1830 Ind. Eng. Chem. Res.

1999, 38, 1830-1836

Selective Rhenium Recovery from Spent Reforming Catalysts

T. N. Angelidis,* D. Rosopoulou, and V. Tzitzios
Laboratory of General and Inorganic Chemical Technology, Department of Chemistry (Box 114),
Aristotle University, GR 54006, Thessaloniki, Greece

Reforming catalysts (0.3% Pt, 0.3% Re) are used extensively in industry for the improvement of
the octane number of fuels. After deactivation the catalysts are treated for the recovery of Pt
and Re. The aim of this study was to simplify the conventional recovery process by the application
of a slight alkali solution (NaHCO3) for the selective dissolution of Re. The process was tested
in batch and packed column reactors with crushed and uncrushed catalyst extrudes. The influence
on the reaction yield of NaHCO3 concentration, pH, temperature and space velocity was examined
and the optimum conditions were determined. The Re dissolution process seemed to follow first-
order kinetics, and the recovery yield was up to 97% for crushed and up to 87% for uncrushed
catalyst samples.

1. Introduction The metal and acidic components are supported on an

Byproduct molybdenite or tungsten molybdenite con-
centrates from copper mines are the most important
source of rhenium.1,2 The rhenium content is low,
generally in the few hundred parts per million range.
Almost all these concentrates are roasted to technical
grade molybdic oxide, the most common molybdenum
product sold commercially.2 Rhenium oxide is volatilized
at high roasting temperatures and condensed down-
stream at lower temperatures, eventually reparting to
the scrubber liquor as a dilute solution.1,2
Worldwide rhenium production is about 50 tons per
year.3 Rhenium existed as a curiosity with little practi-
cal application for its first 50 years. (It was discovered
in Berlin in 1925.)4,5 Use was limited to a few specialty
and high-temperature alloy applications. In the early
1960s interest in the potential for catalytic use of
rhenium developed, and by the early 1970s significant
catalytic use had began. Currently, the main use of
rhenium is in catalysts (90%), nickel-cobalt base su-
peralloys, and rhenium-molybdenum and rhenium-
tungsten alloys.3
The major catalytic use of rhenium is in petroleum-
reforming catalysts used to produce high-octane hydro-
carbons for low-lead, lead-free gasoline. Bimetallic
platinum-rhenium catalysts have replaced many of the
platinum catalysts used previously. Rhenium-containing
reforming catalysts tolerate greater amounts of carbon
formation and make it possible to operate at lower
pressures and higher temperatures, which leads to
improved yields and octane ratings.6
Reforming catalysts are dual functional in that they
promote simultaneously reactions that are specific func-
tions of the metal (platinum) and/or acidic properties
of the catalyst. The metal provides the hydrogenation-
dehydrogenation activity. The acid activity of the cata-
lysts provides all the other reforming reactions (pro-
duction or breakage of carbon bonds) and is supplied
by the addition of halogens (usually chlorine) to the
catalyst base. Rhenium acts as a promoter, as men-
tioned above, and does not catalyze any specific reaction.
* Corresponding author: E-mail: angelid@chem.auth.gr.
10.1021/ie9806242 CCC: $18.00 © 1999 American Chemical Society
Published on Web 04/03/1999
alumina base (γ- or η-alumina) with a high active
surface.7-9
Reforming catalysts remain in use for many years and
can be regenerated in situ and reactivated by heat and
chemical additives (chlorides). These procedures invert
platinum particles agglomeration (sintering) and acidic
components losses. When the catalyst loses activity
permanently resulting in marked loss of yield, it is then
ready for recycling. This loss is generally caused by slow
deterioration of substrate, agglomeration of active con-
stituents (metallic clusters), poisoning by coke, sulfur,
or metallic compounds, or overheating and loss of
surface area and active reaction sites of the alumina
substrate.6-10
The processing of spent reforming catalysts does not
only involve chemical and metallurgical activity, it also
encompasses commercial and accounting controls be-
cause of the high monetary value of the material. The
most common precious metals loading is 0.3% Pt and
0.3% Re. At 1997 market prices, this material had a
recoverable value of about $32 per kg of which $1.55
was due to Re.6
At the end of the catalyst life cycle, it is discharged
from the reactors and shipped to the reclamation
facility. The feed material to the processing stream
contains the original catalyst components in addition
to coke, base metals, and hydrocarbon residuals. Coke
and hydrocarbon materials are normally removed in situ
before shipping by heating and burning.
Rhenium is recovered from the spent catalysts by
pyrometallurgical or hydrometallurgical processes. Py-
rometallurgical processes involve chlorination at high
temperatures (1173-1223 K) for recovery of rhenium
along with platinum as volatile chlorides;10,11 heating
at high temperatures (1073 K) in a gas flow containing
water. The rhenium oxide dissolved in water, precipi-
tates on the walls;10 annealing with Na2CO3 or anneal-
ing in oxidation atmosphere.10,11 Pyrometallurgical pro-
cessing is not so attractive for Re-bearing materials
because the Re would not be economically recoverable
from the resultant slags and losses of volatile rhenium
oxides might occur.6

