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Alquilacon P-Cresol
Alquilacon P-Cresol
1
2 z Catalysis
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4
5
Clay-Based Solid Acid Catalyst for the Alkylation of
6 p-Cresol with tert-Butyl Alcohol
7
8 Lakshmy Muraleedharan, Bellundagere, M. Chandrashekara, Bangalore, S. Jai Prakash,
9 Yajnavalkya, and S. Bhat*[a]
10
11
12
Dealuminated montmorillonite, prepared by p-toluenesul- to coke formation. Correlation studies were made for D3-MMT
13
phonic acid (pTSA) treatment, was found to be an efficient catalyst between volume accessibility factor (VAF) and PC
14
catalyst in the liquid phase alkylation of p-cresol (PC) with tert- conversion. These studies suggested that mesopores and types
15
butyl alcohol (TBA) in the synthesis of 2-tert-butyl p-cresol (2- of acidities (Brønsted, Lewis and combination of both)
16
TBC). Comparative studies revealed that catalytic activity of generated after pTSA treatment were found to play role
17
montmorillonite clay sample treated with 0.5 M pTSA (D3-MMT) supplementing each other in enhancing the PC conversion. The
18
was superior to aluminium exchanged montmorillonite (Ex- regenerated catalyst recovered from the reaction mixture under
19
MMT) and zeolites (beta and HZSM-5) during alkylation reaction microwave heating retained its catalytic activity after three
20
under microwave irradiation. Thermogravimetric analysis (TG- cycles under optimized conditions.
21
DTG) showed that the deactivation of zeolites was mainly due
22
23
They require only facile workup procedures and the catalyst
24 Introduction
samples can be easily regenerated and reused.
25
Tertiary butyl substituted para-cresols are commercially impor- Clays are widespread, easily available and low cost sub-
26
tant organic compounds owing to their varied industrial stances. Modified montmorillonite clays are versatile catalysts
27
applications. Friedel-Craft’s alkylation of p-cresol (PC) with tert- for several acid catalyzed organic reactions.[8–11] Acid treatment
28
butyl alcohol (TBA) gives 2-tert-butyl p-cresol (2-TBC) and 2, 6- of montmorillonite clays is generally done by heating it with
29
di-tert-butyl p-cresol (2, 6-DTBC) commercially known as highly corrosive mineral acid solutions under reflux conditions
30
butylated hydroxy toluene (BHT). BHT have several commercial for several hours. This results in the uncontrolled structural
31
importance since they are widely used in the manufacturing of damage of clays.[12,13] However, the use of organic acids, which
32
antioxidants, cosmetics, polymerization inhibitors, jet fuels, are moderately strong, such as pTSA results in the controlled
33
petroleum additives, UV absorber and others.[1–3] dealumination of the clay layer structure.[14]
34
The use of homogeneous Brønsted or Lewis acid catalysts Literatures are available on the liquid phase alkylation of p-
35
including mineral acids, AlCl3, FeCl3 and ZnCl2 in Friedel Craft’s cresol with TBA using catalysts such as heteropoly acids
36
alkylation results in undesired by-products, and environmen- supported on transition metal oxide, ionic liquids, 12-Tungsto-
37
tally hazardous toxic wastes. It also involves tedious workup phosphoric acid immobilized on modified macroporous
38
procedures and further causes corrosion to the instruments.[4–7] phenol-furfural sulphonic acid resin and sulphated zirconia.[15–19]
39
Therefore, heterogeneous catalysts with outstanding versatility The reactions have also been carried out in vapour phase
40
have been successfully applied in the alkylation reaction. The reactor using zirconia or titanium supported heteropoly
41
solid acid catalysts such as chemically modified clays and acid.[20,21] The above mentioned methods in the alkylation of p-
42
zeolites are eco-friendly, safe, cost effective and have control- cresol with TBA require longer time duration to achieve the
43
lable acidic properties. The alkylation reaction catalyzed by equilibrium conversion. The use of solid acids, such as
44
these catalysts can be efficiently carried out under mild reaction supported heteropoly acids having high catalytic efficiency,
45
conditions with high selectivity towards the desired products. results in high solubility in polar media and hence there is
46
difficulty in separation from the reaction medium.[22] The main
47
drawback of sulphated zirconia is that it is prone to
48
deactivation after one reaction usage due to the formation of
49 [a] Dr. L. Muraleedharan, Dr. Bellundagere, M. Chandrashekara,
coke precursors. Ionic liquids suffer from drawbacks such as
50 Prof. Bangalore, S. J. Prakash, Prof. Yajnavalkya, S. Bhat
Chemistry Research Laboratory toxicity during their preparation, high cost and their disposal
51
Bangalore Institute of Technology after reaction.[23–26] Hence to make the alkylation reaction as
52 K.R. Road, Bangalore - 560004, India green as possible, alkylation of p-cresol with TBA was carried
53 Tel.: + 91 80 26615865
out using reusable pTSA treated montmorillonite clay catalyst
54 Fax: + 91 80 26426796
E-mail: bhatys@yahoo.com under solvent free conditions and microwave irradiation.
