaceous compounds having low car. content by digestion with mineral acid and selective pre- tion as brown. Coupled Plasma Emission Spectrometer.5 [0041] The present process involves thermal desorp. (iii) dissolution of metals present in the ashed spectrophotomertically. 0. 7 EP 1 636 393 B1 8 [0038] Palladium is estimated. ascorbic acid and ing ligands like oxime. furnace for 3 hours at 150°C and subsequently calcined ladium or other metals are brought into solution by oxi. high temperature incineration to recover precious metals. which contained pal- rate method of estimation of metals ions at ppm/ppb lev.096).605 in air at lower temperature.882g bon number compounds at around 500°C and use of ther. The detailed procedure is as follow: 10 for metal recovery. covery of the metals salts with very high purity. The pH of [0042] The inventive steps in the process are (i) the the filtrate so obtained was raised initially to 6. whereby removal of oligomerized organic compounds in inert at. and 4 ml of 1% (w/v) 15 Example I ascorbic acid solution.02x10-4 at λmax = 410 5 Selective precipitation of the metal salts results into re- nm (a=0.745 g of the pre- tion of oligomerized nitro or amino organic compounds cipitate was obtained at pH 6. The precipitates were collected and dried. of the filtrate obtained at pH 6 was raised to 9. The volume was made up to 100 ml with water in a 100 ml volumetric flask.5 and the precipitates were collected and dried. H2SO4) containing excess of iodide. Wt of Palladium) temperature up to 400°C. which contains no palla- generated during hydrogenation of nitroaromatics and dium. The brown-colored mix- dization with aqueous solution as salt of mineral acid. [PdI4]2-. for a period of 5 hrs. This is most accu. of precipitates contain 0. A calibration curve is obtained by prepar. in acidic aqueous solu. 0. was dried as: 20 for 3 hour at 150°C.red complex. 1. To this the scope of the present invention. and absorb.02ε4 mol-1cm-1 for [PdI4]2 weight of the ash containing precious metal was found species at 410 nm 25 to be 4. 55 9. [0046] The precipitates obtained at pH 6 and pH 9. ladium. 20% carbon and Wt of Palladium in the diluted solution can be obtained rest water placed in an electric muffle furnace. [0039] Accurately measured volume/weight of the [0044] The following examples are given by way of il- sample solution/solid containing (w/v) not more than 1 lustration and therefore should not be constructed to limit mg of Pd was taken in a 100 ml volumetric flask. hydroxyoxime and derivatives etc. The reaction mixture was ing the pH of the solution. This oxidation step being ex. 35 was analyzed for palladium content. The 45 [0047] 566g of spent catalyst was dried in an electric ashed catalyst contains the insoluble oxides of the pal. (Mol. It [0040] Palladium has also be estimated spectropho. The dried spent catalyst containing Pd. temperature.red complex. 1. extraction technique and use of costly organic complex- like concentrated hydrochloric acid. (hydrochloric acid. and the brown-fired mixture so obtained was digested in 2M hydrochloric acid for 5 hours at 90°C. othermic in nature initiates the oxidation of carbon sup- port which result into thermal cascading effect and oxi.59g palladium determine spectrophotomertically. at 400°C for a period of 5 hours.026g of precipitate collected at pH 9. 5% m-dinitrotoluene. filtered to separate ash and dissolved matter. containing 0.65g palladium evidencing 100% mal energy generated for initiating oxidation of carbon recovery of palladium as palladium chloride determined support. potassium iodide. ture so obtained was digested in 2M-hydrochloride acid Metals that are present in the aqueous solution as salt for 3 hours while maintaining the temperature at 80°C of mineral acid are selectively precipitated out by adjust. was added 10 ml of 6N hydrochloric acid. This prod- ing a palladium iodide complex solution by dissolving the uct does not require any further purification steps. [0043] The process has advantage of obviating very palladium forms a brown. g showing 98% recovery by above process. [PdI4]2-. A calibration curve was obtained by dissolving a 30 tered to remove impurity especially of iron and other met- known amount of palladium chloride in hydrochloric acid als. In an acid medium cipitation of the metal salt by control of solution pH. Example II dizes the entire carbonaceous matter present in the cat- alyst contains without supplying of additional heat. [0045] 715g of spent catalyst. solvent known amounts of palladium chloride and other reagent.3g. was raised to 6 and precipitate formed were fil- els.5 contains get adsorbed on the active sites present on the surface 0.458 nm using Perkin Elmer’s Inductively cipitate collected and dried. The pH and receding its intensity on ICP spectrometer for palla. was filtered with Buckner funnel after cooling to ambient tomertically using ICP spectrometer. 0.15% Iron. 20 ml of 20% (w/v) potassium iodide solution. The pH of the filtrate. The pow- A = Absorbance of the 100 ml solution at 410 nm dery-fired product was obtained. All the carbon burnt and ε = Extinction coefficient.15% palla- ance at 410 nm against water was measured dium. based compound which are relatively of lower carbon number 40 on initial palladium impregnated on the carbon was 0.5 and pre- dium at 340. The mo. 5 . 50 and under continuous stirring. the precipitates of iron chloride were removed by filtra- mosphere prior to oxidation of carbonaceous compounds tion. The of the catalyst followed by oxidation of the carbonaceous total palladium content adsorbed on the carbon. lar absorptivity of the complex is 1.. Fe and organic compounds was fired at an elevated Wt ofPd per 100 ml = (A/ε).

