Applied Catalysis Ar General, 101 (1993) 199-206

Elsevier Science Publishers B.V., Amsterdam

199
APCAT A2545
Catalyst characterization by a probe reaction. Effect of
tin addition in PtSn/Al,O,*
Jorge SBnchez, Nerva Segovia, Alexander Moronta, Arnedo Arteaga,
Geomar Arteaga and Eduardo Choren
Centro de Superficies y Catcilisis (CESUC), Apartado 1.5251, Maracaibo 4003A (Venezuela)
(Received 7 January 1993, revised manuscript received 6 April 1993)
Abstract
Ethylene hydrogenation as a probe reaction was used to characterize PtSn/Al,03 catalysts. The ef-
fects of the amount of tin and the impregnation order of platinum and tin on the activity for ethylene
hydrogenation, the hydrogen number and the hydrogen uptake were studied. Two series of catalysts
were prepared by two different successive impregnations of aqueous solutions of platinum and tin com-
pounds. The platinum content was constant at 0.5 wt.-% and the tin content was varied over the range
0.0 to 0.45 wt.%. The presence of tin caused a decrease in both the ethylene hydrogenation activity and
the hydrogen number values in the two series of bimetallic catalysts. Hydrogen uptake decreased on the
Pt-Sn catalysts and increased on the Sn-Pt catalysts when the atomic Sn/Pt ratio was increased. As
shown in the literature, these results can be related to a chemical change of the platinum due to the
presence of tin either by forming Pt-Sn clusters or by interaction between platinum and tin ions on the
alumina surface.
Key words: alumina; bimetallic; hydrogenation; PtSn; probe reaction; titration
INTRODUCTION
Bimetallic Pt-X/Al,O, catalysts (X= Re, Ir, Sn, Pb or Ge) are commonly
used in naphta reforming [ 11. These catalysts have a higher stability and se-
lectivity on reforming reactions than monometallic Pt/Al,O, catalysts, prob-
ably due to the inhibition of coke-forming reactions [2,3]. The effects of the
second metal are very specific and depend on the nature of the metal, atomic
X/Pt ratio, preparation techniques, reaction and reaction conditions [ 21.
Several structural models have been postulated to explain the behaviour of
PtSn-supported catalysts. The formation of platinum ensembles of high activ-
ity and bimetallic Pt-Sn ensembles of low activity [3-71 has been proposed.
Burch [8] suggested the existence of an interaction between small platinum
Correspondence to: Dr. J. SBnchez, Centro de Superficies y Catglisis, CESUC, Apartado 15251,
Maracaibo 4003A, Venezuela.
*Paper presented at the XIII Iberoamerican Symposium, Segovia (Spain), 6-10 July 1992.
0926-860X/93/$06.00 0 1993 Elsevier Science Publishers B.V. All rights reserved.
200
J. Sknchez et al.jAppl. Catal. A lOl(l993) 199-206
partilcles and tin(I1) ions trapped on the alumina surface. Adkins and Davis
[ 91 proposed that tin is present as a fine film strongly interacting with alumina
form.ing a tin aluminate shell over which metallic platinum is supported.
Handy et al. [lo], using transmission electron microscopy (TEM) studies,
have suggested the formation of PtSn alloys in PtSn/A1203 catalysts with high
metal loadings, and when the metal loadings are low, tin may be stabilized in
an oxidic state on the alumina surface, in a similar way to the model proposed
by Adkins and Davis [ 91.
Choren et al. [ 11,121 have proposed and used ethylene hydrogenation as a
probe reaction to characterize Pt/Al,O, catalysts. They found that the turn-
over frequency for ethylene hydrogenation is constant when the hydrogen
number is used as the number of active sites. This hydrogen number was de-
fined as the number of active hydrogen (NAH) for Pt/Al,O, catalysts.