55
Supporting information for this article is available on the WWW under Literature reports are available on the microwave dealumina-
56
https://doi.org/10.1002/slct.201702098 tion of montmorillonite clays using various concentrations of
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pTSA solutions. Role of pores generated due to the deal- Table 1. Alkylation of PC with TBA over various solid acid catalysts.
1
umination were investigated previously in our laboratory in few
2 % PC conversion % Selectivity
organic transformations.[14,27,28] To the best of our knowledge no Catalyst 2-TBC TBE
3
literature is available on the study of alkylation of p-cresol with
4 MMT-Untreated - - -
TBA over pTSA treated montmorillonite clay under microwave
5 D1-MMT 32.86 98.5 1.5
heating. In the present paper, we report the catalytic activity of D2-MMT 44.45 97.7 2.3
6
pTSA treated montmorillonite clay catalyst in the Friedel-Craft’s D3-MMT 72.84 93.7 6.3
7
alkylation of p-cresol with TBA to yield 2-TBC. D4-MMT 70.52 93.8 6.2
8 Ex-MMT 64.03 95.56 4.44
9 HB 33.38 100 -
10 HZ - - -
Results and discussions
11 Reaction conditions: Mole ratio 1:1 (PC: TBA), Catalyst amount 0.3 g,
12 Catalyst characterization Temperature 373 K, Reaction time 10 minutes.
13
Montmorillonite clay was treated with 0.1 M, 0.2 M, 0.5 M and
14
1.0 M aqueous pTSA solutions under microwave irradiation.
15
These organic acid treated clays were designated as D1-, D2-, with that of original clay. These results indicated no change in
16
D3- and D4-MMT, respectively. Aluminium exchanged mont- the structural integrity of clay after the dealumination. An
17
morillonite clay prepared was designated as Ex-MMT. The beta increase in pTSA concentration from 0.1 M to 0.5 M resulted in
18
zeolite and ZSM-5 in their H-form are designated as HB and HZ, the enhancement of the specific surface area, acidity (Brønsted
19
respectively. (Preparation of catalysts in detail is given in and Lewis) and both micro- and mesoporosity (Table 2). Beyond
20
Supporting Information). 0.5 M, however, no significant changes in the catalyst character-
21
Powder XRD results of various pTSA treated montmorillon- istics were observed.[14]
22
ite clay samples (Figure 1) showed no changes in XRD patterns The FTIR spectra of pyridine adsorbed on the parent and
23
pTSA treated montmorillonite clay samples are presented in
24
Figure 2. Pyridine chemisorbed Lewis and Brønsted acid sites of
25
clay were assigned wave numbers 1450 cm 1 and 1545 cm 1,
26
respectively. Peak at 1491 cm 1 was ascribed as the contribu-
27
tion of both Lewis and Brønsted acid sites. As shown in
28
Figure 2, it can be observed that both Lewis and Brønsted
29
acidity of montmorillonite clay enhances with increase in the
30
pTSA concentration from 0.1 M to 0.5 M.
31
32
33 Catalytic performance by different catalyst
34
Alkylation of p-cresol with TBA mainly gave 2-TBC, 2, 6 DTBC
35
and tert-butyl phenyl ether (TBE) as shown in Scheme 1.