contains 0. were collected and dried. (iv) reacting the acid with the spent catalyst un- ner funnel after cooling to ambient temperature followed der continuous stirring. the carbon so ob- for 3 hours while maintaining the temperature at 80°C tained was dried at 100°C in an oven.052g palladium determine spectrophotomer- tically giving 8% recovery by above process. 0. which contains out at a temperature in the range of 350 to 450°C no palladium. 15 to 25% and 60 to 80% respectively. From these results. The reaction mixture was filtrate. tained above was further purified and gave 0. The precip. The brown-colored mix.0 ml (6M ing 98% recovery by above process. The precipitates the precipitates of iron chloride were removed by filtra. A process as claimed in claim 1 wherein the heat [0051] 200 of a spent catalyst containing placed in an 55 treatment is carried out in inert atmosphere or in air. of the 45 treatment of the spent catalyst in step (i) is carried precipitate was obtained at pH about 6. of 200 Nl/hour. A process for the recovery of palladium from spent clear that both the methods gave identical results and catalyst generated from hydrogenation plant. [0050] The precipitates obtained at about pH 6 and at 2. Iron. The pH of the and under continuous stirring. [0049] 250g of an spent catalyst placed in an electric (ii) cooling the spent catalyst obtained from step muffle furnace was first dried for 3 hour at 150°C. The pH of the filtrate was then raised (vii) drying the metal salt to above 9 and precipitates collected and dried.1 to 0.1 to 0. 9 EP 1 636 393 B1 10 Example III ature at 400°C for 5 hour to remove organic residue (tar and nitro aromatics and aromatic amine).5) was dissolved in 25. [0052] 1.087 50 dium. the residue was heated at a temperature (iii) digesting the thermally treated and cooled at 400°C over the period of 2-4 hour to remove organic spent catalyst in a mineral acid selected from residue (tar and nitro aromatics and aromatic amine). Weight of Pd(dmg)2 = 0. with 100%. The precipitates were filtrate. A process as claimed in claim 1 wherein the Palla- itate obtained above was further purified and gave 0. The pH of the filtrate was raised to bon particles from the liquid. Carbon and moisture content in the spent g PdCl2 with 100%. which is equivalent to 25 mg of PdCl2. It was filtered with Buck. It was filtered with Buckner funnel at 400°C for a period of 3 hours. it is 1.2. 0. which contained palladium.0476 g. atmosphere is obtained using a gas selected from 6 .16 g PdCl2 lution (prepared in ethanol. 25mg 15 0.5 were analyzed for palladium content. whereby 10 pecially of iron and other metals. 3M hydrochloric acid for 8 hours. the residue was heated at a temper. 250 mg/25 ml) and the mix. electric muffle furnace was first dried for 3 hour at 150°C.5 contains ysis using Dimethylglyxime as complexing agent. The pH of the filtrate obtained tion. the also show that the recovered PdCl2 is 100% pure.05g of precipitate collected at pH 9. The pH of 6 and precipitate formed filtered to remove impurity es- the filtrate so obtained was raised initially to 6.5 and precipitate collected and 9. The pH of the second filtrate was again raised to at pH 6 was raised to 9. The precipitate ob- HCl) and to this was added 20 ml Dimethylglyoxime so. After nitrogen gas was introduced into the furnace at the 5. Example V 4.5 and the precipitates were collected and dried and dried. if any. was raised to about filtered to separate ash and dissolved matter. by washing with dilute hydrochloric acid was dried at (v) filtering the reaction mixture to separate car- 100°C in an oven. catalyst is maintained between 0. 1.1g of precipitate collected above pH 9 and for a period selected from 4 to 6 hours. the group consisting of nitric acid. 25 process comprising Example IV (i) thermally treating finally divided spent cata- lyst generated from a hydrogenation plant. hydrochloric The spent residue so obtained was digested in 2500 ml 35 acid and sulfuric acid.5 M aqueous hydrochloric acid.2. The spent res- [0048] 566g of spent catalyst was dried in an electric idue so obtained was digested in 2000 ml.163g palladium determine spectrophotomertically giv- isolated solid (at pH =9. After that it was filtered in a pre-weighed G-3 crucible and washed with 20 cold and hot water and the precipitate so obtained was Claims dried at 110°C. After 30 (i) above to room temperature ranging between nitrogen gas was introduced into the furnace at the rate 20 to 40°C in air. 3. collected and dried. recovered PdCl2 was also estimated by Gravimetric anal.2 g. 50% hydro- furnace for 3 hours at 150°C and subsequently calcined chloric acid for 7 hours. A process as claimed in claim 4 wherein the inert rate of 200 Nl/hour. ture was stirred and kept for 1 hour. about 6 and precipitate formed filtered to remove impurity 40 (vi) precipitating palladium as metal salt from the especially of iron and other metals. 5 after cooling to ambient temperature followed by washing ture so obtained was digested in 2M-hydrochloride acid with 0. A process as claimed in claim 1 wherein the thermal pH 9.