In this work ethylene hydrogenation is used as a probe reaction to charac-
terize PtSn/AlzO,, with 0.5 wt.-% platinum and up to 0.45 wt.-% tin (atomic
Sn/Ft ratio between 0 and 1.5).
EXPERIMENTAL
PtSn/Al,O, catalysts were prepared by incipient wetness impregnation of
y-alumina with aqueous solutions of H,PtCl, and SnCl, in 1 M HCl. Two series
of catalysts with an inverted impregnation order of the aqueous solutions of
platinum and tin compounds were prepared. In the Pt-Sn catalysts, platinum
was added first and then tin and in the Sn-Pt catalysts, tin was added first,
followed by platinum. The samples were dried at 390 K after each impregna-
tion. The platinum content was 0.5 wt.-% and the tin content varied from 0.0
to 0.45 wt.-% (atomic Sn/Pt ratios between 0 and 1.5).
Th.e apparatus, materials and procedures are described in previous works
[ 11,121. The catalyst sample was dried for 2 h at 390 K in argon, heated to 670
K (10 K/min) in argon and then treated in a hydrogen flow for 2 h at 670 K,
cooled to room temperature in hydrogen and swept with argon for 10 min. From
this point on, the successive ethylene-hydrogen titrations were carried out at
room temperature as indicated below.
Step 1
Hydrogen adsorbed on the catalyst was titrated with ethylene pulses until
the amount of ethane formed was negligible (E,, total amount of ethane pro-
duced in this step). The stoichiometric amount of hydrogen atoms titrated in
this step per total platinum atoms is called the hydrogen number (HN):
HN= B&/P&.
J. S&zchez et al./Appl. Catal. A I01 (1993) 199-206 201
Step 2
The adsorbed ethylene was titrated with pulses of hydrogen until the hydro-
gen peak area in successive chromatograms was constant. The HC (E) value is
given by the difference between the amount of hydrogen consumed, HT, and
the amount of ethane formed in the titration, E,; that is, HC( E) = HT- E,.
The amount of hydrogen chemisorbed directly, HC, was measured on a clean
catalyst by the hydrogen pulse method. The initial rates of ethylene hydrogen-
ation were measured at 273 K and atmospheric pressure in a flow of hydrogen
(30% vol.) and etlhylene (7% vol. ) with argon as diluent [ 11,121.
RESULTS AND DISCUSSION
Table 1 shows the composition of the catalysts, the values of HN and HC(E)
calculated from tbe results of the succesive ethylene-hydrogen titrations. The
last column of Table 1 corresponds to the hydrogen uptakes (HC) on clean
catalysts. Figs. 1-3, respectively, show the dependence of the H/Pt ratio, HN
and the initial activity for ethylene hydrogenation with respect to the content
of tin. The H/Pt ratio was calculated from the hydrogen uptake on clean cat-
alysts (HC).
TABLE 1
Ethylene and hydrogen titrations. Amount of catalyst sample, 250 mg
Catalyst
(wt.--%)
Era
HTb
EZC
HN HC(E) HC
(wml) (wol) (wol) (,umol 1 0-d 1
Pt-SnfAl,O,
0.5 Pt
0.5 Pt-0.075 Sn
0.5 Pt-0.15 Sn
0.5 Pt-0.30 Sn
0.5 Pt-0.45 Sn
3.24 4.00 1.56 1.03 2.44 2.73
2.90 2.46 1.57 0.93 0.89 2.09
2.62 2.06 0.89 0.83 1.17 2.37
2.07 1.26 0.61 0.66 0.65 2.14
1.82 0.83 0.55 0.59 0.28 1.89
Sn-Pt/Al,O,
0.5 Pt 3.24 4.00 1.56 1.03 2.44 2.73
0.5 Ptt0.075 Sn 2.57 3.62 1.40 0.82 2.22 2.60
0.5 Pt-0.15 Sn 2.34 2.17 0.84 0.74 1.33 3.23
0.5 Pt-0.30 Sn 1.96 2.97 1.34 0.62 1.63 3.70
0.5 PttO-45\Sn 1.67 2.88 1.35 0.53 1.53 3.85
aE,: Amount of ethane formed in the titration by ethylene of adsorbed H, at room temperature,
after catalyst treatment with hydrogen at high temperature.
bAmount of H, consumed in the titration by hydrogen of ethylene adsorbed.