36
The results of alkylation reaction over various pTSA treated
37
clay, aluminium exchanged montmorillonite clay and zeolites,
38
carried out under microwave irradiation, are summarized in
39
Table 1. The alkylation reaction mainly gave 2-TBC and TBE as
40
the products. Nearly 90% of TBA conversion was observed
41
during the course of reaction. From these results it may be
42 Figure 1. XRD patterns of a) MMT-Untreated b) D1-MMT c) D2-MMTd) D3- observed that D3-MMT showed better conversion of PC (73%)
43 MMT e) D4-MMT.
with almost 94% selectivity toward 2-TBC, whereas, D1- and
44
D2-MMT as well as Ex-MMT gave lower conversions. Alkylation
45
46
47
48 Table 2. Alkylation of p-cresol with TBA over different modified montmorillonite catalysts.
49
% PC conversion % Selectivity Interlayer Al (meq/g clay) Pyridine FT-IR acidity (mmol g 1)
50
Catalyst 2-TBC TBE B L B+L
51
52 D1-MMT 32.86 98.5 1.5 0.25 30 26 56
D2-MMT 44.45 97.7 2.3 0.31 36 32 68
53
D3-MMT 72.84 93.7 6.3 0.68 67 63 130
54 D4-MMT 70.52 93.8 6.2 0.70 68 64 132
55 Ex-MMT 64.03 95.56 4.44 0.62 74 70 144
56 Reaction conditions: Mole ratio 1:1 (PC: TBA), Catalyst amount 0.3 g, Temperature 373 K, Reaction Time 10 minutes.
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as D3-MMT (MW), HB (MW) and HZ (MW), respectively. For D3-
1
MMT (MW) sample, weight loss less than 2% was observed in
2
comparison with that of D3-MMT catalyst. However, a notice-
3
able weight loss of nearly 12% was observed for the zeolite HB
4
(MW) and HZ (MW) catalyst samples that begin at about 473 K,
5
(Figure S1, supporting information). The weight loss in TGA
6
profile at high temperatures is mainly due to the removal of
7
coke deposits. This clearly indicates the built up of coke
8
precursors on HB (MW) and HZ (MW) catalysts during the
9
alkylation reaction.
10
The coking tendency is an intrinsic property of zeolite pore
11
structure and depends on the reaction temperature.[29–32] At low
12
reaction temperatures (> 473 K), coke formed is mainly due to
13
the condensation of olefins resulting in low volatile oligomers.
14
Coking occurs rapidly on acid catalysts from alkenes due to
15
their quick transformation through bimolecular reactions
16
(oligomerization, alkylation, hydrogen transfer).[32–34] Hence, the
17
lower PC conversion during the alkylation reaction with the
18
Figure 2. FTIR spectra of pyridine adsorbed on a) MMT–Untreated b) D1- large pore beta zeolite is attributed to higher acidity of the
19 MMT c) D2-MMT d) D3-MMT e) D4-MMT. catalyst resulting in the dehydration of TBA to isobutene and
20
its rapid oligomerization to bulky products within the pores of
21
beta zeolite.
22
of PC with TBA in the absence of catalyst gave negligible TGA-DTG profiles of used catalysts, (a) D3-MMT (MW), (b)
23
conversion under identical conditions. HB (MW) and (c) HZ (MW) are shown in Figure S2, of the
24
The results from Table 1 clearly show that D3-MMT is a supporting information. The derivative thermogram of HB
25
better catalyst than Ex-MMT for the alkylation reaction. The (MW) (Figure S2 (b)) showed peaks mainly at 540 K and 800 K,
26
efficiency of D3-MMT catalyst in the alkylation of PC with TBA indicating the formation of low boiling and high boiling
27
was further established by comparing its catalytic performance polymers.[35–38] DTG profile of HZ (MW) (Figure S2 (c)) showed a
28
with HB and HZ. However, the TBA conversion was nearly 90% peak around 470 K, indicating the occurrence of catalytic
29
during the alkylation reaction for all the above discussed deactivation due to the formation of low boiling polymers. The
30
catalysts except for MMT-Untreated, which was nearly 57%. It peak corresponding to 400 K generally observed in all deriva-
31
can be seen from the table that the conversion of PC was only tive thermograms of the catalyst samples is associated with
32
33% for HB which was much lower in comparison with the removal of physisorbed water and volatile species. The
33
conversion over D3-MMT. Alkylation of PC was not observed oligomerized products formed at these temperatures were
34
during the reaction when carried over HZ. In the case of negligible in D3-MMT (MW) catalyst sample as shown in
35
zeolites, the main reaction was probably due to the conversion Figure S2 (a).
