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(11) EP 1 636 393 B1
(12) EUROPEAN PATENT SPECIFICATION
Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).
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3 EP 1 636 393 B1 4
drocarbons and kerosene. The preferred solvent is ker- generation and recovery of palladium from spent residue,
osene. The aqueous phase was separated from the or- obtained from a catalytic process performed in homoge-
ganic phase, followed by stripping of palladium from the neous conditions, which is subjected to heating ca. 550
association with the oxime compounds in the organic to 600C to decompose the organic fragment. The resi-
phase by extraction with an aqueous ammonia solution. 5 due is then acid treated to obtain corresponding palladi-
The drawback of the process is that it involves multistage um salt. However, this invention has a limited scope in
processes. Moreover recovery of solvent for further re- the sense that it is only concerned with degradation of
uses makes the process complicated. metal complex having lower aliphatic mono-carboxylic
[0009] U. S. Patent No. 4,435,258 (1984) to Melka, Jr., acids as the organic moiety.
et al., discloses the recovery of palladium from spent 10 [0014] US Patent No. 4,331,634 (1982) to Shanton;
electroless catalytic baths by dissolving the palladium to Kenneth J. and Grant; Richard A, wherein strongly acidic
form a true solution followed by electro-deposition em- solution of sulphuric, hydrochloric, perchloric or nitric acid
ploying a nickel anode and a nickel or copper cathode. is used as stripping solvent for the extraction of the pal-
The recovery includes the steps of (a) dissolving the col- ladium from the organic acidic solution containing oxime
loidal palladium in the bath so as to form a true solution 15 as extracting reagent. The organic phase may also con-
by the addition of an oxidizing agent, e.g., hydrogen per- tain an anionic phase transfer material or catalyst to aid
oxide, (b) heating the bath to a temperature and for a the extraction process. In this patent, the oximes em-
time sufficient to essentially remove excess hydrogen ployed for the extraction of palladium are hydroxyoxime
peroxide; (c) placing the solution in an electrolytic cell and derivatives, which are expensive considering the in-
having (i) a nickel anode, and (ii) a cathode comprised 20 dustrial application.
of a metal or metallic surface which is non-contaminating [0015] Y. Baba, K, Inoue, K. Yoshizuka and T Furu-
or easily separable from the palladium to be deposited; sawa, (Industrial Engineering Chemistry-Research, Vol-
and (d) electrowinning palladium from the solution onto ume 29, (1990), page 2111) have described the use of
the cathode at a voltage which tends to minimize and non-cheating oximes such as dodecanal oxime, decanal
substantially reduce tin deposits. 25 oxime, octanal oxime and hexanol oxime for the extrac-
[0010] It has been found that with continued use, the tion of palladium metal. 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. When contamination reaches an are expensive considering the industrial application
extent such that the bath becomes ineffective or the elec- [0016] According to above prior art, most of the metal
troless plating becomes less adherent than desirable, 30 recovery methods are applicable to the homogeneous
and must then be discarded, as waste hence may not be reaction mixtures and employ chelating agents for ex-
suitable for commercial application. tracting metal ions. Process known in the prior art for
[0011] U. S. Patent No. 4,105,742 (1978) to Edwards, recovery of metals from supported catalysts also makes
et al., 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- 35 structure.
rocomplexes thereof together with other platinum group
metals and/or base metals in 0.01 to 2M acid solutions Objects of the invention
comprises contacting the starting solution with a suitable
extractant; the extractant soluble in water-immiscible sol- [0017] The main object of the present invention is to
vent, carried in an organic phase and comprising func- 40 provide an improved process for the recovery of palladi-
tional groups of the formula R.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.
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. 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, are nitro aromatic compounds.
not suitable for industrial application. [0019] Still another object of the present invention is
[0012] C. S. Patent No. 251467 (1988); to Pauko Jan, to recover 100% palladium with more then 99% purity.
(Chemical Abstract 109 (24): 213964) disclose the re- [0020] Yet another object of the present invention is to
covery of palladium from wastewater by sorption on ac- 50 recover carbon black as a vatue added product that can
tivated carbon, pretreated with an alkali metal salt of Eth- be reused
ylenediaminetetraacetic acid (EDTA). The wastewater is
required to be acidified to pH 3-7.5 before treating with Summary of the invention
activated carbon with EDTA solution to recover precious
metals. However, 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- provide an improved process for the recovery 100% pal-
ous systems. ladium from spent catalyst with more than 99% purity.