Amount of ethane formed in the titration by hydrogen of ethylene adsorbed after titration with
hydrogen.
202 J . Sinchez et al./Appl. Catal. A 101 (1993) 199-206
H/P1
0
0.50 I .oo
Atomic ratio SdPt
1.50
Fig. 1. Chemisorption of hydrogen on (0 ) Pt-Sn/Al,O, and ( l ) Sn-Pt/Al,O, catalysts.
Atomic ratio Sn/Pt
Fig. 2. Hydrogen number of (0 ) Pt-Sn/Al,O, and (0 ) Sn-Pt/Al,O catalysts.
Table 1 and Fig. 2 show a decrease in the values of HN with tin addition for
both the Pt-Sn and Sn-Pt series of catalysts. Fig. 3 shows that in both series
of Pt-Sn catalysts, the initial rate for ethylene hydrogenation decreased when
J. Srinchez et al./Appl. Catal. A 101 (1993) 199-206
203
Atomic ratio Sn/Pt
Fig. 3. Initial activity of ethylene hydrogenation at atmospheric pressure and 273 K on (0 ) Pt-
Sri/AI,,,, and (0) Sn-Pt/Al,O, catalysts.
tin was added. It was also observed that deactivation of the monometallic plat-
inum catalyst was more pronounced than for the bimetallic PtSn catalysts.
Choren et al. [ 11.1 showed that on Pt/A1203 the catalytic activity for ethyl-
ene hydrogenation is proportional to HN values and not to the H/Pt ratio
calculated from hydrogen chemisorption. That is, a decrease in the HN values
must correspond to a decrease in the activity for ethylene hydrogenation, as
shown in Fig. 3.
Palazov et al. [ 131 observed that hydrogenation activities for ethylene, l-
hexene and benzene decreased with tin addition in PtSn/A120s. This inhibi-
tion is most pronounced for benzene hydrogenation. Baronetti et al. [7] ob-
tained a higher activity for cyclohexane dehydrogenation and cyclopentane
hydrogenolysis in the Pt/A120Z than for PtSn/A120s. These results are in
agreement with the decrease of HN values and activity for ethylene hydrogen-
ation when tin is added, as observed herein.
Table 1 shows the values of HC and HC(E) for both series of catalysts. The
values of HC and HC(E) are approximately equal in the Pt/A1203 catalyst,
but when tin is added the values of HC are higher than those of HC (E) . Choren
et al. [ 111 found tbat both Hes have similar values for Pt/Al,O,, and they
recommended the use of HC(E) = HT- E, as the measure of the amount of
hydrogen chemisorbed on these catalysts.
HC( E) values decreased with tin content, being higher in the tin-platinum
catalysts. The step in which HC( E) is determined involves the titration with
hydrogen of adsorbed ethylene. This suggests that part of the ethylene ad-
204
J . Scinchez et al./Appl. Catal. A 101 (1993) 199-206
sorbed in the hydrogen titration is inactive and blocks a fraction of the plati-
num atoms exposed.
As shown in Fig. 1, in the Pt-Sn catalysts the H/Pt ratio diminished with
the addition of tin; in contrast, the H/Pt ratio increased with the tin content
in the Sn-Pt catalysts. Contrasting results in the variation of hydrogen uptake
with respect to the amount of tin added are reported in the literature. Vijlter
et al. [ 21, Palazov et al. [ 131, and Lieske and Vijlter [ 141, for example, found
that tin decreased the amount of hydrogen chemisorbed on PtSn/AIZOB; on the
other hand, Burch [ 81 and Muller et al. [ 151 observed an increase in hydrogen
uptake with increasing amounts of tin, while Balakrishnan and Schwank [ 161
found an initial increase in hydrogen uptake upon addition of small amounts
of tin (Sn/Pt < 0.5)) and then that the amount of hydrogen chemisorbed tended
to drop off with further additions of tin.
