Catalytic hydrodeoxygenation of anisole: An insight into the role of metals in transalkylation reactions in bio-oil upgrading

Article abstract of DOI:10.1039/c6gc03198f

Alkylbenzene was observed during continuous hydrodeoxygenation of anisole in toluene. Besides acidic compositions, metals in catalysts play an important role in the transalkylation reaction during the HDO of anisole. Some metals (e.g. NiMo) that enabled partial hydrogenation could temporarily destroy aromaticity, resulting in a high yield of alkylated products. In addition, a high temperature facilitated transalkylation, while temperatures over 400°C caused severe aromatic condensation.

Full text of DOI:10.1039/c6gc03198f

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G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
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Catalytic hydrodeoxygenation of anisole: an insight into the role
of metals on transalkylation reactions in bio-oil upgrading
Hongliang Wang,a Maoqi Fengb and Bin Yanga*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Alkylbenzene
was
observed
during
continuous (300°C~500°C) with hydrogen to remove oxygen to form
hydrodeoxygenation of anisole in toluene. Besides acidic hydrocarbons and water. A series of reactions, including
compositions, metals in catalysts play an important role in hydrogenation,
hydrogenolysis,
decarboxylation,
and
transalkylation reaction during the HDO of anisole. Some metals transalkylation can occur during this process.3 Tremendous
(e.g. NiMo) that enabled partial hydrogenation could transitorily efforts have been devoted to reveal the bio-oil HDO reaction
destroy the aromaticity, resulting in high yield of alkylated pathways. However, most of the published work has focused
products. In addition, high temperature facilitated transalkylation, on hydrogenation, hydrogenolysis or deoxygenation reactions,
while over 400°C caused severe aromatic condensation.
with little attention having been paid on transalkylation
reactions.14,
15
Phenolic compounds with methoxy groups
Lignocellulosic biomass is a promising renewable organic represent a significant fraction of bio-oil, especially for lignin-
resource with abundant supplies that can be used for replacing derived bio-oil. It was reported that at least 60% of the
fossil resources in the production of carbon based fuels.1, 2 compounds in lignin-derived pyrolysis oil contained one or
Lignin is one of the three main compositions of lignocellulosic more methoxy groups.13, 16Transalkylation reactions involving
biomass with relatively higher C/O ratio as compared to the transfer of methyl groups from methoxy groups to
cellulose and hemicellulose. More importantly, lignin is the aromatic rings to form alkylphenols or alkybenzenes has been
only highly aromatic renewable source that can be directly reported in bio-oil HDO reactions, especially when the
converted to high quality fuels.3, 4 However, most of the lignin catalysts incorporate acidic functions (such as using Al2O3 or
generated from the biorefinery process or the pulp and paper zeolites as the support).17-19 Transalkylation reactions can help
industry are currently underutilized.5 Consequently, extensive to build up the carbon chain and minimize carbon loss and
efforts in recent years have been devoted to efficiently hydrogen consumption during bio-oil HDO upgrading (Scheme
valorise lignin.6-10 Among all these attempts, the production of
1 Route II). Besides, the produced alkylated products
bio-oil from lignin or the whole lignocellulosic biomass via (alkylphenols or alkybenzenes) usually have high octane
pyrolysis is one of the most developed strategies.11, 12 Bio-oils numbers that are perfect for fuel blend usage. Moreover,
cannot be directly used in today’s infrastructure as fuels due to transalkylation reactions can stabilize aromatic rings and
their
hydrodeoxygenation (HDO) upgrading process is usually (coking, see Scheme 1 Route III). Therefore, it is important to
high
oxygen
contents.
Thus,
a
catalytic prevent the formation of condensed aromatics or chars
needed.13
understand and fully use the transalkylation reactions in the
Catalytic
HDO
is
similar
to
the
catalytic HDO upgrading of bio-oils.
hydrodesulfurization (HDS) and hydrodenitrogenation (HDN)
that have been well established in the petroleum refining
industry.13 Therefore, traditional HDS or HDN catalysts such as
metal sulfides (e.g., molybdenum disulfide) are widely used in
bio-oil HDO upgrading.13 Noble metal (e.g., ruthenium) based
catalysts are also well developed in this respect.13 Overall,
significant improvements in the development of optimal
catalysts that are active, selective, and stable for bio-oil HDO
upgrading have been done in recent years.3, 13 Bio-oil HDO
conversion usually takes place at high temperatures
Scheme 1. Selective conversion of anisole to alkylphenols or
alkylbenzenes.
b
Chemistry
& Chemical Engineering Division, Southwest Research Institute, San
Antonio, TX 78238, USA.