[0013] JP Patent No. 54 9597 (1978) discloses the re- The spent catalyst obtained from hydrogenation plant
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5 EP 1 636 393 B1 6
contains i) Pd in the range 0.1 to 0.2%; ii) Fe in the range metal salt is dried in an air dried oven at a temperature
0.1 to 0.2%; iii) Carbon in the range 15 to 25%; iv) Mois- in the range of 90 -110C.
ture in the range 60 to 80% and v) 3 to 6 % tar of dinitro- [0031] In yet another embodiment of the invention the
toluene was used to recover precious palladium as pal- recovery of palladium as metal salt is 100%.
ladium salt. The spent catalyst was subjected to heat 5 [0032] In a further embodiment of the invention, carbon
treatment at ca. 500C 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.
dissolve the palladium metal as corresponding salt and [0033] In yet another embodiment of the invention, the
separate the carbon particles by filtration. Solid palladium metal salt is palladium chloride.
chloride with high purity was obtained by adjusting the 10
pH of filtrate. This product does not require any further Detailed description of the invention
purification steps. 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. 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, the process com- (i) thermal treatment of finally divided spent catalyst
prising in the temperature range of 350 to 450C for a period
selected from 4 to 6 hours.
(i) thermally treating finaly divided spent catalyst 20 (ii) maintaining an inert atmosphere during heat
generated from a hydrogenation plant; treatment using gases like nitrogen, argon, helium
(ii) cooling the spent catalyst obtained from step (i) and the like gases.
above to room temperature ranging between 20 to (iii) cooling the spent catalyst to room temperature
40C in air; (i.e.20 to 40C) in air.
(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, hydrochloric acid
consisting of nitric acid, hydrochloric acid and sulfuric or sulfuric acid at a concentration in the range 2 to
acid; 6 molar.
(iv) reacting the acid with the spent catalyst under (v) allowing the acid to react with the spent catalyst
continuous stirring; 30 under continuous stirring at a temperature in the
(v) filtering the reaction mixture to separate carbon range of 50 to 90C and for a period of 4 to 6 hours.
particles from the liquid; (vi) filtering the reaction mixture to separate carbon
(vi) precipitating palladium as metal salt; particles from the liquid by known techniques.
(vii) drying the metal salt (vii) precipitating the palladium as metal salt in the
35 pH range 6 to 11.
[0023] In one embodiment of the invention, 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 to110C
a temperature in the range of 350 to 450C and for a
period selected from 4 to 6 hours. [0035] The catalyst generated from the hydrogenation
[0024] In another embodiment of the invention, the Pal- 40 plant contains i) Pd in the range 0.1 to 0.2%; ii) Fe in the
ladium, Iron, Carbon and moisture content in the spent range 0.1 to 0.2%; iii) Carbon in the range 15 to 25%; iv)
catalyst is maintained between 0.1 to 0.2; 0.1 to 0.2; 15 Moisture in the range 60 to 80% and v) 3 to 6 % tar of
to 25% and 60 to 80% respectively. dinitrotoluene may be used to recover palladium metal.
[0025] In yet another embodiment of the invention, the [0036] The finely divided spent catalyst may be sub-
heat treatment is carried out in inert atmosphere or in air. 45 jected to heat treatment in the temperature range
[0026] In yet another embodiment of the invention, the 350-450C for a period of 4 to 6 hours. 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, argon and helium. like nitrogen, argon or helium and like gases. The cal-
[0027] In another embodiment of the invention, the cined catalyst is preferably digested in mineral acids like
concentration of mineral acid for digestion is maintained 50 nitric acid, hydrochloric acid or sulfuric acid and like acids.
between to 2 to 6 molar. The digestion of the spent catalyst in acid is preferably
[0028] In a further embodiment of the invention, the carried out at temperature in the range of 50 to 90C for
temperature and time needed for acid digestion is main- a period selected from 4 to 6 hours. The acid concentra-
tained between 50 to 90C and 4 to 6 hours respectively. tion used for the digestion can vary in the range of 2 to
[0029] In yet another embodiment of the invention, the 55 6 molar.
