Characterization of CrAPO-5 materials in test reactions of conversion of 2-methyl-3-butyn-2-ol and isopropanol

Article abstract of DOI:10.1006/jcat.2002.3611

CrAPO-5 materials with various amounts of Cr(III) stably incorporated into the framework positions were tested in the reactions of conversion of 2-methyl-3-butyn-2-ol (MBOH) and isopropanol. The results were compared with those obtained over similar materials containing extraframework chromium species and over nonsubstituted AlPO₄-5. The products of the reactions indicated an increased acidity of catalytic sites in CrAPO-5 compared to that in AlPO₄-5. The yield of conversion depends mainly on the amount of chromium and its distribution. The multivalent extraframework Cr species yielded similar catalytic effects as framework Cr centers. However, their activity dropped very quickly due both to the hindrances to alcohol molecules in accessing the catalytic sites in the pores clogged by these species and to the faster coking.

Full text of DOI:10.1006/jcat.2002.3611

Journal of Catalysis 208, 270–275 (2002)
doi:10.1006/jcat.2002.3611
Characterization of CrAPO-5 Materials in Test Reactions of Conversion
of 2-Methyl-3-butyn-2-ol and Isopropanol
∗
,
∗, ,1
Gabriela Zadrozna, † Emmanuelle Souvage,‡ and Jan Kornatowski §
∗
Institute of Chemical Technology II, University of Technology, 85747 Munich, Germany; †Institute of Organic Chemistry and Technology,
Cracow University of Technology, 31-155 Krakow, Poland; ‡Institut f u¨ r Brennstoffchemie, Rheinisch–Westf a¨ lische Technische
Hochschule, 52074 Aachen, Germany; and §Faculty of Chemistry, N. Copernicus Universtity, 87-100 Torun, Poland
Received June 26, 2001; revised March 18, 2002; accepted March 18, 2002
framework of AlPO4-5 has appeared to be possible under
CrAPO-5 materials with various amounts of Cr(III) stably significantly modified conditions of synthesis (16–20) and
incorporated into the framework positions were tested in the can be best achieved with use of cotemplates (18–20). These
reactions of conversion of 2-methyl-3-butyn-2-ol (MBOH) and iso-
propanol. The results were compared with those obtained over simi-
lar materials containing extraframework chromium species and
materials have extensively been characterized. The struc-
ture has been determined from X-ray diffraction patterns
(
XRD) (16, 19), crystal dimensions and morphology from
over nonsubstituted AlPO
cated an increased acidity of catalytic sites in CrAPO-5 compared
to that in AlPO -5. The yield of conversion depends mainly on
4
-5. The products of the reactions indi-
scanning electron microscopy (SEM) (16, 19, 20), and sorp-
tion properties and accessibility to the pores from adsorp-
tion measurements for nitrogen, water, and benzene (16, 17,
4
the amount of chromium and its distribution. The multivalent ex-
traframework Cr species yielded similar catalytic effects as frame-
work Cr centers. However, their activity dropped very quickly due
19), aswellasfromfluorescenceinvestigations(19), amount
of Cr from chemical analysis (ICP) (16–20), state and stabil-
both to the hindrances to alcohol molecules in accessing the cata- ity of chromium in the crystals from electron paramagnetic
lytic sites in the pores clogged by these species and to the faster resonance (EPR) (18), UV–vis spectroscopy (16, 19),
2
7
31
coking.
ꢀc 2002 Elsevier Science (USA)
nuclear magnetic resonance ( Al and P MAS NMR)
Key Words: CrAPO-5; isomorphous substitution of Cr; conver- (19), thermogravimetric analyses (TG, DTG, DSC) (19),
sion of methylbutynol; conversion of isopropanol; activity of frame-
work Cr.
ion exchange tests (19), and leaching tests (19). All these
techniques have indicated a stable incorporation of the
3
+
3+
Cr ions into framework positions for Al . Chromium is
fourfold bonded to the framework atoms and its coordina-
tion is complemented by two additional ligands (water after
calcination) to the distorted octahedral one (19). Given this
wide variety of methods, the catalytic tests are the necessary
complement for fuller characterization of the CrAPO-5
materials.
Two catalytic reactions were employed to test the behav-
ior of the synthesized CrAPO-5 materials and to obtain in-
formation about the nature of the catalytic centers (21–25).
