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Recycling of precious

metal catalysts
A look at the best available technologies for efficient and environmentally
sound recycling of complex spent catalysts used in both oil refining and
petrochemical processes
Christian Hagelken Michel Verhelst
Umicore Precious Metals Refining

P
recious metal catalysts are crucial
for many technical syntheses. The HC, C, S
main application fields in oil
refining are catalytic reforming,
isomerisation and hydrocracking. Such ? Off-site
precious metal-bearing catalysts are also regeneration HC, C, S
used in bulk and speciality chemicals
productions such as vinyl acetate
monomer (VAM), purified terephtalic
acid (PTA) and many hydrogenation Catalyst Treatment
Metals
processes. The noble metals involved are use in Discharge Transport of residues
recovery
process
mainly platinum (Pt) and palladium
(Pd), but also the other platinum group
metals (PGM) ruthenium (Ru), iridium
Pd, Pt, Au... Catalyst support
(Ir) and rhodium (Rh), as well as gold Cu, Ni, Pb,... Offgas
(Au) and silver (Ag), either alone or in Process effluents
combination. Often, other metals (for Other residues
example, Sn, Pb, Ni, Co, Ge) are used as
promoters. All these metals are coated Responsibilities: Smelter/metals refiner
on various carriers such as alumina,
silica, zeolites and carbon. Catalyst user = Spent generator
Due to the high value of precious
metals, the recycling of the spent Figure 1 Recycling chain and responsibilities two options
catalyst at the end of its useful life is
crucial for the overall economic
performance of a catalytic process. environmental performance of the to ensure that all the operators involved
Refining companies specialising in selected refiner? in the recycling chain are acting in an
precious metals recycling have Besides their valuable content of EHS-compliant way when treating the
developed suitable technologies for the precious metals (Pt, Pd, Au, and so on), spent catalyst. This responsibility is
efficient reclaiming of these valuable spent catalysts also contain a complex related to individual regulations in
metals. However, selecting the right mix of different substances, such as: specific countries, to the Basel liability
recovery process and recycling company Catalytic base metals and promoters: protocol as well as to the principles of
for a specific spent catalyst is not easy. Sn, Pb, Ni, Co, and so forth responsible care, to which the chemical
Focus is usually on economical Fe, Ni, Cr from process corrosion of and oil-refining industry have
considerations the total cost to be paid reactor walls and tubes committed themselves.
and the amount of metals finally Hazardous elements by way of Whether the spent catalyst is sent for
returned from the recycling chain. In contamination through the feed/crude off-site regeneration or not (prior to
this context, the reliability and accuracy oil (As, Hg and more) shipping to a precious metals refinery)
of the weighing and sampling Halogens (Cl, F, and so on) such as may render the whole recycling loop
preparation is crucial, since the found in isomerisation catalysts more difficult to monitor. It might
analytical metals content obtained on Carbon (for example, high coked be more appropriate to consider a one-
the retained sample is the basis for all heel CCR catalysts) and hydrocarbon stop treatment at a precious metals
further calculations. Along with the contamination from the catalytic refiner, taking care of the whole
economical questions, the environ- process. spent package in an environmentally
mental issues must not be neglected: In one way or another, the recycling sound way.
What environmental, health and chain (Figure 1) has to cope with these
safety (EHS) risks arise in a certain complex mixtures. Just reclaiming the Metals refining
recycling chain? valuable metals is not sufficient; the When it comes to sending out precious
What liabilities are the spent whole recovery chain has to be metal-bearing spent catalysts on a
generator exposed to? evaluated for its environmental soluble carrier (typically a -Al2O3-
How secure can the spent generator soundness. carrier, which is soluble in caustic or
be about the technical, commercial and The generator of a spent catalyst has sulphuric acid) for recovery, the