36
of TBA to oligomerised products resulting in their deactivation. No conversion of PC was observed when the reaction was
37
Thus, the activity of D3-MMT for alkylation was found to be carried over HZ which can be attributed to the pore diameter
38
much higher than the highly acidic zeolites. Further investiga- limitations of the zeolite. This was further confirmed by
39
tions of the recovered catalyst samples were characterized by comparing the pore diameter of the D3-MMT, HB and HZ and
40
TGA. The catalyst samples recovered from the alkylation the molecular dimensions of the reactants and products. The
41
reaction mixture after microwave irradiation were designated molecular dimensions of the reactant and products in the
42
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50
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56 Scheme 1. Schematic representation of catalytic alkylation of p-cresol with tert-butyl alcohol under microwave irradiation.
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alkylation reactions were calculated by Chem Bio 3D software.
1
The calculated molecular dimensions of these molecules are (i)
2
PC - 6.54 Å 3 4.98 Å, (ii) TBA - 4.30 Å 3 4.12 Å, (iii) 2-TBC -
3
6.77 Å 3 6.53 Å and (iv) TBE - 8.97 Å 3 7.81 Å. The pore
4
diameter of HZ equals to 5.4 Å 3 5.6 Å [100] and 5.1 3 5.6 Å
5
[010] and that of HB equals to 7.5 Å 3 5 Å [100] and 5.6 Å 3
6
6.5 Å [100]. The diameter of these zeolites is lower or almost
7
similar to those of the reactants or products formed during the
8
reaction, apparently limiting the diffusion of these molecules
9
within the pores of zeolites. The average pore diameter of D3-
10
and D4-MMT as determined by BJH method is 35.3 Å which is
11
much larger than the molecular dimensions of either the
12
reactant or product molecules. Thus the pore dimensions of
13
D3- and D4-MMT facilitated higher PC conversion and lower
14
coke formation. D3- and D4-MMT showed almost the same PC
15
conversion but D3-MMT required much lower pTSA concen-
16
tration for its preparation. It was therefore selected as the
17
catalyst for investigations reported in the following sections.
18 Figure 3. TGA-DTG profiles of D3-MMT (CH) catalyst.
19
20 Microwave Versus conventional
21
The effect of reaction time on alkylation of PC by TBA using D3- Influence of reaction parameters
22
MMT was also studied under conventional heating by varying
23
the time from 10 to 420 minutes. Under conventional The alkylation reactions of PC with TBA under microwave
24
condition, a maximum conversion of 28% for PC was observed irradiation were optimized using D3-MMT catalyst in neat
25
even after 180 minutes with a selectivity of 93% towards 2-TBC conditions and the results summarized below.
26
and 7% towards TBE. The per cent PC conversion remained Conversion of PC and selectivity of 2-TBC increased with
27
constant even after further increase in the reaction time. This the increase in temperature and reached equilibrium at 373 K
28
poor conversion during the alkylation reaction was perhaps as (Figure 4). Beyond 373 K the selectivity of 2, 6-DTBC increased
29
a result of catalyst deactivation during conventional heating.
30
However, the PC conversion under microwave irradiation was
31
found to be much better as well as faster with almost similar
32
selectivity towards 2-TBC and TBE in comparison to the
33
conventional heating. Maximum conversion of PC (28%) was
34
obtained in 180 minutes under conventional heating while PC
35
conversion of 72% was achieved in 10 minutes under micro-
36
wave heating.