wobei in dem ver- ature and time needed for acid digestion is main. wobei die Kohlenstoff- haltenen verbrauchten Katalysators auf Raum. die ausgewählt aus der Gruppe bestehend aus Salpetersäure. wobei die für den Säu- reaufschluss erforderliche Temperatur und Zeit zwi- 12. 40 (ii) Abkühlen des aus dem obigen Schritt (i) er. 2. Verfahren nach Anspruch 1. catalyseur usagé généré par une unité d’hydrogé- lenstoffpartikeln von der Flüssigkeit abzutren. 15 9. Verfahren nach Anspruch 1. A process as claimed in claim 1 wherein the temper. (i) Wärmebehandeln des fein zerteilten ver. der Kohlenstoffgehalt tively. 8. der aus einer Hydrier. wobei die Wärmebe- the pH of the filtrate in the range of 6 to 11. wobei die Wärmebe- handlung des verbrauchten Katalysators in Schritt 6. anlage stammt. Argon und Helium ausge- wählten Gases erlangt wird. wobei das Metallsalz abgekühlten verbrauchten Katalysators in einer Palladiumchlorid ist. (i) bei einer Temperatur im Bereich von 350 bis 450 tration of mineral acid for digestion is maintained be. A process as claimed in claim 1 wherein the recovery 20 of palladium as metal salt is 100%. d’hydrogénation . wobei die molare Kon- zentration der Mineralsäure für den Aufschluss zwi- 11. A process as claimed in claim 1 wherein the metal 5. partikeln als Nebenprodukt in Form von Ruß zurück- temperatur im Bereich zwischen 20 bis 40 °C in gewonnen werden. Verfahren nach Anspruch 4. Verfahren nach Anspruch 1. (vi) Ausfällen von Palladium als Metallsalz aus 55 (i) le traitement thermique d’un catalyseur fine- dem Filtrat. 1. 10. Verfahren nach Anspruch 1. Revendications (iv) Reagieren der Säure mit dem verbrauchten 50 Katalysator unter ständigem Rühren. A process as claimed in claim 1 wherein the concen. A process as claimed in claim 1 wherein the carbon schen 2 bis 6 gehalten wird. 25 7. wobei das Palladium Patentansprüche als Metallsalz ausgefällt wird.2. 11 EP 1 636 393 B1 12 the group consisting of nitrogen. wobei die inerte Atmo- salt is dried in an air dried oven at a temperature in sphäre unter Verwendung eines aus der Gruppe be- the range of 90 -110°C. Verfahren nach Anspruch 1. Mineralsäure. argon and helium. Eisen zwischen 0. Salzsäure und Schwefelsäure ist. Verfahren nach Anspruch 1. Verfahren zur Rückgewinnung von Palladium aus einem verbrauchten Katalysator. Verfahren nach Anspruch 1. wobei das Verfahren folgendes 35 einem Lufttrockenofen bei einer Temperatur im Be- umfasst: reich von 90-110 °C getrocknet wird. der aus einer Hy. particles are recovered as by product in the form of carbon black. 4 bis 6 Stunden gehalten salt is palladium chloride. A process as claimed in claim 1 wherein the metal schen 50 bis 90 °C bzw. nung von Palladium als Metallsalz zu 100 % erfolgt. handlung in inerter Atmosphäre oder in Luft erfolgt. 6. (ii) le refroidissement du catalyseur usagé obte- 7 . 1. wobei die Rückgewin- brauchten Katalysators. stehend aus Stickstoff. 9. nation. 3. A process as claimed in claim 1 wherein the palla- dium is precipitated as a metal salt by maintaining 4. Verfahren nach Anspruch 1. °C und über einen aus 4 bis 6 Stunden ausgewählten tween to 2 to 6 molar. Luft. ment divisé usagé généré par une unité (vii) Trocknen des Metallsalzes. wobei das Metallsalz in drieranlage stammt. 10. wird. 30 8. um Koh. Verfahren nach Anspruch 1. brauchten Katalysator der Gehalt an Palladium und tained between 50 to 90°C and 4 to 6 hours respec. 5 Zeitraum erfolgt. 11. Verfahren nach Anspruch 1. (iii) Aufschließen des wärmebehandelten und 45 12.1 bis 0. le procédé comprenant : nen. Procédé de récupération du palladium à partir d’un (v) Filtrieren des Reaktionsgemischs. indem der pH-Wert des Filtrats im Bereich von 6 bis 11 gehalten wird. 10 zwischen 15 bis 25 % und der Feuchtegehalt zwi- schen 60 bis 80 % gehalten wird. 7.