Figure 1. The conventional rhenium recovery process from spent
reforming catalysts. Rhenium recovery from the leaching solution
is accomplished by ion exchange.6
The spent-catalyst hydrometallurgical processing com-
prises several unit operations aimed at the recovery of
the various components of the spent catalyst, alumina,
platinum, and rhenium. The first task is to reduce the
bulk by dissolution of alumina. Alumina is dissolved
with both acids and alkali to form soluble salts.6,10,12
During the 1960s, 1970s, and early 1980s, caustic
dissolution was used as the primary technique at many
processing facilities. However difficulties in Re recovery
from the caustic medium and residues resulted in
abandonment of this process in favor of the sulfuric acid
dissolution.6,13
The conventional sulfuric acid dissolution process is
shown in Figure 1. During sulfuric acid dissolution
alumina and Re are almost completely dissolved as well
as a part of the fine particle’s size Pt (up to 10%). After
reduction to remove any contained Pt the slurry is
transferred to settling and filtered. The remaining solids
are transferred to Pt-processing facilities, whereas the
filtrate containing aluminum sulfate and Re is filtered
repeatedly to remove all fine insoluble matter and then
is directed to the Re recovery facilities. Re is recovered
by the application of either liquid ion exchange (LIX)
or solid ion exchange (SIX). In both cases the active
compounds are organic amines. Other separation tech-
niques such as pressure reduction by hydrogen or sulfur
dioxide,14 ion exchange applying various active
materials,12,13,15 and solvent extraction13 may be used.
After elution the elute is neutralized by ammonia gas
or ammonium hydroxide and then is evaporated to
super-saturated solutions, cooled, and allowed to crys-
Ind. Eng. Chem. Res., Vol. 38, No. 5, 1999 1831
Figure 2. Proposed simplified rhenium recovery process.
tallize. After multistage dissolution and crystallization
steps, pure NH4ReO4 crystals are obtained.6,12
The main aim of the present research is to examine
to what extent a slight alkali (produced by a common
and cheap reagent, such as NaHCO3) leaching process
may dissolve selectively Re causing a simplification to
the whole recovery procedure. The expected result is
shown in Figure 2, where the simplified recovery process
is shown. Compared with the conventional process
(Figure 1), the fundamental difference is the substitu-
tion of the complicate and expensive ion-exchange
process for Re separation.
2. Thermodynamic Consideration
The exact nature of rhenium compounds on spent
catalysts is not completely known and may vary with
the type of catalyst. Researchers have suggested that
the rhenium is present in a metallic state and possibly
alloyed with platinum or in an oxide state, in mixtures,
etc.6 The reforming process is taking place at high
pressure, in temperatures from 733 to 798 K, and in
the presence of hydrogen (hydrogen to hydrocarbon feed
mole ratios from 3 to 10).8 Under these reducing
conditions the presence of rhenium in metallic form
seems to prevail, because the main rhenium oxides are
reduced to metallic rhenium according to the following
thermodynamic consideration (thermodynamic data
from HRC16 at 773 K; H2 pressure, 1 atm):
ReO2 + 2H2 f Re + 2H2O
∆G ) -26 kcal/mol (1)
ReO3 + 3H2 f Re + 3H2O
∆G ) -56 kcal/mol (2)
Re2O7 + 7H2 f 2Re + 7H2O
∆G ) -143.6 kcal/mol (3)
When the catalyst is removed from the reactor, metallic
rhenium is unstable at atmospheric condition and is
readily oxidized according to the reactions (thermody-
1832 Ind. Eng. Chem. Res., Vol. 38, No. 5, 1999
Figure 3. Potential pH equilibrium for rhenium in aqueous
solution at 298 K (rhenium concentration, 10-3 M). Full lines
represent equilibrium between solid phases and liquid-solid
phases, thin dotted lines represent the equilibrium between liquid
phases, the double dotted lines determine the leaching working
area, and the double arrow line represents the active working area.
namic data from HRC16 at 298 K and O2 pressure, 1
atm):
Re + 3.5O2 f Re2O7 ∆G ) -260.3 kcal/mol
Re + O2 f ReO2 ∆G ) 93.5 kcal/mol
Re + 1.5O2 f ReO3 ∆G ) -121.2 kcal/mol
To predict the behavior of rhenium during a dissolu-
tion hydrometallurgical process thermodynamic data
were applied for the more common rhenium forms
(metallic rhenium and main rhenium oxides and dis-
solved species in aqueous solution).17 In Figure 3 an
E-pH diagram is shown, depicting the thermodynamic
stability regions of the various solid and soluble Re
species in aqueous solution (without complexing agents).
According to Figure 3 the following conclusions are
obtained:
•It is almost impossible for Re metal to exist in the
catalyst, because it is readily oxidized to reactions 4, 5,
and 6
•Perrhenic anhydrite is readily soluble in pure water
to form perrhenic acid:
Re2O7 + H2O f 2ReO4- + 2H +
•Rhenium trioxide disproportionates in an alkali envi-
ronment to form perrhenic ions and rhenium dioxide
3ReO3 + 2OH- f 2ReO4- + ReO2 + H2O
and in an acid environment to form perrhenic ions and
rhenous ions
3ReO3 + 2H+ f 2ReO4- + Re3+ + H2O
Figure 4. γ-Alumina solubility in aqueous solution at 298 K. Full
lines represent equilibrium between solid and liquid phases, thin
line represents equilibrium between liquid phases, the double
dotted lines determine the leaching working area, and the double
arrow line represents the active working area.
•Rhenium dioxide disproportionates in alkali environ-
ment to form perrhenic ions and rhenium sesquioxide
(4) 3ReO2 + 2OH- f ReO4- + Re2O3 + H2O (10)
and in an acid environment to form perrhenic ions and
(5)
rhenous ions
(6) 2ReO2 + 2H+ f Re3+ + ReO3 + H2O (11)
•Rhenium sesquioxide disproportionates in alkali
environment to form perrhenic ions and rhenides ions
Re2O3 + 2OH- f ReO4- + Re- + H2O (12)
and in acid environment to form rhenous ions
Re2O3 + 6H+ f 2Re3+ + 3H2O (13)
According to the sequence of reactions above the final
products in an alkali environment are perrhenic ions
and rhenides ions, whereas in an acidic environment,
perrhenic ions and rhenous ions. In practice, rhenide
ions are not stable at atmospheric conditions and are
readily oxidized to perrhenic ions:
Re- + 2O2 f ReO4- (14)
(7)
The rhenous ions are oxidized to perrhenic ions during
the acid-leaching procedure, because of the mild oxida-
tive action of the concentrate sulfuric acid applied in
this case. So, in both cases the final product is a
perrhenic ion solution.
(8) In alkali leaching, alumina is dissolved by strong
alkali (NaOH) in autoclaves at high pressure and
temperature. The application of a weak alkali (i.e.,
NaHCO3) may cause a selective rhenium dissolution at
atmospheric conditions, because alumina is not expected
to dissolve considerably in the slight alkali environment,
(9) pH 6-9, provided by NaHCO3 solutions (Figure 4).