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tolerance for contaminants (carbon,
Base and hydrocarbons, sulphur, nuisance
special metals elements, fines, and so on).
HC Rh Pb As a result, more and more soluble
Zn Pt Ni
Ir Hg S Ru Fe catalysts are finding their way into larger
Te
Se SiO2 As Sn smelters, offering an all-in-one solution
Co Au Cu S Bi
Ag C Pd for the untreated spent and, equally
In
Sb Cd Al2O3 importantly, putting all environmental
stakes in the same location.
At the Umicore Hoboken plant
Umicore-Processes Purified located near Antwerp in Belgium, the
Purified untreated spent catalyst as well as
waste
offgas
water numerous recycling materials (for
C
example, spent automotive catalysts and
HC Energy precious metal-bearing electronic scrap)
Sulphuric Depositories
recovery are fed into a large 250 000 MT/yr
acid << 0.1%/yr
S smelter, followed by separation into
Hg, Cd,...
different process streams. When it comes
to the spent precious metal catalysts, any
Base & special metals High-grade materials are disintegrated into single
Cu, Ni, Co, Sn, precious metals Slag for elements that find their way through the
Pb, Cd, As, Sb, Ag, Au, Pt, Pd, dyke
enforcement process (Figure 2). Even the bulk carrier
Se, Te, In,... Rh, Ir, Ru materials (alumina, silica), which are
going into the slag, are turned into
useful products for different applications
Figure 2 Disintegration and recycling of complex metals containing wastes in a such as dyke reinforcements or other
state-of-the-art precious metals smelter and refinery specific construction materials.
Process gas treatment generates
generator basically has the choice the slags in a smelter), the pyro- sulphuric acid as a by-product, the
between a pyro-metallurgical or a metallurgical process usually has a caloric value of combustibles like carbon
hydro-metallurgical recovery process, broader range of applications, such as or sulphur is used as fuel, off-gases are
the former being primarily a smelting, the recovery of spent catalysts on cleaned, process waters are sent to a
the latter being a wet chemical process. insoluble carriers (for example, carbon water-treatment plant, making the
While a hydro-metallurgical process also or zeolites based) as well as for certain whole plant not only a 100 per cent
offers rhenium-recovery (Re is lost with larger, modern smelters a high level of materials-recovery unit but also a nearly
zero-waste facility when it comes to the
overall environment.
Sulphuric acid The newly built smelter located at the
plant Hoboken plant includes a state-of-the-
art periphery (for example, off-gas- and
water-treatment plants) and a new
Process Matte precious metals refinery. Figure 3 shows
Lead the principle of the flow sheet.
blast
Gas furnace
SO2 Environmental liabilities
Finding the right balance between
Cu-smelter economical and ecological performance
Slag is crucial when dealing with all kinds of
Cu bullion Lead Aggregate for raw materials coming from various
Umicore bullion concrete:
140 000 t origins. To ensure a long-term
Leaching & plant
electro- commitment towards suppliers and
in Olen
winning Lead people, EHS should have high priority
Speiss refinery in the recycling of spent catalyst.
At the Hoboken plant, an
Ni: 2000 t
As: 1000 t environmental management system has
been implemented in accordance with
Precious metals residues ISO 14001 and in close connection with
the quality system (certified against ISO
Cupellation 9001). The plant has also been
Special successfully audited by several large,
metals
refinery international oil-refining companies.
The environmental performance of
PM-r efinery
the plant is continuously monitored by
H2SO4: Cu: Ag: 2400 t In: 30t Pb: 125 000 t
Umicore and by the authorities. This is
100 000 t >35 000 t Au: >100 t Se: 600 t Sn: 1500 t reported to the Flemish authorities in
PGM: 100 t Te: 150 t Sb: 3000 t detail and to the public in an annual
Bi: 400 t environmental report. A whole range of
measures is in place to prevent dust
Figure 3 Umicores smelter and refinery emission: dust-free emptying of the