37
TGA-DTG profiles of the recovered clay sample from the
38
conventionally heated reaction [designated as D3-MMT (CH)]
39
are shown in Figure 3. Thermogram showed a total weight loss
40
of nearly l3% for D3-MMT (CH). The weight losses at lower and
41
higher temperature (430 K, 700 K and 850 K) were due to the
42
formation of low and high boiling oligomerised products. Pater
43
et al. have reported the composition of coke formed during the
44
liquid-phase alkylation of isobutene with 2-butene over
45
HFAU4.5 zeolite at 50 8C as alkyl bicyclic olefinic compounds.[39]
46
The result clearly indicates the formation of coke precursors on
47 Figure 4. Effect of temperature on alkylation of PC with TBA using D3-MMT
D3-MMT (CH) samples during the liquid phase alkylation of PC
48 catalyst. Reaction conditions: Mole ratio 1:1 (PC: TBA), Catalyst amount 0.3 g,
with TBA under conventional heating. On the other hand, the Reaction time 10 minutes.
49
TGA-DTG profile of recovered clay sample after alkylation under
50
microwave irradiation using D3-MMT showed no such loss
51
indicating negligible coking (Figure S2 (a)).
52
gradually. Decreased PC conversion at a temperature beyond
53
373 K can be attributed to de-alkylation of products at these
54
temperature.[21,40]
55
When the mole ratio of PC: TBA was increased from 1:3 to
56
2:1, as shown in Figure 5, the selectivity of 2-TBC increased
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1
2
3
4
5
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12
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14
15
16
Figure 7. Effect of reaction time on alkylation of PC with TBA using D3-MMT.
17 Figure 5. Effect of mole variation of reactants on alkylation of PC with TBA
Reaction conditions: Mole ratio 2:1 (PC: TBA), Catalyst amount 0.5 g,
18 using D3-MMT catalyst. Reaction conditions: Catalyst amount 0.3 g, Temper-
Temperature 373 K.
ature 373 K, Reaction time 30 minutes.
19
20
21
Effect of acidity and porosity of the catalyst in the alkylation
22
from 66 to 97%. The selectivity of 2-TBC reached a stable value
23
for higher PC: TBA ratios. To understand the role of acidity in the alkylation reaction of
24
The conversion of PC increased with the increase in the PC with TBA, a comparative study was made between the PC
25
catalyst amount up to 0.5 g of D3-MMT catalyst which is conversion (Table 1) and (i) Brønsted (B), (ii) Lewis (L), (iii)
26
obviously related to the increase of active sites (Figure 6). combination of the acidities (B + L) (obtained from pyridine FT-
27
IR measurement) and (iv) the interlayer aluminium content of
28
the different modified montmorillonite clays. The results are
29
given in Table 2.
30
From these results it may be observed that there is an
31
increment in the interlayer aluminium content fromD1- to D4-
32
MMT with the increase in the pTSA concentration from 0.1 M to
33
1 M. However, D3- and D4-MMT showed almost the same
34
results in all the parameters measured indicating a saturation
35
effect beyond 0.5 M. Apparently, further increase beyond 0.5 M
36
causes insignificant increase in dealumination. Preserving the
37
clay structure may perhaps be the reason for the resistance to
38
dealumination beyond 0.5 M pTSA.
39
The presence of interlayer cations accounts for the acidity
40
of different modified clay samples.[41,42] Acidities of the treated
41
montmorillonite samples increase due to migration of the
42
dislodged Al from the octahedral layer of clay structure to the
43
interlayer as a result of increase in pTSA concentration.[14,27] D3-
44
MMT showed a conversion of PC (73%) while D1- and D2-MMT
45
Figure 6. Effect of catalyst amount on the alkylation of PC with TBA using showed lower activities proportionate to the interlayer Al
46
D3-MMT. Reaction conditions: Mole ratio 2:1 (PC: TBA), Temperature 373 K, content and acidity. Even though the acidity as well as the
47 Reaction time30 minutes. interlayer Al content of Ex-MMT catalyst was comparable to
48
that of D3-MMT (Table 2), the per cent PC conversion was lower
49
for the former than the latter during the alkylation reaction.