The test Reaction 1, conversion of 2-methyl-3-butyn-2-ol
INTRODUCTION
Catalytic properties of chromium, especially in the redox
reactions, evoked high interest in the molecular sieves con-
taining Cr. These materials were expected to reveal favor-
able catalytic properties (1) in relation to oxides or homo-
geneous catalysts in the form of solutions, due to creation
of separated and well-distributed catalytic centers. Addi-
tionally, such heterogeneous crystalline solids might offer
easier managing in the catalytic processes.
(
MBOH), was applied to determine the acid–base
properties/character of the examined materials.
Substitution of Cr into aluminophosphate molecular
sieves of AlPO4-5 (AFI structure type) has long been tried
Conversion of MBOH, the simplest tertiary alkynol, pro-
ceeds, depending on the character of catalysts, as shown
in Scheme 1. The conversion over acidic catalysts such
as ZSM-5 or silica–alumina leads to dehydration, yielding
-methyl-3-buten-1-yne (MBYNE) with almost 100% se-
lectivity (21–24). In parallel, small quantities of 3-methyl-
-buten-1-al (PRENAL) can be obtained (23, 24). The de-
(
2–15). Catalytic activity of Cr-containing AlPO4-5 mate-
rials has been reported in numerous papers (e.g., 6–10).
However, all these contributions have either given no evi-
dence for framework incorporation of Cr or concluded that
chromium was not located in framework positions (e.g., 10–
3
1
2). A stable incorporation of higher amounts of Cr into the
2
hydration activity is then related to the surface acidity. The
conversion over solid basic catalysts like magnesium oxide,
zinc oxide, or alkali-exchanged X zeolites results only in
1
To whom correspondence should be addressed. Fax: +49-89-289 13
5
44. E-mail: jan.kornatowski@ch.tum.de.
270
0
ꢀ
021-9517/02 $35.00
c 2002 Elsevier Science (USA)
All rights reserved.

CATALYTIC ACTIVITY OF CrAPO-5
271
MBYNE
HMB
PRENAL
als and their Cr centers. It was especially interesting due to
the unusual state of Cr with four framework bonds and two
additional ligands, which is unusual for zeolite-like mate-
rials. Catalytic behavior and properties of active sites of
CrAPO-5 have been characterized in relation to the mate-
rials with extraframework Cr species and to nonsubstituted
acidic
H
+
O
MIPK
O
O
amphoteric
basic
H
4
AlPO -5.
+
+
HO
HO
MBOH
EXPERIMENTAL
O
The CrAPO-5 samples were synthesized as described
elsewhere (16–19). The as-prepared crystalline products
were calcined at 773 K under air for at least 48 h. The
materials were characterized by numerous techniques (cf.
SCHEME 1
acetone and acetylene (22, 23). Over amphoteric cata- Introduction). For details, see Refs. (16–20).
lysts, MBOH yields essentially 3-methyl-3-butene-2-one
Test Reactions
(
MIPK), which can be accompanied by acetone and acety-
lene at clearly lower selectivities (22). The latter products
are formed following the basic mechanism. Over ampho-
teric ZrO2, 3-hydroxy-3-methyl-2-butanone (HMB) can be
formed with 76% selectivity.
The test Reaction 2 (Scheme 2), conversion of isopro-
panol (propanol-2), was chosen to confirm the character of
catalytic sites in CrAPO-5. The conversion is possible over
all acidic sites of any strength and results in dehydration
to propene, which is the main product of the reaction (22,
A fixed-bed reactor was used as the standard method.
All catalysts (500 mg) were first activated at 473 K under a
nitrogen flow (2.6 L/h) for 2 h. Next, the temperature was
increased to 623 or 553 K for the conversion of MBOH or
isopropanol, respectively. Then, the reactant stream, pre-
heated in a saturator system, was admitted into the reactor
under the N2 flow (2 and 4 L/h for Reactions 1 and 2, re-
spectively). The effluents were analyzed online with a gas
chromatograph after an initial 10 min (0 h in each Table)
and then every hour. The same reactions were performed
over nonsubstituted AlPO4-5.