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The use of model compounds to illustrate the should be noted that the carbon balance was not 100% in all
characteristics of lignin or lignin-derived bio-oil catalytic runs, indicating that char (or char precursors) (high boiling
processes is very helpful and practical. Methoxyl (–OCH3) and point, undetectable by GC-MS) formed in the reaction. The
hydroxyl (–OH) are the major functional groups that are found type 3 products (condensed aromatics) are usually considered
in
(methoxybenzene) and phenol are widely chosen to represent carbon balance
lignin-derived bio-oil.13,20 Both of them are abundant in bio-oil.
The main product distributions are similar for NiMo/Al2O3
Anisole has an isolated methoxyl group on the aromatic ring, and MoP/Al2O3, with the most prevalent products to be phenol
which contains Caromatic-O-Cmethyl moieties that is perfect for the and alkylphenols (type products). A further analysis of the
lignin-derived
compounds.
Accordingly,
anisole as char precursor, which increased with the decrease of
.
1
investigation of demethylation or transalkylation reactions. compositions of phenol and alkylphenols produced by the two
Phenol only has an aromatic ring and a hydroxyl group, and it catalysts reveals an obvious difference, as depicted in Figure 1.
is the simplest aromatic compound that contains oxygen Phenol accounts for more than 60% of the type 1 products
moieties in bio-oil. The use of these two model compounds produced by the catalysis of MoP/Al2O3. However, it only
will greatly simplify the analysis of product distribution and accounts for about 30% of the products over NiMo/Al2O3
provide fundamental insights into the catalytic process of bio- catalysis, with the other 70% to be methylated phenols. This
oil upgrading.
result clearly demonstrates that the metal function of the
Resasco et al. investigated the HDO conversion of anisole catalyst has an important effect on transalkylation reaction. In
over the catalysis of HBeta and Pt/HBeta. They found the this respect, NiMo/Al2O3 is better than MoP/Al2O3 for methyl
addition of Pt to the acidic H-Bata zeolite could significantly transfer in the HDO of anisole. Besides, a relatively higher
increase the reaction rates of methyl-transfer. Inspired by this, ratio of benzene and alkyl benzenes (type
2 products) were
as well as to get more insights into the role of metals in alkyl- produced by the catalysis of NiMo/Al2O3 than by that of
transfer reaction occurred in the HDO of anisole, in this study, MoP/Al2O3, indicating NiMo/Al2O3 has higher catalytic activity
we employed metals with different hydrogenation activities in in deoxygenation reactions than MoP/Al2O3. Moreover, a small
metal-acid bifunctional catalysts for anisole HDO conversion quantity of aromatic ring saturated products (type
with the focus on methyl-transfer reaction.19
4:
cycloparaffin) was generated with NiMo/Al2O3 while none of
Bio-oil can hardly be used as feed alone due to its high them was detected with MoP/Al2O3. All these results reveal
viscosity and cold flow problems. In most cases, a certain that NiMo/Al2O3 has higher catalytic activities in
amount of solvents should be added to improve its flow transalkylation, deoxygenation, and hydrogenation reactions.
property. In this study, to mimic the diluted bio-oil feed, the The HDO conversion of anisole by the catalysis of γ-Al2O3 at
catalytic conversion of anisole was carried out in toluene. 350 °C was low (about 75 wt%). Phenols, alkylphenols, and
Three different commercialized catalysts (MoP, NiMo, Ru) condensed aromatics with hydroxy group or methoxyl group
supported on γ-Al2O3 were initially tested for this reaction were the main products. The distribution of methylated
under low hydrogen pressure (20 psig) at 350°C, as listed in products was lower than that obtained from MoP/Al2O3
Table 1 Runs 1~3. γ-Al2O3 is one of the most widely used acidic catalysis. These results suggest that metals in the bifunctional
supports in the preparation of bifunctional heterogeneous catalysts are not only essential for oxygen removal reactions
catalysts. It has been speculated that the methyl transfer but also important for transalkylation reactions.