50
The alkylation of PC with TBA reached a highest yield of These results indicate superior catalytic performance of D3-
51
48.22% for 2-TBC with selectivity around 97% in 45 minutes MMT apparently due to the better access of the reaction
52
and there was no further change in yield with increase in substrates to the active catalytic sites present in the interlayer
53
reaction period. Results are shown in Figure 7. of the clay. Hence, further work was required to understand the
54
access created on the surface by dealumination to reach the
55
active sites in the formation of 2-TBC. These studies were
56
carried out by relating PC conversion with catalyst character-
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1 Table 3. Amount of interlayer aluminium, pyridine adsorbed FT-IR acidity, micropore and mesopore volumes of pTSA treated clay samples and Ex-MMT
catalyst.
2
3 Interlayer Al Pyridine FT-IR acidity (B + L) Micropore(a) volume Mesopore(b) volume Specific surface area
Catalyst (meq/g clay) (mmol g 1) (cm3/g) (cm3/g) (m2)
4
5 MMT-Untreated - - 0.011 0.067 29.6
6 D1-MMT 0.25 56 0.015 0.068 92.1
D2-MMT 0.31 68 0.019 0.074 110
7
D3-MMT 0.68 130 0.024 0.076 133
8 D4-MMT 0.70 132 0.025 0.076 134
9 Ex-MMT 0.62 144 0.011 0.067 22.8
10
(a) For pore size < 20 Å.
11 (b) For pore size 20–500 Å.
12
13
14 Table 4. Correlation studies between PC conversion and acidity factors, micropore and mesopore volume and specific surface area.
15 %PC Conver- Pyridine FT-IR acidity Interlayer Al (meq/g Micropore vol- Mesopore vol- Specific surface area
16 sion (mmol g 1) clay) ume ume (m2)
17 Catalyst B L B+L (cm3/g) (cm3/g)
18 MMT-Un- 0 0 0 0 0 0.011 0.067 29.6
19 treated
20 D1-MMT 32.86 30 26 56 0.25 0.015 0.068 92.1
21 D2-MMT 44.45 36 32 68 0.31 0.019 0.074 110
D3-MMT 72.84 67 63 130 0.68 0.024 0.076 133
22 D4-MMT 70.52 68 64 132 0.7 0.025 0.076 134
23 Ex-MMT 64.03 74 70 144 0.62 0.011 0.067 22.8
24 Correl. Coeff., r 0.975 0.970 0.973 0.983 0.658 0.641 0.542
25 Reaction conditions: Mole ratio 1:1 (PC: TBA), Catalyst amount 0.3 g, Temperature 373 K, Reaction time 10 minutes.
26 BET Specific surface area (sd; 3.34), micropore volume by de Boer t-method (sd; 0.003), Brønsted (sd; 3.92), Lewis acidity (sd; 2.42)and B + L acidity (sd;
27 2.97) as Pyridine FT-IR. %PC Conversion (sd; 2.32).
*sd-standard deviation.
28
29
30
31
istics of different modified clay samples. The results are shown sitates its role to be considered in the correlation. This is
32
in Table 3. justified because of the fact that both acidity and pore volume
33
It may be observed from Table 3 that the gradual increase have a concurrent role in the conversion of PC. A factor called
34
in pTSA concentration from 0.1 M to 0.5 M gave rise to a volume accessibility factor (VAF) has been used by earlier
35
variation in the characteristics such as surface area, both micro- workers to relate combination of two parameters with the
36
and mesoporosity, in addition to acidity. catalytic activity.[43,44] The factor VAF is defined as the product of
37
Ex-MMT catalyst has lower micro- and mesoporosity as well pore volume and acidity of the catalyst samples. It is the pore
38
as specific surface area than D3-MMT catalyst. The surface area volume that is effectively available for the reactant molecule to
39
of Ex-MMT catalyst, however, is similar to that of the untreated get access to the acid sites. VAF has applicability for the pores
40
montmorillonite clay. It is clear from Table 3 that the acidity of on the catalyst surface generated due to chemical treatment
41
the treated clay increased with the strength of the pTSA and that facilitates the diffusion of the reagent molecule to come in
42
reached almost to the level of Ex-MMT but additionally brought contact with the acid sites and get activated. In the present
43
about a considerable increase in the pore volume and surface study, pores generated by pTSA treatment facilitate the TBA
44
area. The pores are created in the structure due to deal- molecule to diffuse through the pores to come into contact
45
umination and evidently are responsible for the enhancement with the interlayer hydrated Al ions with Brønsted character or
46
in acidity. It appears that approach to the acid sites through the Al ions on the edge sites with Lewis character and get
47
these generated pores has a role to play in the catalytic activity. protonated. To know whether such a process is facilitated by
48
To relate the role of pores present in these pTSA modified clay the micro- or mesopores with the B, L or B + L sites, the VAF
49
catalyst samples, correlation factor (r) was calculated between was calculated by multiplying both micro and mesopore
50
PC conversion and various catalyst parameters of the treated volumes individually with the B, L and B + L sites for all the
51
clays and Ex-MMT. The details of the correlation studies are catalyst samples. The correlation of VAFs with the PC
52
given in Table 4. conversion values for micro [(VAF)micro] and meso [(VAF)meso]
53
Table 4 shows a good correlation between PC conversion pore volumes are given in Table 5 and Table 6, respectively.