2
5). A small amount of diisopropylether (DIPE) can also
be formed as by-product via intermolecular dehydration of
propanol-2 (22, 25). Over basic centers, dehydrogenation
of isopropanol to acetone occurs (22). However, basicity of
a catalyst can only be revealed when a small amount of a
redox component is present (22). With no redox properties,
RESULTS AND DISCUSSION
The CrAPO-5 crystals were of the form of hexagonal
formation of acetone occurs only at a higher temperature, prisms typical of the AFI structure type. Their dimensions
above 573 K (26).
as well as the content of Cr are given in Table 1. The struc-
in the framework of ture after calcination (XRD) remained unchanged (16–20).
Substitution of Cr3 for Al
+
3+
AlPO4-5 does not induce an additional framework charge
The CrAPO-5 materials used in the test reactions
and ion-exchange ability (19). The only result is a com- (Table 1) are divided into two groups: (i) samples 1–4,
positional heterogeneity which can influence sorption which show high sorption (HS) capacities for nitrogen and
properties of the materials (17). This indicates that the
Cr heteroatoms create sorption centers able to interact
with molecules adsorbed in the pores. In this light, it was
interesting to examine the CrAPO-5 materials in catalytic
reactions in order to check the activity and/or character
of the chromium centers and to compare the results with
those published previously (6–10) for the materials with
undefined states of Cr. The aim of the study was to broaden
the qualitative characteristics of the new CrAPO-5 materi-
TABLE 1
Characteristics of the Examined CrAPO-5 and Reference
4
AlPO -5 Materials
Volume of
Dimensions of
crystals
(l × d) (µm)
Sample
no.
adsorbed
nitrogen (cm /g)
Cr content
(mmol/g)
3
a
u.c./Cr
1
2
3
4
69.0
76.0
76.0
94.0
0.321
0.157
0.135
0.065
2
3.5
4
10–20 × 40–50
10–50 × 10–50
5–50 × 5–60
+
+
H2O (Dehydration)
H+
10
50–70 × 50–70;
1
0–20 × 50–60
OH
5
6
15.0
7.0
67.0
0.109
0.046
—
5.5
14
—
200–400 × 50–60
400 × 30–50
H2 (Dehydrogenation)
O
OH-
AlPO4-5
150–200 × 30–40
a
SCHEME 2
l, Length; d, width of the crystals.

2
72
ZADROZNA, SOUVAGE, AND KORNATOWSKI
TABLE 2
Conversion of MBOH over CrAPO-5 Samples 1–4 (Table 1)
Selectivity (%)
Conversion (%)
MBYNE
Acetylene
Acetone
Time
(h)
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
0
1
2
3
4
5
6
7
8
47.75
27.61
19.86
16.09
15.20
14.29
33.80
19.68
17.74
20.18
22.23
25.28
10.14
10.92
13.29
13.97
15.63
16.26
16.89
16.94
29.15
7.57
53.43
33.94
26.76
21.84
13.62
6.08
47.54
23.05
11.69
6.87
55.73
23.60
11.03
5.99
0
0
0
0
0
71.06
43.43
15.87
6.62
3.06
0
0
0
0
16.82
24.07
26.72
28.59
30.28
34.33
14.64
21.27
25.47
26.46
27.04
16.25
28.33
32.99
34.68
36.64
36.76
36.78
36.87
36.66
10.14
20.64
30.58
33.99
35.32
36.59
36.43
36.51
36.40
29.72
42.00
46.52
49.57
56.09
59.59
37.82
55.68
62.83
66.67
68.49
28.02
48.06
55.97
59.31
63.30
63.24
63.22
63.13
63.34
18.77
35.93
53.56
59.39
61.62
63.41
63.57
63.49
63.60
12.38
20.30
25.30
29.95
32.29
33.27
30.73
4.47
benzene (16–19), and (ii) samples 5–6, which reveal very water ligands, which is reflected in the reversible change of
low sorption (LS) capacities. The crystals of well-sorbing color (19). For this reason, the experiments were carried
samples are shorter (c-axis, direction of the channels) and out at 623 K. For both groups of the CrAPO-5 materi-
exhibit higher contents of Cr. The HS materials contain pre- als and for AlPO4-5, three compounds were found among
dominantly the Cr3 ions stably incorporated into frame- the products of the MBOH conversion, 3-methyl-3-buten-
work positions (16–19). These ions cannot undergo redox 1-yne (MBYNE), acetylene, and acetone, but no PRENAL
reactions and their pseudotetrahedral coordination sphere (Table 2–4). The conversion for both groups of CrAPO-5
in the framework is complemented by two additional wa- was always higher at the beginning of the process; then it
ter ligands (in the calcined state), located in the pores, to decreased significantly after 1 h and was maintained at the
the favored (pseudo) octahedral one. In the LS materials, same level or slightly increased for the next several hours.