Although other weak alkalis may be applied, because
the procedure depends on pH and not on the nature of
the alkali, NaHCO3 was selected as a common and
inexpensive reagent. The main metallic contaminants
of the reforming catalysts (iron and copper)7,8 are also
slightly soluble in this pH region. So, the leachate
produced under this condition will be rather pure,
containing only perrhenic ions; and a less expensive and
elaborate procedure is required.
Experimental Section
3.1. Materials. The spent catalyst used for the
rhenium recovery tests was obtained from the naphtha
reforming facilities of the EKO refinery (Thessaloniki,
Greece). The catalyst has the commercial name KX-120
(Cyanamid-Ketjen) and contains platinum and rhenium
as active constituents.
The chemical composition and the physical charac-
teristics of the fresh catalyst (dry base) were as fol-
lows: Pt ) 0.3% w/w, Re ) 0.3% w/w, Cl ) 0.91% w/w,
Fe ) 0.02% w/w, Cu ) 24 ppm; specific surface, 193 m2/
g; density, 0.7 g L-1; mean diameter, 1.63 mm; mean
length, 4.6 mm; shape, extrudes.
The samples of spent catalysts were derived from the
naphtha reforming reactor after decoking by air heating
and were analyzed after dissolution in aqua-regia for
the active constituents and the main metallic contami-
nants. Pt, Cu, and Fe were analyzed by atomic absorp-
tion spectroscopy (AAS) (Perkin-Elmer 2380), Re by the
spectrophotometric R-furildioxime method,19 using a
Hitachi U-2000 spectrophotometer. Chemical analysis
of selected samples gave the following results (dry
base): Re, 0.290% w/w (SD ) 0.006, n ) 5); Pt, 0.287%
w/w (SD ) 0.005, n ) 5); Fe, 0.03% w/w; Cu, 30 ppm.
The specific surface after the decoking procedure was
162 m2 g-1. Differences from the nominal values are
attributed to changes and losses during use, regenera-
tion cycles and the decoking procedure.
3.2. Batch Experiments. Selective rhenium dissolu-
tion was initially studied by batch experiments. Of the
leaching solution (NaHCO3) 50 mL were placed with 1
g of crushed or uncrushed catalyst in 100-mL conical
flasks. The flasks were agitated for 2 h in an agitated
temperature-controlled water bath. Preliminary tests
show that the reaction reaches equilibrium after 90 min,
so the time of reaction was fixed at 2 h. At the end of
the experiment the solids were washed with deionized
water, and the concentration of rhenium was deter-
mined both in the liquids as well as in the solid phase
by the R-furildioxime method. The main metallic im-
purities, iron and copper, were also determined in the
liquid phase by AAS. Crushed-catalyst samples were
produced by crushing the long extrudes to pieces with
lengths from 1 to 2 mm.
The standard condition applied at the batch experi-
ments were: reaction time, 2 h; NaHCO3, 0.1 M;
temperature, 313 K; solution, 50 mL; solids, 1 g.
3.3. Packed Column Experiments. The NaHCO3
leaching procedure was carried out using a fixed-bed
laboratory glass reactor with internal diameter, 1.8 mm.
Five grams of catalyst were used to form a column 4.5
cm in height. Two beds of glass balls (diameter, 3 mm;
bed height, 5 cm each) were placed before and after the
catalyst bed to normalize the liquid flow through the
Ind. Eng. Chem. Res., Vol. 38, No. 5, 1999 1833
Figure 5. Rhenium recovery yield as a function of the NaHCO3
concentration (standard conditions). The vertical lines represent
the stoichiometrically required concentration of NaHCO3 for Re2O3
and ReO2 dissolution.
catalytic bed. The leaching solution was pumped con-
tinually through the catalyst bed from the bottom of the
reactor (upflow) by a peristaltic pump. Aliquots were
derived at certain times at the outlet of the reactor and
analyzed for rhenium. At the end of every experimental
run rhenium concentration was determined in the bulk
of the leaching solution collected at the outlet of the
reactor.
The standard condition applied at the packed column
experiments, if not otherwise stated, were: NaHCO3
concentration, 0.05 M; temperature, 298 K; catalyst
weight, 5 g; sample volume, 20 mL; sampling interval,
5 min.
4. Results and Discussion
4.1. Batch Experiments. A series of experiments
was carried out to study the effect of the initial NaHCO3
concentration on the yield of rhenium recovery. The
results are shown in Figure 5 for crushed and uncrushed
catalyst samples. Even without NaHCO3 deionized
water (pH ) 6) dissolves a quantity of rhenium (about