54
and acidity and consequently with the interlayer Al. Since, The values of correlation coefficient, r, as shown in Table 5
55
pores are responsible for the increase in acidity; the propor- and Table 6 are obtained by correlating (VAF)micro and (VAF)meso
56
tionate increase in pore volume with dealumination neces- with PC conversion. The objective was to find the extent of
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for providing XRD, ICP-AES and TG-DTG data of the catalyst [22] C. Gonzalez- Arellano, S. De, R. Luque, Catal. Sci. Technol. 2014, 4, 4242–
1 4249.
samples.
2 [23] C. Pretti, C. Chiappe, D. Pieraccini, M. Gregori, F. Abramo, G. Monni, L.
3 Intorre, Green Chem. 2006, 8, 238–240.
[24] D. Zhao, Y. Liao, Z. Zhang, CLEAN - Soil Air Water 2007, 35, 42–48.
4 Conflict of Interest [25] J. Ranke, S. Stolte, R. Stçrmann, J. Arning, B. Jastorff, Chem. Rev. 2007,
5 107, 2183–2206.
The authors declare no conflict of interest.
6 [26] M. Smiglak, W. M. Reichert, J. D. Holbrey, J. S. Wilkes, L. Sun, J. S.
7 Thrasher, K. Kirichenko, Chem. Commun. 2006, 24, 2554–2556.
Keywords: 2-tert-Butyl p-cresol · p-Cresol · Microwave · p- [27] S. Ramesh, B. S. Jai Prakash, Y. S. Bhat, Appl. Catal. A 2011, 413–414, 157–
8
162.
9 Toluenesulphonic acid · VAF [28] N. J. Venkatesha, B. M. Chandrasekhar, B. S. Jai Prakash, Y. S. Bhat, J. Mol.
10 Catal. A 2014, 392, 181–187.
[1] J. Pospisil, Poly. Deg. Stab. 1988, 20, 181–202. [29] L. D. Rollmann, J. Catal. 1977, 47, 113–121.
11
[2] J. Murphy, The Additives for Plastics Handbook, Elsevier Advanced [30] L. D. Rollmann, D. E. Walsh, J. Catal. 1979, 56, 139–140.
12 Technology, Oxford, 1996. [31] M. Guisnet, P. Magnoux, Appl. Catal. 1989, 54, 1–27.
13 [3] G. A. Olah, Friedel-Crafts and Related Reactions, Interscience Publishers, [32] P. Magnoux, C. Canaff, F. Machado, M. Guisnet, J. Catal. 1992, 134, 286–
14 New York, 1963. 298.
[4] G. Sartori, R. Maggi, Advances in Friedel-Crafts Acylation Reactions: [33] M. Guinset, P. Magnoux, Stud. Surf. Sci. Catal. 1994, 88, 53–68.
15
Catalytic and Green Processes, CRC Press (an imprint of the Taylor & [34] M. Guisnet, P. Magnoux, Zeolite Microporous Solids: Synthesis, Structure
16 Francis Group), Boca Raton, Florida, 2009. and Reactivity, (Eds.: E. G. Derouane, F.Lemos, C. Naccache, F. RamaR-
17 [5] N. E. Poh, H. Nur, M. N. M. Muhid, H. Hamdan, Catal. Today 2006, 114, ibeiro, NATO AS1 Series C, Kluwer, Dordrecht, 1992, pp. 457–458.