reaction was mainly catalysed by the acidic function of the
Transalkylation reaction even in the HDO of the simplest
catalysts.17 As shown in Table 1, anisole conversion was high lignin model compounds like anisole is a relatively complicated
over all of the three tested catalysts. Especially, when process which involves several steps and can be affected by
NiMo/Al2O3 or Ru/Al2O3 was used, almost all of the anisole was other reactions. The first step in the transalkylation reaction is
converted. Mainly six types of products were detected by GC- the cleavage of Caromatic-O-Cmethyl ether bonds. The bond
MS. The first five kinds of products are classified according to dissociation energy of sp3 hybrid Cmethyl-O bonds is about
their chemical structures. Type
cyclohexanone, cyclohexanol, olefins, aliphatic ethers, etc. It
6
products mainly include 80~100kJ mol-1, lower than those of sp2 hybrid Caromatic-O
Table 1. Catalytic HDO conversion of anisole in toluene under different conditionsa
Run
Catalyst
Temperature
(°C)
Conversion
(wt.%)
Product distribution
1
2
3
0
0
0
0
4
0
5
0
0
7.38
0
6
1
2
3
4
5
MoP/Al2O3
NiMo/Al2O3
Ru/Al2O3
NiMo/Al2O3
NiMo/Al2O3
350
350
350
300
375
94
>99
>99
91
89.54
78.66
4.41
99.01
52.77
1.81
13.87
2.25
0.99
24.40
8.65
5.25
17.44
0
2.28
68.52
0
>99
5.66
7.68
5.90
3.59
6
NiMo/Al2O3
NiMo/Al2O3
400
350
>99
>99
40.26
75.25
25.33
14.88
11.34
2.78
10.55
2.76
11.32
0
1.2
4.33
7 b
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a Reaction conditions:10 wt.% anisole in toluene, Hydrogen pressure= 20 psig, liquid flow =4.0 mL/min, b liquid flow=0.5 mL/min. The detailed
experimental information could be found in the supplementary information.
2 are mainly phenol and benzene, respectively. Much less
alkylated products produced from Ru/Al2O3 than that from
NiMo/Al2O3 and MoP/Al2O3 indicate that Ru/Al2O3 has a
relatively low catalytic
Figure 1. The composition of phenol and alkylphenols produced by the
catalysis of MoP/Al2O3 and NiMo/Al2O3.
bonds.21, 22 Thus, it is more likely that the ether bond in anisole
is cleaved at the methyl side to yield phenols other than at the
aromatic side to yield benzenes. Indeed, phenol and
alkylphenols are the most abundant products that were found
in our study by the catalysis of NiMo/Al2O3 or MoP/Al2O3. Both
Figure 2. The effect of reaction temperature on the yields of non-
the metal catalysed hydrogenolysis and the acid catalysed
methylated products (phenol and benzene) and hexamethylbenzene from
hydrolysis can promote the cleavage of Cmethyl-O bonds. In our
the HDO.
case, no water was added except for a trace amount that
might be generated from dehydration reactions. Therefore,
activity in transalkylation reaction under current reaction
the cleavage of Cmethyl-O bonds was probably catalysed by
conditions. This result is probably due to the high
metal promoted hydrogenolysis reaction. Nickel has relatively
hydrogenation catalytic activity of ruthenium that can quickly
high catalytic activities in hydrogenolysis reactions, which can
destroy the aromaticity of anisole at the initial stage of the
account for the higher anisole conversion by the catalysis of
reaction. Additionally, the yield of type 6 products (mainly
NiMo/Al2O3 than that by MoP/Al2O3. Deoxygenation reactions
cyclohexanone and cyclohexanol, around 17%) was obviously
such as dehydroxylation usually accompany methyl transfer
higher from Ru/Al2O3 catalysis than the other two catalysts.
reaction. NiMo/Al2O3 produced
a much higher ratio of
These results suggest that catalysts with too high
hydrogenation catalytic activity are not beneficial for
transalkylation reaction due to the quick saturation of
aromatic rings.
