Catalysis Meets Nonthermal Separation for the Production of (Alkyl)phenols and Hydrocarbons from Pyrolysis Oil

Article abstract of DOI:10.1002/anie.201610405

A simple and efficient hydrodeoxygenation strategy is described to selectively generate and separate high-value alkylphenols from pyrolysis bio-oil, produced directly from lignocellulosic biomass. The overall process is efficient and only requires low pressures of hydrogen gas (5 bar). Initially, an investigation using model compounds indicates that MoC_x/C is a promising catalyst for targeted hydrodeoxygenation, enabling selective retention of the desired Ar?OH substituents. By applying this procedure to pyrolysis bio-oil, the primary products (phenol/4-alkylphenols and hydrocarbons) are easily separable from each other by short-path column chromatography, serving as potential valuable feedstocks for industry. The strategy requires no prior fractionation of the lignocellulosic biomass, no further synthetic steps, and no input of additional (e.g., petrochemical) platform molecules.

Full text of DOI:10.1002/anie.201610405

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201610405
German Edition: DOI: 10.1002/ange.201610405
Biomass Hot Paper
Catalysis Meets Nonthermal Separation for the Production of
Alkyl)phenols and Hydrocarbons from Pyrolysis Oil
(
Zhengwen Cao, Jan Engelhardt, Michael Dierks, Matthew T. Clough, Guang-Hui Wang,
Eleni Heracleous, Angelos Lappas, Roberto Rinaldi,* and Ferdi Schꢀth*
Abstract: A simple and efficient hydrodeoxygenation strategy
is described to selectively generate and separate high-value
alkylphenols from pyrolysis bio-oil, produced directly from
lignocellulosic biomass. The overall process is efficient and
only requires low pressures of hydrogen gas (5 bar). Initially,
an investigation using model compounds indicates that MoCx/
C is a promising catalyst for targeted hydrodeoxygenation,
enabling selective retention of the desired ArꢀOH substituents.
is considered excessive. Therefore, for application at a large-
scale biorefinery, a strategy based on the pyrolysis of whole
[
1i]
biomass is still preferred. Thermal pyrolysis is one impor-
tant technology for lignocellulosic (LC) biomass deconstruc-
tion, whereby high-temperature treatment yields a bio-oil on
[
5]
the second timescale. Although the depolymerization of LC
biomass during pyrolysis leads to the formation of high-value
aromatic chemicals, relatively little attention has been
devoted to the extraction of high-value species from the
pyrolysis oil, mostly because of the expense associated with
the separation of complex mixtures of highly oxygenated
By applying this procedure to pyrolysis bio-oil, the primary
products (phenol/4-alkylphenols and hydrocarbons) are easily
separable from each other by short-path column chromatog-
raphy, serving as potential valuable feedstocks for industry.
The strategy requires no prior fractionation of the lignocellu-
losic biomass, no further synthetic steps, and no input of
additional (e.g., petrochemical) platform molecules.
[
6]
species.
4-Alkylphenol species are resistant to dehydroxylation,
[
7]
owing to the high dissociation energies of ArꢀOH bonds.
The constituents of LC pyrolysis bio-oil contain an array of
both aliphatic and aromatic CꢀO-bonded substituents. Con-
M
irroring the petroleum-based economy, it is crucial for
sidering nonthermal separation (e.g. industrial flash chroma-
tography), a strategy centered around selective hydrodeox-
ygenation (SHDO) of aliphatic CꢀO bonds, whilst leaving
ArꢀOH substituents intact, would be highly advantageous. In
a bio-based economy to maximize the revenue obtained from
[
1]
both fuels and chemicals. 4-Alkylphenols are unique
candidate value-added products for targeted extraction from
pyrolysis bio-oil, with the potential to serve as replacements
for petroleum-derived phenols in applications such as non-
ionic surfactants, lubricant additives, phenolic resins, polymer
additives, and agrochemicals. Annual worldwide production
of all alkylphenols exceeds 450000 metric tons, and the cost of
raw materials is the largest single contributor to total
this way, the high-value-added alkylphenol species could be
generated through pyrolysis, SHDO, and nonthermal separa-
tion steps while retaining the hydrocarbons as a fuel fraction.