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. 6 to 11 to precipitate palladium as a metal salt such as
[0030] In yet another embodiment of the invention, the palladium chloride.
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7 EP 1 636 393 B1 8
[0038] Palladium is estimated, in acidic aqueous solu- content by digestion with mineral acid and selective pre-
tion as brown- red complex, [PdI4]2-. In an acid medium cipitation of the metal salt by control of solution pH.
(hydrochloric acid, H2SO4) containing excess of iodide, [0043] The process has advantage of obviating very
palladium forms a brown- red complex, [PdI4]2-. The mo- high temperature incineration to recover precious metals.
lar absorptivity of the complex is 1.02x10-4 at max = 410 5 Selective precipitation of the metal salts results into re-
nm (a=0.096). A calibration curve is obtained by prepar- covery of the metals salts with very high purity. This prod-
ing a palladium iodide complex solution by dissolving the uct does not require any further purification steps, solvent
known amounts of palladium chloride and other reagent, extraction technique and use of costly organic complex-
like concentrated hydrochloric acid, ascorbic acid and ing ligands like oxime, hydroxyoxime and derivatives etc.,
potassium iodide. The detailed procedure is as follow: 10 for metal recovery.
[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. To this the scope of the present invention.
was added 10 ml of 6N hydrochloric acid, 20 ml of 20%
(w/v) potassium iodide solution, and 4 ml of 1% (w/v) 15 Example I
ascorbic acid solution. The volume was made up to 100
ml with water in a 100 ml volumetric flask, and absorb- [0045] 715g of spent catalyst, containing 0.15% palla-
ance at 410 nm against water was measured dium, 0.15% Iron, 5% m-dinitrotoluene, 20% carbon and
Wt of Palladium in the diluted solution can be obtained rest water placed in an electric muffle furnace, was dried
as: 20 for 3 hour at 150C. The dried spent catalyst containing
Pd, Fe and organic compounds was fired at an elevated
Wt ofPd per 100 ml = (A/). (Mol. Wt of Palladium) temperature up to 400C. for a period of 5 hrs. The pow-
A = Absorbance of the 100 ml solution at 410 nm dery-fired product was obtained. All the carbon burnt and
= Extinction coefficient, 1.024 mol-1cm-1 for [PdI4]2 weight of the ash containing precious metal was found
species at 410 nm 25 to be 4.3g, and the brown-fired mixture so obtained was
digested in 2M hydrochloric acid for 5 hours at 90C. It
[0040] Palladium has also be estimated spectropho- was filtered with Buckner funnel after cooling to ambient
tomertically using ICP spectrometer. This is most accu- temperature. The pH of the filtrate, which contained pal-
rate method of estimation of metals ions at ppm/ppb lev- ladium, was raised to 6 and precipitate formed were fil-
els. 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. The precipitates were collected and dried. The pH
and receding its intensity on ICP spectrometer for palla- of the filtrate obtained at pH 6 was raised to 9.5 and pre-
dium at 340.458 nm using Perkin Elmers Inductively cipitate collected and dried.
Coupled Plasma Emission Spectrometer. [0046] The precipitates obtained at pH 6 and pH 9.5
[0041] The present process involves thermal desorp- 35 was analyzed for palladium content. 0.745 g of the pre-
tion of oligomerized nitro or amino organic compounds cipitate was obtained at pH 6, which contains no palla-
generated during hydrogenation of nitroaromatics and dium. 1.026g of precipitate collected at pH 9.5 contains
get adsorbed on the active sites present on the surface 0.59g palladium determine spectrophotomertically. The
of the catalyst followed by oxidation of the carbonaceous total palladium content adsorbed on the carbon, based
compound which are relatively of lower carbon number 40 on initial palladium impregnated on the carbon was 0.605
in air at lower temperature. This oxidation step being ex- g showing 98% recovery by above process.
