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Article history:
Received 25 June 2015
Received in revised form 21 October 2015
Accepted 31 October 2015
Available online 15 November 2015
Keywords:
Hydrocracking
Molecular sieves
FeW catalysts
Phenanthrene
Al-SBA-15
a b s t r a c t
Catalysts for heavy oil hydrocracking require an enhanced mesoporosity (higher pore diameters) and a
moderate acidic function (mild acidity) to treat the bulky molecules present in this kind of feedstock and
to yield middle distillates (MD). In this work, we have synthesized ve different kinds of mesoporous
silica based on SBA-15 by modifying some of the variables of their synthesis with the aim at enhancing
mesoporosity. NH4 F and 1,3,5-trimethylbenzene (TMB) were used to modify the mesostructured arrangement in SBA-15. TMB modied SBA-15 materials exhibited the highest textural properties (2.16 cm3 g1
and 17 nm) in comparison to NH4 F modied silica (1.90 cm3 g1 and 10.8 nm) and pristine SBA-15 silica
(1.03 cm3 g1 and 12 nm). The acidity of the SBA-15 based materials was modied by a post-synthesis
grafting procedure to Si/Al molar ratios of 10, 25, and 40. SBA-15 based materials modied with both
Al and TMB were used as supports for FeW suldes. These catalysts were tested in the hydrocracking
of phenanthrene. In general, all of the catalysts supported on Al-SBA-15 based materials were selective to the ring opening reaction of phenanthrene in contrast to the results obtained over a commercial
NiMo/-Al2 O3 catalyst. Such trend was associated to the presence of Brnsted acid sites on the surface
of the Al modied supports as shown 27 Al MAS NMR analysis.
2015 Elsevier B.V. All rights reserved.
1. Introduction
The increase in the demand of middle distillates (MD) production by rening heavy oils remains a challenging task [14]. The
efciency of conventional catalysts processing heavy oils is poor
due to diffusional limitations. Therefore, researchers have focused
on developing materials with larger pores to use them as supports
of the catalysts aiming the conversion of heavy oils into MD [57].
It is possible to synthesize and modify silica based materials
such as MCM-41 (Mobil Composition of Matter No 41), SBA-15
(Santa Barbara Amorphous No 5), and MCF (Mesocellular Foam),
and use them as catalytic supports for upgrading heavy oils [811].
In particular, SBA-15 is a type of mesoporous silica, which possesses wide pore volume, narrow pore size distributions, and better
hydrothermal stability as compared to, for example MCM-41 [12].
Therefore, SBA-15 is an interesting candidate for supported catalysts for hydroconversion of heavy oils [1214]. SBA-15 is formed
2. Experimental
2.1. Mesoporous silica synthesis
Five kinds of SBA-15 based materials were prepared by adapting the procedures employed in some literature reports [8,15,17].
Pluronic P123 (EO20 PO70 EO20 , Mav = 5800, Aldrich) was used as a
structural direction agent (SDA), and tetraethylortosilicate (TEOS,
98% Aldrich) as a silica source. Synthesis was conducted in strong
acid media conditions (pH < 1) in accordance to the following nominal molar ratio: 1.0 TEOS:0.0169 P123:4.42 HCl:186 H2 O. The effect
of NH4 F and TMB (1,3,5-trimethylbenzene) addition to the structure of SBA-15 was studied. NH4 F (99% Aldrich) and TMB (98%, Alfa
Aesar) were always added to the synthesis mixture before TEOS
incorporation.
In a typical synthesis of SBA-15, 10 g of P123 were completely
dissolved in an aqueous solution of 1.3 M HCl (37 vol.%, Merck) and
under stirring (500 rpm). Then, 24 mL of TEOS was added dropwise and kept under stirring for 1 h. Subsequently temperature was
increased to 311 K and thus kept during 24 h. The milky suspension
thus obtained was then transferred into a 500 mL PTFE vessel, and
placed inside a mufe furnace at 403 K for 24 h for the hydrothermal
treatment. Afterwards, the vessel was allowed to cool down. The
recovered solid product was ltered and washed with deionized
water, and left to dry at ambient conditions. The recovered powder was calcined, with a heating rate of 2 K/min in a ow of dry air
(100 mL/min) at 773 K during 6 h in order to remove the template.
NH4 F modied silica materials were synthesized by adding
0.10 g and 0.15 g of NH4 F to the synthesis mixture before TEOS
incorporation, those samples were labeled: SBA-F(0.10) and SBAF(0.15), the value in brackets indicates the amount of NH4 F added.