dehydroxylation products (benzene and alkylbenzenes) than
MoP/Al2O3. This may be attributed to the higher
hydrogenation catalytic activity of Ni in NiMo/Al2O3. Similar to
the ether bonds, the bond strength of Caromatic-OH is around 84
kJ mol-1, higher than that of the Caliphatic-OH bonds due to the
delocalization of the lone pair orbital of oxygen in the hydroxyl
group onto the π orbital of the aromatic ring.22 Thus, a partial
hydrogenation of the aromatic ring near the Caromatic–OH bond
could result in temporary destroying the delocalization effect
and weakening the C-OH bonds. A further dehydrogenation
reaction by the catalysis of metals will restore the aromatic
The effect of reaction temperature on anisole HDO
conversion over NiMo/Al2O3 catalysis was investigated. At the
temperature of 300°C, about 90% anisole was converted, while
almost all the products were detected to be phenol and
alkylphenols (99%) among which phenol accounted for over 40%.
Increasing the reaction temperature to 350°C can significantly
improve the distribution of benzene and alkylbenzenes (from 1% at
300°C to 14 % at 350°C). When the reaction temperature was
increased to 375°C, 24% benzene and alkylbenzenes was produced,
while phenol and alkylphenols was decreased to 53%. The changes
structure. Thus,
a relatively highly active catalyst in
hydrogenolysis and hydrogenation reactions will benefit
transalkylation reactions, and can improve the yield of
alkylbenzenes.
of type
1 and type 2 products with reaction temperature revealed
that high temperature is in favour of dehydroxylation reaction
which benefits the transformation of phenol and alkylphenols to
benzene and alkylbenzenes. Further increasing the reaction
temperature to 400°C leads to a further decrease of phenol and
alkylphenols to around 40%. However, benzene and alkylbenzenes
Noble metal based catalysts have been extensively used for
the HDO conversion of lignin or lignin-derived bio-oils.14, 20 In
this respect, ruthenium is the most inexpensive one and has
high catalytic activities in hydrogenolysis and hydrogenation
reactions.23-25 The product distribution from anisole
conversion by the catalysis of Ru/Al2O3 is totally different from
that by the catalysis of NiMo/Al2O3 or MoP/Al2O3. As listed in
Table 1 Run 3, most products formed from Ru/Al2O3 catalysis
were cycloparaffin, which indicates Ru can facilely promote
the aromatic ring saturation (hydrogenation) reaction.
Cyclohexane without any alkylated methyl groups accounted
for more than 70% of the cycloparaffin products, with the
remainder to be cyclopentanes, which mainly were produced
from isomerization reactions. The products in type 1 and type
did not change a lot. Meanwhile, the type 3~5 products (condensed
aromatics, cycloparaffin, ring-opening hydrocarbons) increased
significantly, indicating a portion of benzene and alkylbenzenes
were converted to these products at 400°C. Reaction temperature
also has a great influence on the alkylation reaction. The yield of
non-alkylated products (benzene and phenol) and fully alkylated
product (hexamethylbenzene) with the change of reaction
temperature was investigated. As depicted in Figure 2, non-
alkylated products decreased almost linearly with the increase of
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the temperature. The total yield of phenol and benzene was near toluene. It is well known that alkylation reaction is a kind of
45% at 300°C. However, it decreased to around 10% when the electrophilic reaction. Any substituent group that can increase
temperature increased to 400 °C. On the contrary, the yield of the electron density of the aromatic ring will promote the
hexamethylbenzene increased obviously with the reaction alkylation reaction. Thus, an electron-donating substituent
temperature. Hexamethylbenzene yield increased seven folds from group on the aromatic ring will promote alkylation reaction.
300°C to 400°C. Thus, a relatively high temperature is beneficial for Based on the comprehensive consideration of the inductive
the transalkylation reaction, but too high temperatures can also effect and the conjugative effect, the electron donating ability
lead to the increase of condensation and aromatic ring saturation of the substituent groups should decrease as follows: -OH>-
reactions that reduces the yield of alkylphenols and alkybenzenes.
OCH3>-CH3>H, which means the alkylation reactions would
As compared with the effect of temperature, the increase more easily occur in phenol than in anisole followed by
of the reaction time by reducing the liquid flow from 4 mL/min toluene and benzene. Thus, the methyl groups in alkylphenols
to 0.5 mL/min seems to have little influence on the anisole and alkylbenzenes are more likely from anisole itself rather
conversion as well as the main product distribution, as listed in than from toluene.