othermic in nature initiates the oxidation of carbon sup-
port which result into thermal cascading effect and oxi- Example II
dizes the entire carbonaceous matter present in the cat-
alyst contains without supplying of additional heat. The 45 [0047] 566g of spent catalyst was dried in an electric
ashed catalyst contains the insoluble oxides of the pal- furnace for 3 hours at 150C and subsequently calcined
ladium or other metals are brought into solution by oxi- at 400C for a period of 5 hours. The brown-colored mix-
dization with aqueous solution as salt of mineral acid. 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 80C
of mineral acid are selectively precipitated out by adjust- 50 and under continuous stirring. The reaction mixture was
ing the pH of the solution. filtered to separate ash and dissolved matter. 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- the precipitates of iron chloride were removed by filtra-
mosphere prior to oxidation of carbonaceous compounds tion. The pH of the second filtrate was again raised to
ii) oxidation of carbonaceous compounds having low car- 55 9.5 and the precipitates were collected and dried. 0.882g
bon number compounds at around 500C and use of ther- of precipitates contain 0.65g palladium evidencing 100%
mal energy generated for initiating oxidation of carbon recovery of palladium as palladium chloride determined
support, (iii) dissolution of metals present in the ashed spectrophotomertically.
5
9 EP 1 636 393 B1 10
Example III ature at 400C for 5 hour to remove organic residue (tar
and nitro aromatics and aromatic amine). The spent res-
[0048] 566g of spent catalyst was dried in an electric idue so obtained was digested in 2000 ml, 50% hydro-
furnace for 3 hours at 150C and subsequently calcined chloric acid for 7 hours. It was filtered with Buckner funnel
at 400C for a period of 3 hours. The brown-colored mix- 5 after cooling to ambient temperature followed by washing
ture so obtained was digested in 2M-hydrochloride acid with 0.5 M aqueous hydrochloric acid, the carbon so ob-
for 3 hours while maintaining the temperature at 80C tained was dried at 100C in an oven. The pH of the
and under continuous stirring. The reaction mixture was filtrate, which contained palladium, was raised to about
filtered to separate ash and dissolved matter. The pH of 6 and precipitate formed filtered to remove impurity es-
the filtrate so obtained was raised initially to 6, whereby 10 pecially of iron and other metals, if any. The precipitates
the precipitates of iron chloride were removed by filtra- were collected and dried. The pH of the filtrate obtained
tion. The pH of the second filtrate was again raised to at pH 6 was raised to 9.5 and precipitate collected and
9.5 and the precipitates were collected and dried and dried.
recovered PdCl2 was also estimated by Gravimetric anal- [0052] 1.05g of precipitate collected at pH 9.5 contains
ysis using Dimethylglyxime as complexing agent. 25mg 15 0.163g palladium determine spectrophotomertically giv-
isolated solid (at pH =9.5) was dissolved in 25.0 ml (6M ing 98% recovery by above process. The precipitate ob-
HCl) and to this was added 20 ml Dimethylglyoxime so- tained above was further purified and gave 0.16 g PdCl2
lution (prepared in ethanol, 250 mg/25 ml) and the mix- with 100%.
ture was stirred and kept for 1 hour. 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 110C. Weight of Pd(dmg)2 = 0.0476 g, which is
equivalent to 25 mg of PdCl2. From these results, it is 1. A process for the recovery of palladium from spent
clear that both the methods gave identical results and catalyst generated from hydrogenation plant, the
also show that the recovered PdCl2 is 100% pure. 25 process comprising
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11 EP 1 636 393 B1 12
the group consisting of nitrogen, argon and helium. 2. Verfahren nach Anspruch 1, wobei die Wrmebe-
handlung des verbrauchten Katalysators in Schritt
6. A process as claimed in claim 1 wherein the concen- (i) bei einer Temperatur im Bereich von 350 bis 450
tration of mineral acid for digestion is maintained be- C und ber einen aus 4 bis 6 Stunden ausgewhlten
tween to 2 to 6 molar. 5 Zeitraum erfolgt.
7. A process as claimed in claim 1 wherein the temper- 3. Verfahren nach Anspruch 1, wobei in dem ver-
ature and time needed for acid digestion is main- brauchten Katalysator der Gehalt an Palladium und
tained between 50 to 90C and 4 to 6 hours respec- Eisen zwischen 0,1 bis 0,2, der Kohlenstoffgehalt
tively. 10 zwischen 15 bis 25 % und der Feuchtegehalt zwi-
schen 60 bis 80 % gehalten wird.