chromium occurs mainly as multivalent extraframework AlPO4-5 showed a very rapid decrease in the conversion
species which cause strong clogging of the pores (16–19). (Table 4). This decline of the yield over all the CrAPO-5
In spite of these differences, the catalytic properties of all materials was accompanied by a decrease in selectivity
the CrAPO-5 materials are similar to a high extent (see to MBYNE with a simultaneous increase in selectivity to
Tables 2–4 and 5–7 for conversion of MBOH and iso- acetylene and acetone. For AlPO4-5, all these values re-
propanol, respectively). These surprising observations are mained constant.
+
in agreement with the EPR investigations (18), which also
did not reveal significant differences between the HS and follows the Cr content of the catalysts except sample 4. This
LS materials. sample shows the initial conversion between those of cata-
As seen in Table 2, the yield of the MBOH conversion
The conversion of MBOH proceeds with a very low yield lysts 2 and 3 in spite of a more than two times lower content
of several percent at temperatures below 553 K. The yield of Cr. Moreover, the conversion over sample 1 decreases
starts to increase above 573 K when Cr loses its two with reaction time to values similar to those for sample 5
(
3
see Table 3), while the conversions over samples 2 and
pass a minimum and likely tend to stabilize at higher
TABLE 3
values. The conversion over sample 4, after passing the
minimum, seems to stabilize at values higher even than
the initial one. These observations confirm the activity of
Conversion of MBOH over CrAPO-5 Samples 5 and 6 (Table 1)
Selectivity (%)
Conversion
(%)
MBYNE
Acetylene
Acetone
Time
TABLE 4
(
h)
5
6
5
6
5
6
5
6
4
Conversion of MBOH over AlPO -5 (Table 1)
0
1
2
3
4
5
6
54.74 24.44 61.70 67.68 13.99 12.23 24.30 20.07
Selectivity (%)
Acetylene
26.30
17.70
14.41
8.76 42.97 48.23 21.04 18.93 35.99 32.84
7.28 34.91 30.58 24.10 25.67 40.99 43.75
8.36 27.55 17.21 26.66 30.27 45.80 52.51
Time
Conversion
(%)
(
h)
MBYNE
Acetone
13.70 10.96 21.46
14.32 14.64 16.69
15.39 18.41 12.73
9.53 29.03 33.34 49.51 57.13
5.59 30.84 34.70 52.47 59.72
0
1
2
64.40
26.09
4.57
98.30
98.52
100.00
0.46
0.23
0
1.24
1.26
0
0
32.14 36.55 55.14 63.45

CATALYTIC ACTIVITY OF CrAPO-5
273
the Cr centers in the conversion process but suggest si- ters located at external surface of the crystals can more
multaneously a significant role of another, likely space/ easily leave the reaction zone and a consecutive cracking
steric, factor(s). From this point of view, the changes of reaction is less probable than in the channels. Whatever
the conversion correspond especially well to the values of the case is, as long as the active sites are not covered with
sorption capacities (Table 1), which illustrate the possibility coke deposits (primarily formed on acidic centers (23)), one
of diffusion of sorbate molecules into the channels.
can observe more MBYNE among the products. However,
The highest selectivity to MBYNE is shown by catalyst from the presented changes in the yield and selectivity of
of the lowest content of Cr, while the other three cata- particular products, it is not possible to estimate what part
4
lysts reveal similar selectivities. However, the selectivities of MBYNE was formed inside the CrAPO-5 channels or
decrease rapidly with time, except for catalyst 1, for which on the external surface and what part was cracked.
the drop is much slower. Selectivities to acetylene and ace-
Samples 5 and 6 showed a similar behavior (Table 3) al-
tone are significantly different for the particular catalysts at though the selectivity to MBYNE did not fall so rapidly.
the beginning of the process. They increase with time and, The results suggest either that these catalysts contain more
surprisingly, tend to equalize for all samples.