In the following, we present a novel strategy, consisting of
three steps, to convert LC biomass into alkylphenols and
hydrocarbons (Figure 1). The SHDO of pyrolysis oil is
catalyzed by molybdenum carbide supported on carbon
[2]
[
3]
manufacturing costs (60–80%). One reasonable procedure
is to separate the holocellulose and lignin fractions, followed
by depolymerization and dehydration to the desired chem-
under low H pressures, whereby exploitation of the high
2
ArꢀOH bond energy enables selective cleavage of other
oxygen-containing functional groups found in the pyrolysis
bio-oil. For a wide range of highly oxygenated compounds, the
valuable phenolic moiety is preserved throughout the course
of the SHDO process. This step is followed by simple and
economic separation of phenol and alkylphenol species from
the upgraded product mixture. The resulting product mixtures
after SHDO are primarily composed of a monolignol-derived
[
1h,4]
icals.
However, in this manner, the cost of pre-separation
[*] Dr. Z. Cao, J. Engelhardt, M. Dierks, Dr. M. T. Clough, Dr. G.-H. Wang,
Prof. Dr. F. Schꢀth
Max-Planck-Institut fꢀr Kohlenforschung
45470 Mꢀlheim an der Ruhr (Germany)
E-mail: schueth@mpi-muelheim.mpg.de
(alkyl)phenol fraction and a hydrocarbon fraction. These
Dr. E. Heracleous, Dr. A. Lappas
fractions are easily separated by means of a short-path silica
gel column (solvent I: n-hexane, solvent II: ethyl acetate;
Figure 1). As a third step, after flash chromatographic
separation, the generated hydrocarbons and ethyl acetate
solution may be re-applied to the extraction of additional
Chemical Process Engineering Research Institute
Center for Research and Technology Hellas
P.O. Box 361, 57001 Thessaloniki (Greece)
and
School of Science & Technology, International Hellenic University
P.O. Box 361, 57001 Thessaloniki (Greece)
(alkyl)phenols after the next SHDO cycle.
Dr. R. Rinaldi
Typically, an HDO reaction of pyrolysis bio-oil proceeds
Department of Chemical Engineering, South Kensington Campus
Imperial College London, London, SW7 2AZ (UK)
E-mail: rrinaldi@imperial.ac.uk
in two stages: 1) initial low-temperature treatment eliminates
reactive functional groups (e.g. ketone, aldehyde, alcohol or
alkenyl groups), and 2) subsequent reaction under high
pressures of hydrogen cleaves phenolic substituents (e.g.
phenyl alkyl ethers, diphenyl ethers, benzofuran linkages, and
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
http://dx.doi.org/10.1002/anie.201610405.
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1
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ingly, of the investigated catalysts, molybdenum carbide
supported on carbon, MoC /C, clearly exhibited the greatest
x
[10b]
selectivity towards phenol (Table 1).
In fact, the selectivity
towards phenol by HDO of guaiacol over MoC /C was
x
promisingly high (75% yield at 99% conversion). Under
HDO conditions, guaiacol may be expected to undergo either
“
direct” HDO to phenol or anisole or (“indirect”) full
hydrogenation to 2-methoxycyclohexan-1-ol followed by
[
7c,11]
HDO (Scheme 1).
However, the predominance of
Figure 1. A simplified representation of the strategy for the production
of high-value, low-volume chemicals (alkylphenols) and low-value,
high-volume fuels from LC biomass: Thermal pyrolysis of the biomass
to pyrolysis oil; Low-pressure selective hydrodeoxygenation (SHDO) of
the bio-oil affords mixtures of alkylphenols/phenol and hydrocarbons;
Hydrocarbon and alkylphenol/phenol fractions are separated over
silica, using n-hexane and ethyl acetate.
Scheme 1. Various possible HDO pathways of guaiacol.
phenol ArꢀOH bonds) by hydrogenation and hydrodeoxyge-
a guaiacol!phenol!benzene HDO pathway with MoC /C
x
[8]
nation pathways. For the proposed strategy, it is crucial to
selectively maintain the phenolic hydroxy group, whilst
simultaneously cleaving phenyl alkyl ether and diphenyl
allows kinetic control (low pressure, low temperature).