8. A process as claimed in claim 1 wherein the palla-
dium is precipitated as a metal salt by maintaining 4. Verfahren nach Anspruch 1, wobei die Wrmebe-
the pH of the filtrate in the range of 6 to 11. handlung in inerter Atmosphre oder in Luft erfolgt.
15
9. A process as claimed in claim 1 wherein the metal 5. Verfahren nach Anspruch 4, wobei die inerte Atmo-
salt is dried in an air dried oven at a temperature in sphre unter Verwendung eines aus der Gruppe be-
the range of 90 -110C. stehend aus Stickstoff, Argon und Helium ausge-
whlten Gases erlangt wird.
10. A process as claimed in claim 1 wherein the recovery 20
of palladium as metal salt is 100%. 6. Verfahren nach Anspruch 1, wobei die molare Kon-
zentration der Mineralsure fr den Aufschluss zwi-
11. A process as claimed in claim 1 wherein the carbon schen 2 bis 6 gehalten wird.
particles are recovered as by product in the form of
carbon black. 25 7. Verfahren nach Anspruch 1, wobei die fr den Su-
reaufschluss erforderliche Temperatur und Zeit zwi-
12. A process as claimed in claim 1 wherein the metal schen 50 bis 90 C bzw. 4 bis 6 Stunden gehalten
salt is palladium chloride. wird.
(i) Wrmebehandeln des fein zerteilten ver- 10. Verfahren nach Anspruch 1, wobei die Rckgewin-
brauchten Katalysators, der aus einer Hydrier- nung von Palladium als Metallsalz zu 100 % erfolgt.
anlage stammt; 40
(ii) Abkhlen des aus dem obigen Schritt (i) er- 11. Verfahren nach Anspruch 1, wobei die Kohlenstoff-
haltenen verbrauchten Katalysators auf Raum- partikeln als Nebenprodukt in Form von Ru zurck-
temperatur im Bereich zwischen 20 bis 40 C in gewonnen werden.
Luft;
(iii) Aufschlieen des wrmebehandelten und 45 12. Verfahren nach Anspruch 1, wobei das Metallsalz
abgekhlten verbrauchten Katalysators in einer Palladiumchlorid ist.
Mineralsure, die ausgewhlt aus der Gruppe
bestehend aus Salpetersure, Salzsure und
Schwefelsure ist; Revendications
(iv) Reagieren der Sure mit dem verbrauchten 50
Katalysator unter stndigem Rhren; 1. Procd de rcupration du palladium partir dun
(v) Filtrieren des Reaktionsgemischs, um Koh- catalyseur usag gnr par une unit dhydrog-
lenstoffpartikeln von der Flssigkeit abzutren- nation, le procd comprenant :
nen;
(vi) Ausfllen von Palladium als Metallsalz aus 55 (i) le traitement thermique dun catalyseur fine-
dem Filtrat; ment divis usag gnr par une unit
(vii) Trocknen des Metallsalzes. dhydrognation ;
(ii) le refroidissement du catalyseur usag obte-
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13 EP 1 636 393 B1 14
nu ltape (i) ci-dessus une temprature am- duit secondaire sous la forme de noir de carbone.
biante comprise entre 20 et 40 C dans lair ;
(iii) la digestion du catalyseur usage, trait ther- 12. Procd selon la revendication 1, dans lequel le sel
miquement et refroidi, dans un acide minral mtallique est le chlorure de palladium.
choisi dans le groupe constitu de lacide nitri- 5
que, de lacide chlorhydrique et de lacide
sulfurique ;
(iv) la raction de lacide avec le catalyseur usa-
g sous agitation continue ;
(v) la filtration du mlange ractionnel afin de 10
sparer les particules de carbone et le liquide ;
(vi) la prcipitation du palladium sous forme de
sel mtallique partir du filtrat ;
(vii) le schage du sel mtallique.
15
2. Procd selon la revendication 1, dans lequel le trai-
tement thermique du catalyseur usag ltape (i)
se droule une temprature dans la plage de 350
450 C et sur une priode choisie allant de 4 6
heures. 20
8
EP 1 636 393 B1
This list of references cited by the applicant is for the readers convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.