Burch [ 81 and Balakrishnan and Schwank [ 161 attributed this increased
hydrogen uptake to an increase of platinum dispersion, because tin did not
allow small platinum particles to sinter. Muller et al. [ 151 proposed that with
tin addition hydrogen migrates by spillover onto the tin(I1) sites. This addi-
tional hydrogen adsorbed on the Sn-Pt catalysts is not active for ethylene
hydrogenation, because both HN and activity for ethylene hydrogenation de-
crease with the addition of tin. Therefore, the additional hydrogen is probably
located on different sites from the platinum sites.
The order of the metal impregnations plays an important role in the behav-
iour of bimetallic catalysts. Baronetti et al. [6] found that a red
(PtCl, ( SnC13)2) -- complex is formed during the impregnation step when
platinum is deposited first, followed by tin. In the preparation of the Pt-Sn
catalysts, it was observed that the solution turned red during the impregnation
of the dried Pt/Al,O, precursor with an aqueous solution of SnCl,. This indi-
cated the formation of the Pt-Sn complex that subsequently led to the for-
mation of the bimetallic PtSn clusters or alloys [6]. As stated in the literature,
there is a strong interaction (geometric or electronic) between platinum and
tin [ 2,7] and these clusters or alloys have low activity [ 71. This could be the
reason for the diminution of the activity and HN values when tin is added after
platinum.
In the preparation of Sn-Pt catalysts, the red color was not observed during
the impregnation step, suggesting that most of the platinum atoms did not
form PtSn clusters or alloys, perhaps due to previous air oxidation of Sn2+ to
Sn4+ . Two models have been proposed to describe the structure of the Sn-Pt/
A1203 catalysts. In one, Adkins and Davis [ 91 suggested that tin is present as
an eggshell of tin aluminate surrounding the alumina support with the Pt
supported on the tin aluminate. In the other, Burch [8], Balakrishnan and
Schwank [ 161 and Burch and Garla [ 171 proposed that a very small amount
of tin can be incorporated into the platinum as a solid solution or alloy.
In both cases, the decrease of HN and the initial activity for ethylene hydro-
J. Sdnchez et al./Appl. Catal. A 101 (1993) 199-206
205
genation resulted mainly through an electronic interaction between platinum
and tin. Several authors have found that most of tin is present as tin (II) on
the alumina surface [14-161. The additional hydrogen uptake on the Sn-Pt
catalysts is due to hydrogen spillover resulting in hydrogen atoms being local-
ized on part of the tin (II) sites [ 151.
These results show that the bimetallic PtSn/Alz03 catalysts behave differ-
ently with respect to the monometallic Pt/A1203 catalyst. As tin is inactive for
the adsorption of hydrogen [2,18], and ethylene is only adsorbed on surface
platinum atoms [ 181, this difference can be attributed to a chemical modifi-
cation of the platinum due to the presence of tin.
CONCLUSIONS
Ethylene hydrogenation as a probe reaction is a useful tool to characterize
PtSn/A1203. The hydrogen number and ethylene hydrogenation activity de-
creased with the addition of tin in both series of PtSn catalysts. The hydrogen
uptakes decreased with the addition of tin for the Pt-Sn catalysts and in-
creased for the Sn--Pt catalysts. This additional hydrogen uptake is not active
for ethylene hydrogenation, therefore this hydrogen cannot be associated with
an increase of platinum dispersion due to the presence of tin.
ACKNOWLEDGEMENTS
This work was supported by CONDES (Universidad de1 Zulia, Venezuela).
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