acidic centers (23, 24) taking part in the formation of
Such differences in the catalytic behavior of the materi- MBYNE or that there are other acidic centers which un-
als may be explained as follows. Active sites in CrAPO-5 dergo coking to a lower extent. These are likely the mul-
are sorption centers which slow diffusion of reactants into tivalent extraframework Cr species (16–19). As they clog
the channels (17). Thus, the conversion is somewhat lower the channels, the reaction has to run primarily in the limited
than that over AlPO4-5. However, active sites of AlPO4-5 space of a surface layer of the crystals and, consequently, on
(
structure defects) lose their activity extremely quickly, a lower number of active sites. Thus, the sites should have a
likely as a result of coking. Activity of Cr centers is more higher acidity. The increase in selectivity to acetylene and
stable and is maintained for a longer period. High and al- acetone over samples 5 and 6 is comparable to that over
most constant selectivity values of MBYNE over AlPO4-5 samples 1–4, which suggests that both products are formed
prove that this is the only product of the reaction proceed- over the HS and LS materials in a similar way. All these ob-
ing in this system. For the CrAPO-5 materials, selectivity to servations strongly support the conclusion that acetylene
MBYNE drops with reaction time. However, this decrease and acetone are most probably formed via decomposition
has to be considered as an apparent effect because the high of MBYNE in a consecutive cracking reaction over acidic
temperature of the process favors cracking reactions. The sites.
parallel decrease in selectivity to MBYNE and increase in
From the point of view of incorporation of Cr, the
selectivity to acetylene and acetone suggests that the main changes of conversions and selectivities for the particu-
product, MBYNE, may undergo a consecutive cracking re- lar samples suggest that sample 4 of the lowest content
action resulting in these two light molecules. A higher yield of Cr reveals the most perfect incorporation of Cr and,
of acetone suggests that a part of acetylene is consumed consequently, the most perfect structure of the pores, and
in a polymerization process which might be responsible for the highest possibility for diffusion. As opposed to that,
the observed coking. Such processes are not possible over sample 1 with the highest content of Cr contains probably a
AlPO4-5 due to its too-weak acidity.
small fraction of extraframework Cr and, therefore, it gives
The observed differences between the examined effects more similar to those in samples 5 and 6 than in the
CrAPO-5 samples also suggest an important role of Cr dis- other HS materials.
tribution, which causes variations in accessibility of the Cr
The yield of the isopropanol conversion (Tables 5 and 6)
centers to the reactants. The products formed on the cen- varies between 50 and 98% and propene is almost the only
TABLE 5
Conversion of Propanol-2 over CrAPO-5 Samples 1–4 (Table 1)
Selectivity (%)
Conversion (%)
Propene
DIPE
Acetone
Time
(h)
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
0
1
2
3
4
5
6
92.13
91.81
92.32
92.27
92.74
64.61
60.50
70.31
72.01
78.18
50.20
55.22
56.09
57.31
58.15
58.84
59.14
94.00
99.24
98.40
98.50
98.48
98.67
98.28
97.97
97.88
97.84
97.81
95.83
97.56
97.56
97.56
97.54
97.60
97.59
98.00
0
1.20
1.49
1.48
1.52
1.48
1.96
1.92
1.93
1.93
1.94
1.93
1.93
1.51
0.76
0.66
0.56
0.54
0.39
0.53
0.54
0.64
0.64
0.71
0.66
0.52
0.50
0.51
0.52
0.47
0.49
0.49
0.94
0.94
0.98
0.94
98.00
98.00
1.48
0.52

2
74
ZADROZNA, SOUVAGE, AND KORNATOWSKI
TABLE 6
best accessibility to active sites, while the differences be-
tween particular samples reflect likely varying distribution
of the sites. Lower conversions over the LS samples confirm
a limited accessibility to active sites (clogged pores). The
rapid decrease in the yield of the conversion over AlPO4-5
is caused by coking.