18 257–262. [35] P. J. Grobet, W. J. Mortier, E. F. Vansant, G. Schulz-Ekloff, Innovation in
[6] G. D. Yadav, N. S. Doshi, Appl. Catal. A 2002, 236, 129–147. Zeolite Material science, Stud. Surf. Sci. Catal., 37, Elsevier, Amsterdam
19
[7] A. V. Krishnan, K. Ojha, N. C. Pradhan, Org. Process Res. Dev. 2002, 6, 132– 2011.
20 137. [36] S. Chen, G. Manos, Catal. Lett. 2004, 96, 195–200.
21 [8] G. Nagendrappa, Appl. Clay Sci. 2011, 53, 106–138. [37] B. Wang, G. Manos, J. Catal. 2007, 250, 121–127.
22 [9] R. S. Varma, Tetrahedron, 2002, 58, 1235–1255. [38] X. Guo, Y. Zheng, B. Zhang, J. Chen, Biomass Bioenergy 2009, 33, 1469–
[10] S. Dasgupta, B. Tçrçk, Org. Prep. Proced. Int. 2008, 40, 1–65. 473.
23
[11] B. C. Ranu, K. Chattopadhyay, Green procedures for the synthesis of [39] J. Pater, F. Cardona, C. Canaff, N. S. Gnep, G. Szabo, M. Guisnet, Ind. Eng.
24 useful molecules avoiding hazardous solvents and toxic catalyst, Eco- Chem. Research 1999, 38, 3822–3829.
25 friendly Synthesis of Fine Chemicals, Royal Society of Chemistry, Cam- [40] S. Subramanian, A. Mitra, C. V. V. Satyanarayana, D. K. Chakrabarthy, Appl.
26 bridge, U. K., 2009, pp. 186–219. Catal. A 1997, 159, 229–240.
[12] S. M. Lee, D. Tiwari, Appl. Clay Sci. 2012, 59–60, 84–102. [41] C. R. Reddy, B. Vijayakumar, P. Iyengar, G. Nagendrappa, B. S. Jai Prakash,
27
[13] S. Korichi, A. Elias, A. Mefti, Appl. Clay Sci. 2009, 42, 428–432. J. Mol. Catal. A 2004, 223, 117–223.
28 [14] S. Ramesh, Y. S. Bhat, B. S. Jai Prakash, Clay Miner. 2012, 47, 231–242. [42] C. R. Reddy, Y. S. Bhat, G. Nagendrappa, B. S. Jai Prakash, Catal. Today
29 [15] N. Bhatt, P. Sharma, A. Patel, P. Selvam, Catal. Commun. 2008, 9, 1545– 2009, 141, 157–160.
30 1550. [43] N. J. Venkatesha, Y. S. Bhat, B. S. Jai Prakash, RSC Adv. 2016, 6, 45819–
[16] X. Li, R. Cao, Q. Lin, Green Chem. Lett. Rev. 2014, 7, 179–183. 45828.
31
[17] P. Elavarasan, K. Kondamudi, S. Upadhyayula, World Acad. Sci. Eng. [44] N. J. Venkatesha, B. S. Jai Prakash, Y. S. Bhat, Catal. Sci. Technol. 2015, 5,
32 Technol. 2010, 4, 147–152. 1629–1637.
33 [18] Z. R. Su, T. J. Wang, React. Funct. Polym. 1995, 28, 97–102.
34 [19] G. D. Yadav, Tushar, Znd. Eng. Chem. Res. 1996, 35, 721–731.
[20] S. M. Kumbar, G. V. Shanbhag, F. Lefebvre, S. B. Halligudi, J. Mol. Catal. A:
35 Submitted: September 8, 2017
Chem. 2006, 256, 324–334.
36 [21] B. M. Devassy, G. V. Shanbhag, F. Lefebvre, S. B. Halligudi, J. Mol. Catal. A: Revised: January 5, 2018
37 Chem. 2004, 210, 125–130. Accepted: January 7, 2018
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