TMB modied silica materials were obtained adding the
required amount of TMB to get TMB:P123 mass ratios of 0.15 and
0.75 before dropwise TEOS incorporation and kept under stirring
for 1 h. Those materials were labeled: SBA-TMB(0.15) and SBATMB(0.75), the value in brackets indicates the TMB:P123 mass ratio.
The other steps remained the same as SBA-15 preparation.
99
100
ln
C
i
C0
= kPhen Wf
t
V
(1)
t
V
n
ti ti1
i=1
101
(2)
Vi1
moli
molPhenreaction
(3)
Fig. 2. Pore size distributions of SBA-15 based materials, (a) SBA-15, (b) SBATMB(0.75), (c) SBA-TMB(0.15), (d) SBA-F(0.10), (f) SBA-F(0.15).
and lower than 300, which evidence for an adequate tting of the
BET method for describing the recorded isotherms.
Considering the SBA-15 material, all synthesized materials
exhibited lower SBET values. Among the prepared materials, those
prepared with the addition of NH4 F had the lowest SBET . Such trend
102
Table 1
Physical properties determined from N2 sorption and XRD analysis.
Sample
PDads [nm]
PV [cm3 /g]
CBET
NSBET
d(100) [nm]
-Al2 O3
SBA-15
SBA-F(0.10)
SBA-F(0.15)
SBA-TMB(0.15)
SBA-TMB(0.75)
FeW/Al-SBA-15-10
FeW/Al-SBA-15-25
FeW/Al-SBA-15-40
FeW/Al-SBA-TMB(0.75)-10
FeW/Al-SBA-TMB(0.75)-25
FeW/Al-SBA-TMB(0.75)-40
203
627.3
504.6
342.4
436.3
697.3
378.7
383.3
428.3
351.5
392.8
393.5
12
12
9.3
10.8
15.8
17.2
10.2
10.1
10.3
17.2
17.2
17.2
0.62
1.03
1.58
1.90
1.15
2.16
0.69
0.69
0.70
1.37
1.56
1.47
83
131
166
112
149
166
130
143
249
135
132
272
0.73
0.75
0.83
0.62
0.68
0.69
67.2
83.4
36.2
66.7
101.2
47.8
61.9
53.6
27.6
29.9
47.7
9.5
9.8
10.6
12.4
14.2
9.5
9.5
9.5
14.2
14.2
14.2
7.8
17.7
SBET : BET specic surface area, PV : pore volume, PDads : mesopore diameter corresponding to the maximum of the pore size distribution, CBET : constant BET, NSBET , (normalized
BET surface area) as dened in Eq. (4), Smicro : microporous area by t-plot, d(1 0 0): d spacing, WO3 crystal size as calculated by Scherrers equation.
est amount of Al species for the Si/Al molar ratio of 10, and it is
more evident for Al-SBA-15-x supported catalysts instead of AlSBA-TMB(0.75)-x supported catalysts, because of the higher pore
volume Al-SBA-TMB(0.75) supports possess.
To conrm the presence of nanoparticles of Fe and W oxides
inside the pores of the SBA-15 based catalysts, normalized SBET
values were calculated using the following equation [8]:
NSBET =
SBET catalysts
(1 x)
SBET supports
(4)
Fig. 3. Low angle XRD patterns, (a) silica materials, (b) oxide catalysts.
103
Fig. 4. Wide angle XRD patterns for FeW/Al-SBA-15-x and FeW/Al-SBA-TMB(0.75)-x oxide catalysts, x indicates Si/Al molar ratio.
of the FeW phases, suggesting that either metals were homogeneously dispersed on the support, or their compositions were
below the detection limit of the X-ray signals (<4 nm). The absence
of XRD signals in wide angle region indicates that the particle size
of metals is below the coherence length of X-ray scattering.
Nevertheless, FeW/Al-SBA-TMB(0.75)-25 and FeW/Al-SBATMB(0.75)-40 catalysts exhibited other two peaks in 2 of: 33.2
and 24.4, which are attributed to poorly crystalline oxidized species
of Fe2 O3 and WO3 , respectively. The WO3 crystallite size as calculated by Scherrers equation is reported in Table 1, showing that at
higher Si/Al molar ratios, bigger WO3 particles are formed on the
surface of the Al-SBA-TMB(0.75) supports.
3.1.3. Scanning-electron-microscopy (SEM)
Results in Fig. 5 show the brous hexagonal morphology of the
SBA-15 material synthesized herein. Results are similar to those
previously reported in literature [15].
The effect on morphology by the addition of NH4 F in the synthesis of SBA-15 is illustrated in Fig. 6. The increase of NH4 F content
104
Fig. 8. PAD smoothed curves, (a) FeW/Al-SBA-15-x oxide catalysts, (b) FeW/AlSBA-15-TMB(0.75)-x oxide catalysts, x indicates Si/Al molar ratio.