17% w/w). (This experiment is not shown in Figure 5
because of the logarithmic scale of the concentration
axis.) This indicates that a part of rhenium exists on
the catalyst in the form of Re2O7 and produces HReO4
during dissolution by deionized water according to
reaction 7. As shown in Figure 5, as the concentration
of NaHCO3 increases, the recovery yield follows a sharp
increase and then becomes almost constant at NaHCO3
concentrations greater than 0.01 M. This behavior is
expected from the thermodynamic consideration because
the increase of the NaHCO3 concentration is followed
by a respective pH increase caused by hydrolysis:20
HCO3- + H2O f H2CO3 + OH- (15)
In Figure 6 the measured initial pH values are
determined as a function of the initial NaHCO3 concen-
tration. The stabilization of the recovery yield follows a
1834 Ind. Eng. Chem. Res., Vol. 38, No. 5, 1999
Figure 6. Initial pH values as a function of the concentration of
NaHCO3.
similar behavior with the pH values. It is obvious that
at higher pH values the other rhenium oxides (ReO2,
Re2O3, and ReO3) starts to dissolve according to the
thermodynamic consideration (reactions 8, 10, and 12).
The vertical lines in Figure 5 represent the required
concentration of NaHCO3 for the complete dissolution
of rhenium at the standard experimental conditions
according to the stoichiometry of the respective overall
dissolution reactions:
1. ReO2 dissolution:
3ReO2 + 4HCO3- + 2H2O + 2O2 f 3ReO4- +
4H2CO3 (16)
The stoichiometric ratio [Re]/[NaHCO3] is 3/4.
2. Re2O3 dissolution:
Re2O3 + 2HCO3- + H2O + 2O2 f 2ReO4- +
2H2CO3 (17)
The stoichiometric ratio [Re]/[NaHCO3] is 1/1.
According to the consideration above the relative
NaHCO3 concentrations are 0.0032 and 0.0043 M. The
position of the vertical lines in Figure 5 shows that up
to the yield stabilization the overall quantity of the
added NaHCO3 is consumed by the dissolution reaction.
In the stabilization region there is an excess quantity
of NaHCO3. Acid titration of the solution at the end of
the dissolution experiments in this region show that the
sum of the consumed and the remaining quantity of
NaHCO3 is approximately equal to the initial one. This
means that a small quantity of NaHCO3 is consumed
by side reactions (i.e., alumina dissolution). The differ-
ence (10-15%) may be attributed mainly to NaHCO3
remaining adsorbed on the catalyst species and to losses
by CO2 formation:20
HCO3- f CO2 +OH -
(18)
As shown in Figure 5 the behavior of crushed and
uncrushed catalyst samples differ. Crushed catalyst
Figure 7. Rhenium recovery yield as a function of temperature.
samples present better recovery yields (up to 97%) than
uncrushed (up to 87%). The difference is attributed
to the presence of rhenium in clogged pores. These
rhenium species are not reached by the leaching solu-
tion. After crushing a quantity of these clogged pores
open and the relative rhenium species are available to
dissolution. It is also possible that the system is slightly
kinetically controlled by diffusion through the catalyst
pores or by the dissolution reaction and the stabilization
region is not really in equilibrium. The later is proved
by measurements at increasing temperatures (Figure
7) which show a slight increase of the recovery yield at
higher temperatures.
4.2. Packed Bed Experiments. The application of
a batch process prevails problems in industrial practice
(e.g., mixing problems for uncrushed samples and
restrictions on the processed catalyst quantity). For this
reason the slight alkali process was tested in a packed-
bed reactor that overcomes these disadvantages. The
packed-bed experiments were carried out with continu-
ous flow of the leaching solution to predict the kinetic
behavior of the system. Atmospheric conditions (tem-
perature, 298 K) and uncrushed catalyst samples were
applied.
The mass balance of the reactor for rhenium is given
by:
Q dCr ) rRe dVr (19)
where Q ) the volumetric flow, mL min-1; Cr ) the
rhenium concentration in the reactor, mg L-1; rRe ) the
rate of rhenium dissolution, mg L-1 min-1; Vr ) the
active volume of the reactor (the part that is not covered
by the catalyst extrudes), mL.
For first-order kinetics:
rRe ) -kCr (20)
where k ) a kinetic constant, min-1.
Because (dVr/Q) ) dt (t is the time of reaction in
minutes), eq 19 becomes:
(dCr/dt) ) -kCr (21)
 Ind. Eng. Chem. Res., Vol. 38, No. 5, 1999 1835