Table 1 run 7. The only notable change was the yield of a small
Based on the discussion above, we proposed a reaction
pathway for the HDO conversion of anisole over the
bifunctional
Figure 4. Proposed major reaction pathway in HDO of anisole over catalysis
of NiMo/Al2O3.
Figure 3. Effect of temperature on phenol conversion in toluene over
catalysis of NiMo/Al2O3. The line in the Figure shows the conversion of
phenol with the change of temperature. The stack columns show the
selectivities of products. 1:Benzene, 2:alkylbenzenes, 3:condensed
aromatics, 4: Aliphatic hydrocarbons.
catalyst of NiMo/Al2O3, as shown in Figure 4. The first step in
the reaction is the demethylation of methyl group via the
cleavage of Cmethyl-O bond to form a methyl carbenium ion and
phenol. Then, the methyl carbenium ion would be alkylated
onto the aromatic ring by the catalysis of acidic Al2O3 to form
alkylphenols. The following partial hydrogenation reaction
over NiMo catalysis would transitorily destroy the aromaticity
of alkylphenols, and this would be beneficial for the
subsequent dehydroxylation reaction. After the hydroxyl group
is removed via the formation of water, the partially
hydrogenated ring would be dehydrogenated to restore the
aromatic structure to form alkylbenzenes.
portion of condensed aromatics (around 3%) when the liquid
flow was decreased to 0.5 mL/min.
Since toluene was used as solvent in our study for the HDO
conversion of anisole, we were interested to know if the
methyl groups in the generated alkylphenols or alkylbenzenes
were partly from toluene. To test this assumption, we used
phenol instead of anisole in the HDO reaction. As shown in
Figure 3, phenol conversion was quite low (51%) at a reaction
temperature of 350°C. Most products produced from phenol HDO
in toluene by the same catalyst of NiMo/Al2O3 were benzene and
condensed aromatics. No alkylphenols were found. A trace
amount of alkylbenzenes (mainly xylenes) was detected. This
result indicates that the methyl group in toluene is stable
under current reaction conditions. Increasing the reaction
temperature to 400°C improved the phenol conversion
significantly. However, the product distribution did not change
much except a higher yield of aliphatic hydrocarbons was noted. No
significant alkylphenols were produced even further increasing the
Conclusions
The HDO conversion of anisole and phenol in toluene
solvent by the catalysis of three catalysts (NiMo/Al2O3,
MoP/Al2O3, and Ru/Al2O3) in continuous flow reactor was
studied. Hexamethylbenzene was observed in serendipity.
Metals with moderate hydrogenation activities were found to
promote transalkylation reaction due to temporary removal of
the aromaticity of the molecular by partial hydrogenation
reaction. Metals with really high hydrogenation activities
reaction temperature to 500°C. The yield of alkylbenzenes resulted in low yield of alkylated products because of the
increased slightly, while the yields of condensed aromatics and
aliphatic hydrocarbons increased obviously at a high temperature of
500°C.
One may also argue that anisole as compared with phenol
may more easily receive the methyl group from toluene, and
irreversible breakage of the aromatic ring at the initial of the
reaction by full hydrogenation. A relatively high temperature
is beneficial for transalkylation reaction. However,
temperature higher than 400°C would lead to serious
condensation reactions as well as aromatic ring saturation
reaction, resulting in low yields of alkylated aromatics. Methyl
then a portion of methyl groups in alkylphenols and
alkylbenzenes generated from HDO of anisole may come from
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Acknowledgements
This work was supported by the Sun Grant-U.S. Department of
Transportation (DOT) Award # T0013G-A- Task 8, and the Joint
Center for Aerospace Technology Innovation with the
Bioproducts, Science
&
Engineering Laboratory and
Department of Biological Systems Engineering at Washington
State University. This work was performed in part at the
William R. Wiley Environmental Molecular Sciences Laboratory
(EMSL), a national scientific user facility sponsored by the U.S.
Department of Energy’s Office of Biological and Environmental
Research and located at the Pacific Northwest National
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Laboratory, operated for the Department of Energy by 25.
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High temperature and metal catalysts with moderate hydrogenolysis and hydrogenation activities facilitated
transalkylation during HDO upgrading of lignin-derived bio-oil compounds.
Key words：Bio-oil, Lignin, transalkylation, hydrodeoxygenation, alkylphenols, alkylbenzenes