105
Table 2
PAD quantication of acid sites for oxide catalysts and silica materials.
Acid sites [mmol H+ g1 cat]
Sample
Al-SBA-15-10
Al-SBA-15-25
Al-SBA-15-40
Al-SBA-TMB(0.75)-10
Al-SBA-TMB(0.75)-25
Al-SBA-TMB(0.75)-40
FeW/Al-SBA-15-10
FeW/Al-SBA-15-25
FeW/Al-SBA-15-40
FeW/Al-SBA-TMB(0.75)-10
FeW/Al-SBA-TMB(0.75)-25
FeW/Al-SBA-TMB(0.75)-40
Fig. 9.
27
Silanol (pH:5.53)
1.14
0.66
2.27
0.51
1.36
1.23
1.57
1.21
1.82
2.57
0.54
0.67
0.91
1.55
23.54
1.04
3.16
11.14
3.21
5.63
5.88
7.77
2.75
3.27
2.35
0.94
5.47
1.65
8.99
3.97
5.29
25.55
10.29
20.54
3.21
4.12
related to the mixed group was only evidenced when the active
metals were incorporated (Fig. 8b). This result indicates that the
incorporation of FeW decreases the acid strength of the catalysts
(Table 2).
3.1.5. 27 Al MAS NMR solid measurements
Fig. 9 shows the 27 Al MAS NMR spectra for Al-SBA-15-x and
Al-SBA-TMB(0.75)-x. These materials exhibit two clear signals at a
chemical shift, = 0 ppm ascribed to AlO6 octahedral coordination
group, which is characteristic of the presence of extra structural
aluminum species and other signal at = 52.9 ppm corresponding
to AlO4 tetrahedral aluminum species [43].
The area of each Al peak was computed by a Gaussian integration
of the peaks (Section 2.4.4). In all cases, samples prepared with
a Si/Al molar ratio of 25 exhibited a greater incorporation of Al
within the lattice of SBA-15 supports, as evidenced by the intensity
of the signal corresponding to tetrahedral aluminum coordination
in Fig. 10. This result conrms the formation of Brnsted acid sites
for all catalysts as in agreement to proposed PAD results previously
commented (Fig. 8).
Octahedral aluminum species were found in higher proportion
on the Al-SBA-TMB(0.75)-x supports with a Si/Al molar ratio of 40
support (Fig. 10b). Such a change might be associated to the changes
in the morphology, which went from brous to spherical silica after
the addition of TMB. In this sense, the surface of the SBA-15 based
materials seems to be inuencing the kind of Al species introduced
to the framework of the material.
Fig. 10. Al species peak area for 27 Al MAS NMR spectra, (a) Al-SBA-15-x, (b) Al-SBATMB(0.75)-x, x indicates Si/Al molar ratio.
The post synthesis method of incorporation or chemical grafting proposed to incorporate on the silica framework aluminum
species was satisfactory to generate the acid strength distribution
to the material on the surface of the catalysts supported on these
modied silica.
These results are consistent with the PAD curves, which showed
that the materials with higher content of type III and IIA acid sites
were Al-SBA-15-25 and Al-SBA-TMB(0.75)-25. It is known that the
tetrahedral Al coordination is a precursor of Brnsted acid sites and
octahedral for Lewis acid sites [7,2730,44,45].
106
Fig. 12. Sulded catalysts activity correlated to SBET , (a) FeW/Al-SBA-15-x, (b) FeW/Al-SBA-TMB(0.75)-x, x = Si/Al molar ratio.
107
Sample
NiMo/-Al2 O3
FeW/-Al2 O3
FeW/Al-SBA-15-10
FeW/Al-SBA-15-25
FeW/Al(40)-SBA-15
FeW/Al-SBA-TMB(0.75)-10
FeW/Al-SBA-TMB(0.75)-25
FeW/Al-SBA-TMB(0.75)-40
Al-SBA-TMB(0.75)-10
2.16
0.18
0.21
0.52
0.69
0.84
0.43
0.32
0.12
Fig. 13. Sulded FeW/Al-SBA-15-x and FeW/Al-SBA-TMB(0.75)-x catalysts activity vs. Si/Al molar ratio, x indicates Si/Al molar ratio.
108
Fig. 14. Sulded catalysts selectivity correlated to AlO4 species, (a) FeW/Al-SBA-15-x, (b) FeW/Al-SBA-TMB(0.75)-x, x = Si/Al molar ratio.
Fig. 15. Sulded catalysts selectivity correlated to AlO6 species, (a) FeW/Al-SBA-15-x, (b) FeW/Al-SBA-TMB(0.75)-x, x = Si/Al molar ratio.
109