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shipped drums or big bags, dust-free
sampling procedures, storage of the Contracted metal credit
spent catalysts in containers inside a Sampling losses*
warehouse, emptying of the containers (bias in weights or homogenisation)
under aspiration, transport in covered Analytical losses*
(deviation from reality)
belt systems and more. Besides their Metal losses Pre-treatment losses (regeneration)*
environmental importance, these = kg price Losses during transport & handling*
installations prevent any loss of Discharge losses*
precious metals with the dust fraction,
which further improves sampling
accuracy and metal yields. Process gases
from the smelter are cooled with energy Technical
recovery and cleaned with an processes,
electrofilter and by quenching with accuracy and Financing costs
water injection. The SO2 of the gases is performance = time interest rate
Recycling
transformed to sulphuric acid in the costs metal value
contact plant the gas treatment and
contact process act as a perfect filter.
All process waters are collected and Treatment & refining charges Contracted return time
treated in a physico-chemical water- Penalties/surcharges* Shipment time
treatment plant. About 75 per cent of Representation/analysis Pre-treatment (regeneration)*
the sludge from this water-treatment Pre-treatment (regeneration)* Delay by negotiation & administration*
plant is returned to the smelter. From the Logistics, transport, insurance Time for metals disposition
incoming water, 70 per cent is reused in Administration Lease (interest) rate and conditions
the plant for sprinkling and cooling. The * If not avoidable by selecting the optimum recycling process
metal content of the effluent into the
river Schelde is significantly lower than
Flemish standards. Figure 4 Economic evaluation of a catalyst recycling job

Economic impact
Determining the true bottom isomerisation catalyst with a Pt content Is it really necessary to ship a specific
profitability of a spent catalyst-recycling of about 0.3 per cent, at current Pt prices catalyst for off-site regeneration or could
job is not easy. It requires both of around US$800/troz, a 2 per cent it be sent directly to an appropriate
experience and a complex calculation deviation would result in a discrepancy modern smelter?
that has to consider not only costs but of US$1500/Mton of spent or for a 50 Can the number of contracting
also the time of the precious metals ton lot US$75 000 in total. Hence, an partners be reduced by making use of a
return, as well as the total metal yield of accurate, transparent and reliable total services package offered by the
the selected recycling chain. Figure 4 sampling becomes the first and most precious metals refiner (for example,
shows the main factors and inevitable parameter for selecting your inclusive transport arrangements and
interdependencies. It becomes obvious partner for precious metals reclamation. metals management)?
that not only the final refining step but While transparency should be Could a long-term relationship
also other parts of the selected recycling imposed by the spent generator (for under a frame contract with a
chain, such as off-site regeneration, instance, by appointing a witness), this sufficiently large, flexible and reliable
have to be considered. is in most cases not sufficient for refining partner save costs and efforts in
Compared to the intrinsic value of a assuring reliable and accurate sampling. administration by the spent generator?
spent precious metals catalyst, especially Also, sampling procedures, equipment Could an early technical
for Pt-spent, the reclamation costs in as well as skilled and dedicated workers discussion in a partnership between a
most cases are only a small part. Taking should be part of the evaluation. generator and refiner determine any
risks or uncertainties in the performance beneficial shortcuts in the handling and
of the recycling chain could easily offset Total chain optimisation pre-treatment of the spent?
the recycling cost. In addition, the When looking at the entire recycling The best approach for a true
recycling cost could carry a hidden cost chain for spent precious metal catalysts, optimisation of the recycling chain is
in case of inaccurate sampling. Hence, a in many cases more attention should be open and comprehensive communi-
bottom-line cost calculation is to be paid to the following aspects: cation between the partners involved in
balanced against the general expertise, How EHS compliant is the selected the chain.
professionalism and financial soundness recycling chain?
of the catalyst recycler as well as against How experienced, reliable and
the transparency and EHS compliance of financially sound are the partners Christian Hagelken is senior manager,
the entire recycling chain. involved in the chain? market R&D, for Umicore Precious Metals
How transparent are the processes Refining in Hoboken, Belgium. He joined
Weighing and sampling and how accurate are the handling and the precious metals activity of Degussa in
One of the most important economical sampling of the spent? 1989, which was taken over by Umicore
impacts is how to determine the true What costs, potential metal losses in 2003.
precious metal content of a spent and throughput time implications could Email: christian.hagelueken@eu.umicore.com
catalyst. Any 2 per cent deviation during arise outside the precious metals Michel Verhelst joined Umicore Precious
the catalyst handling, weighing and/or refinery before or after the actual spent Metals Refining in Hoboken, Belgium in
sampling logically corresponds with a 2 catalyst recovery? 2002 as manager, raw materials supply,
per cent deviation in the precious metal On the other hand, other issues might spent catalysts.
credit! For a typical reforming or be simplified (less could be more): Email: michel.verhelst@umicore.com

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