Figure 9. The Co value as a function of volumetric flow.

Figure 8. Rhenium concentration at the outlet of the packed bed The rhenium recovery yield for the packed bed
as a function of time for various volumetric flows. experiments, based on the experimental results, was
calculated as follows:
Table 1. Rhenium Recovery Yield (R%), the
Constant Co, the Kinetic Constant (k), and the R2 Values R% ) (mo- mr)*100/mo (24)
of the Simulation Procedure for Various Values of
Volumetric Flow (Space Velocity)
where R% is the recovery yield, mo is the initial mass
volumetric space velocity,a Co,
flow, mL s-1 s-1 mg L-1 k, min-1 R2 R, % of rhenium in the packed bed (mg), and mr is the
recovered mass of rhenium at the end of each experi-
0.30 0.07 42.5 0.085 0.994 75.6
mental run. mo was measured by analysis of the catalyst
0.81 0.20 24.5 0.095 0.992 82.8
1.49 0.35 9.8 0.068 0.967 76.5 extrudes before treatment. mr was calculated from the
1.67 0.39 8.3 0.077 0.991 77.4 experimental results taking into account the removal
a Space velocity is calculated by the ratio Q/V where Q is the
of a significant quantity of rhenium by the sampling
v
volumetric flow and Vv is the void fraction of the catalyst bed.
procedure as follows:

After integration for the limiting conditions, t ) 0, Cr mr ) VfCf + Σ(Cnv) (25)

) Co, where Co is the outlet concentration after the first
pass of the solution through the reactor when the time
measurement begins during the experiments. The rhe-
nium concentration at the outlet at any time t is given
by:
C ) Co exp(-kt)
The experimental results are shown in Figure 8,
where the outlet concentration of rhenium is plotted as
a function of time for various volumetric flows of the
leaching solution. The fitting of eq 22 on the experi-
mental data was tested statistically, and the respective
constants were calculated through the linear transfor-
mation of eq 22:
where Vf is the total volume collected at the end of each
experimental run (L), Cf is the rhenium concentration
in this volume (mg L-1), Cn is rhenium concentration
in every sample (mg L-1), and v is the volume of each
retrieved sample (L). The calculated recovery yields are
shown in Table 1.
(22)
The rhenium recovery yield may be also calculated
by eq 24 through the calculation of mr by integration of
eq 22 for the limiting conditions t ) 0 and t:
t
mr ) QCo ∫t)0 {exp(-kt)} dt )
QCo(1/k)[1 - exp(-kt)] (26)
Because Co ) A + BQ, eq 26 becomes:

LNC ) (LNCo) - kt (23) mr ) Q(A + BQ)(1/k)[1 - exp(-kt)] (27)

The results are shown in Table 1. The fitting proce-
dure was satisfactory and the reaction rate seems to
follow first-order kinetics concerning the rhenium con-
centration. The kinetic constant seems to be indepen-
dent of volumetric flow (mean value ) 0.081, n ) 4; SD
) 0.011), whereas Co is a linear function of volumetric
flow as shown in Figure 9 (Co ) A + BQ, A ) 47.8; B )
-24.9; and RSQ ) 0.973). The result above confirms
the conclusion that the Knudsen’s diffusion through the
pores of the catalyst or the dissolution reaction is the
rate-controlling step.
and the recovery yield can be calculated for any value
of the volumetric flow. The recovery yield as a function
of volumetric flow for t ) 50 min is shown in Figure 10.
The maximum recovery yield (95%) is achieved at
volumetric flow 0.96 mL s-1 (space velocity, 0.242 s-1).
As shown in Figure 10 the behavior of recovery yield
changes presents two separate regions. At low values
of volumetric flow the recovery yield increases and at
high values increases. It possible that at the first region
the dissolution reaction is under external diffusion
control, whereas in the second one is under pore
1836 Ind. Eng. Chem. Res., Vol. 38, No. 5, 1999
Figure 10. The calculated recovery yield as a function of
volumetric flow. Dotted line represents the optimum conditions
and separates the regions of external and pore diffusion.
diffusion control. The experimental results are in agree-
ment with the second region as shown in Figure 8.
5. Conclusion
The laboratory experiments carried out in batch and
packed column reactors show that rhenium may be
recovered satisfactorily from spent reforming catalysts
by dissolution with a slight alkali leaching solution
(NaHCO3). Recovery yields up to 97% were achieved for
crushed catalyst samples. The application of the above-
mentioned rhenium recovery procedure may simplify
considerably the conventional applied procedure, be-
cause of the substitution of the expensive and compli-
cated separation of rhenium from the product of the
complete dissolution of the catalyst mass by a rather
simple and inexpensive process (Figures 1 and 2). The
dissolution reaction seems to follow first-order kinetics,
and the rate-controlling step seems to be Knudsen’s
diffusion through the catalyst’s pores or the dissolution
reaction. Analysis of the produced liquids showed that
they contain only rhenium, because no copper or iron
was detected in measurable amounts. The above-
mentioned kinetic analysis refers to the specific catalyst
and the obtained results must be applied only qualita-
tively for other type of catalysts, because the catalyst
composition, the working conditions and the decoking
procedure may cause significant differences.
Acknowledgment
The authors thank the administration of the EKO
refinery (Thessaloniki, Greece) for the provision of the
reforming catalyst samples.
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Received for review September 30, 1998
Revised manuscript received December 29, 1998
Accepted February 5, 1999
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