Conversion of Propanol-2 over CrAPO-5 Samples 5 and 6 (Table 1)
Selectivity (%)
Conversion
(
%)
Propene
DIPE
Acetone
Time
(h)
5
6
5
6
5
6
5
6
CONCLUSIONS
0
1
2
3
4
5
6
73.88
78.70
79.72
80.68
81.10
81.77
82.06
56.57
86.35
87.07
87.42
87.95
88.30
88.52
97.01
97.74
97.82
97.76
97.43
97.81
97.94
96.26
97.32
97.36
97.47
97.38
97.38
97.49
2.06
1.73
1.71
1.70
1.71
1.67
1.66
2.74
2.01
1.99
0.93
0.53
0.47
1.00
0.67
0.65
The Cr(III) ions incorporated as heterocenters into an
1.97 0.54 0.56 AFI-type structure reveal, in spite of the lack of an addi-
1.98
1.98
1.98
0.51
0.51
0.40
0.64
0.64
0.53
tional framework charge, increased acidity in comparison
to the framework of AlPO4-5 with structure defects. This
is likely due to two additional water ligands at Cr, which
are located in the pores and complement the coordina-
tion sphere of chromium to the favored (pseudo)octahedral
one. The conversion of 2-methyl-3-butyn-2-ol (MBOH) re-
quires a temperature above 573 K, at which there proceeds
the consecutive reaction of cracking of the main product,
product. Correlation between the yield of conversion and
Cr content of the catalyst is similar to that in the case of
MBOH, i.e., the conversion increases with the Cr content
except for sample 4 with the lowest amount of Cr. The
differences in relation to MBOH are that (i) the yield does
not decrease with time but slightly increases in the initial
period and then stabilizes at a constant level and (ii) the dif-
ferences in the conversion due to the content of Cr are much
higher. The selectivities to propene are stable or vary within
a narrow range between 95 and 99%. Acetone and diiso-
propylether (DIPE) form in amounts below 1% (Table 6),
indicating a marginal role of basic centers in this reaction.
The conversion of isopropanol over AlPO4-5 (Table 7) is
similarly high at the beginning, but it drops considerably
with reaction time, while selectivity to propene stabilizes
at 100%.
3
-methyl-3-buten-1-yne (MBYNE), to acetylene and ace-
tone on the acidic sites of CrAPO-5. The conversion of
isopropanol can proceed at a lower temperature (553 K)
and does not give such an effect, yielding almost exclusively
propene as the product. The yield of the conversion follows,
in general, the content of chromium in CrAPO-5, but it is
dependent also on the distribution of the Cr centers.
The materials with extraframework chromium (multiva-
lent Cr species clogging the pores) also reveal an acidity
higher than that of nonsubstituted AlPO4-5. The conver-
sion over these Cr species results in products and effects
similar to that over the framework Cr, but it is lowered
by (i) hindered accessibility inside the clogged pores and
All these results support the conclusions from the con-
version of MBOH and prove that all the CrAPO-5 samples
Table 1) should have acidic centers. The most important
(
ii) a faster coking. No basic centers are created in the in-
vestigated Cr-containing materials, as concluded from the
isopropanol conversion.
(
is that the conversion of isopropanol confirms the absence
of basic centers in CrAPO-5. Therefore, acetylene and ace-
tone originate, in fact, from cracking of MBYNE. As acidity
of all the catalysts is sufficient for this reaction, the differ-
ences in the conversion have to result from varying distri-
bution of or accessibility to active sites. Thus, the highest,
in average, conversion over the HS materials indicates the
ACKNOWLEDGMENTS
This work was partially supported by the Deutsche Forschungsgemein-
schaft (DFG). Thanks are due to Dr. J. Rakoczy (Cracow) for technical
assistance.
REFERENCES
1
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Organic Compounds.” Academic Press, New York, 1981.
TABLE 7
Conversion of Propanol-2 over AlPO
4
-5 (Table 1)
2. Flanigen, E. M., Lok, B. M. T., Patton, R. L., and Wilson, S. T., U.S.
Patent 4,759,919 (1988).
Selectivity (%)
DIPE
3. Xu, Y., Maddox, P. J., and Thomas, J. M., Polyhedron 8, 819 (1989).
4. Weckhuysen, B. M., and Schoonheydt, R. A., Zeolites 14, 360 (1994).
5. Weckhuysen, B. M., and Schoonheydt, R. A., Stud. Surf. Sci. Catal. 84,
Time
Conversion
(%)
(h)
Propene
Acetone
9
65 (1994).
0
1
2
3
4
8
97.79
94.33
89.01
85.00
77.00
49.00
98.30
98.52
100.00
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1.12
0.99
0
0
0
0.52
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0
0
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1