9. Procédé selon la revendication 1.1 et 0. Procédé selon la revendication 1. dans lequel la ré- cupération du palladium sous forme de sel métalli- que est de 100 %. (iv) la réaction de l’acide avec le catalyseur usa- gé sous agitation continue . 35 6. Procédé selon la revendication 1. (v) la filtration du mélange réactionnel afin de 10 séparer les particules de carbone et le liquide . 7. 20 3. Procédé selon la revendication 1. Procédé selon la revendication 1. Procédé selon la revendication 1. 15 et 25 % et 60 et 80 %. 5 que. Procédé selon la revendication 1. Procédé selon la revendication 1. 0. dans lequel l’at- mosphère inerte est obtenue en utilisant un gaz choi- si dans le groupe constitué de l’azote. (vi) la précipitation du palladium sous forme de sel métallique à partir du filtrat . 30 5.2. dans lequel le trai- tement thermique du catalyseur usagé à l’étape (i) se déroule à une température dans la plage de 350 à 450 °C et sur une période choisie allant de 4 à 6 heures. dans lequel la tem. de l’argon et de l’hélium. dans lequel la con- centration d’acide minéral pour la digestion est main- tenue entre 2 et 6 M. de l’acide chlorhydrique et de l’acide sulfurique .2. dans un acide minéral métallique est le chlorure de palladium. (vii) le séchage du sel métallique. carbone et humidité dans le catalyseur usagé est maintenue respectivement en- tre 0. (iii) la digestion du catalyseur usage. 10.1 et 0. dans lequel le trai- tement thermique se déroule sous atmosphère iner- te ou à l’air libre. fer. 45 ladium est précipité sous forme de sel métallique en maintenant le pH du filtrat dans la plage de 6 à 11. 40 pérature et le temps nécessaires à la digestion dans l’acide sont maintenus respectivement entre 50 et 90 °C et 4 et 6 heures. 8. 25 4. choisi dans le groupe constitué de l’acide nitri. Procédé selon la revendication 4. Procédé selon la revendication 1. duit secondaire sous la forme de noir de carbone. 13 EP 1 636 393 B1 14 nu à l’étape (i) ci-dessus à une température am. dans lequel le sel miquement et refroidi. dans lequel les particules de carbone sont récupérées comme pro- 8 . 15 2. dans lequel le pal. Procédé selon la revendication 1. dans lequel la te- neur en palladium. biante comprise entre 20 et 40 °C dans l’air . dans lequel le sel métallique est séché dans un four à air sec à une 50 température dans la plage de 90 à 110 °C. traité ther. 55 11. 12.

INOUE . T FURU- SAWA. EP 1 636 393 B1 REFERENCES CITED IN THE DESCRIPTION This list of references cited by the applicant is for the reader’s convenience only. Industrial Engineering Chemistry-Research. 29. BABA . vol. and Grant. Dimmit [0008] • US 4331634 A. K. Shanton. Kenneth J. Patent documents cited in the description • US 4705896 A. 1990. Hunter William [0007] • JP 54009597 A [0013] • US 4578250 A. K. Demopoulos [0006] • US 251467 A [0012] • GB 2127001 A. errors or omissions cannot be excluded and the EPO disclaims all liability in this regard. [0009] chard A [0014] Non-patent literature cited in the description • Y. Melka. YOSHIZUKA . Edwards [0011] • US 4654145 A. It does not form part of the European patent document. 2111 [0015] 9 . Even though great care has been taken in compiling the references. Ri- • US 4435258 A. Van Der Puy [0005] • US 4105742 A. Jr.