Previous investigations demonstrated that benzene is the
primary product from the reaction of guaiacol under high
hydrogen pressure and high temperature (25–30 bar, 350–
4008C), and considerable selectivity to phenols was observed
[7a,b,9]
ether bonds.
To explore catalysts for this selective
reaction, we selected o-methoxyphenol (guaiacol) as
a simple lignin model compound, because it incorporates
both the phenyl alkyl ether and the phenolic functional
groups. Table 1 reveals several important trends regarding the
performance of some catalysts, selected based on literature
[
10b,12]
using alcohol solvents without hydrogen.
In contrast,
here the phenolic group is preserved under low hydrogen
pressure and low temperature (5 bar, 3008C). Therefore,
MoC /C was selected as the most promising candidate for
x
[10]
data, for the conversion of guaiacol. First, Pt/C showed high
activity for direct hydrogenation of guaiacol to 2-methoxycy-
clohexan-1-ol. Second, Ni P/C and Ni P/SiO resulted in
further investigation.
Despite the observed selectivity towards phenol from
guaiacol with MoC /C, it was nevertheless important to
2
2
2
x
relatively high anisole yields (although anisole hydrogenolysis
could generate phenol). Third, PtCo/C exhibited undesirably
high activity for the hydrogenation of the aromatic ring to
cyclohexanol and cyclohexanone. Last, the deficit in the “ring
determine whether other varieties of (primarily aliphatic)
CꢀO bonds can be cleaved under the same reaction con-
ditions while retaining the phenolic hydroxy group. Accord-
ingly, HDO reactions were performed on a selection of
additional model compounds, of varying complexity, over
MoC /C (Table 2). In general, the MoC /C catalyst demon-
balance” with Ru/TiO indicates the possible formation of
2
coke, thus contributing to the low yield of phenol. Interest-
x
x
[
a]
Table 1: Conversions and product distributions of different catalysts in the screening test, for HDO of o-methoxyphenol (guaiacol).
[
b]
Cat.
X [%]
Product selectivity [%]
Ring balance [%]
*
Pt/C
50
99
83
36
94
99
1
4
2
0
1
3
8
3
5
16
23
37
3
3
0
8
17
2
7
5
30
0
0
6
18
40
0
0
2
29
0
0
0
0
20
1
49
8
7
0
91
90
92
95
74
97
*
PtCo/C
Ni P/SiO2
Ni P/C
Ru/TiO2
12
20
36
14
76
2
2
MoC /C
0
0
0
x
[a] Reaction conditions: substrate (1 mmol), n-hexadecane (internal standard, 20 mg), catalyst (100 mg), and solvent (2 mL) at 3008C (“*” denotes
2
508C) and 5 bar pressure of H (258C) for 2 h. [b] As the SHDO performed on guaiacol leads to demethoxylation, the C-balance is given relative to the
2
C6-ring products.
2
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Angewandte
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[
a]
Table 2: Identified products evolving from low-pressure HDO of different model compounds over MoC /C.
x
[
c]
Entry
1
Substrate
t [h]
X [%]
93
Main products and selectivity [%]
Ring balance [%]
n-octanol
2
n-C H
97
8
18
97
2
3
4
2
2
8
99
8
95
100
99
27
5
6
2
99
97
4
2
8
2
73
26
83
89
92
98
98
94
[
[
[
b]
b]
b]
7
8
9
[
b]
1
1
1
0
1
2
8
2
8
91
28
91
88
98
89
[
[
b]
b]
[a] Reaction conditions: substrate (1 mmol), n-hexadecane (internal standard, 20 mg), catalyst (100 mg), and solvent (2 mL) at 3008C under 5 bar H2
pressure (258C) for the given time. [b] Reaction conditions: substrate (0.5 mmol), n-hexadecane (internal standard, 20 mg), catalyst (100 mg), and
solvent (2 mL) at 3008C under 5 bar H pressure (258C) for the given time. [c] As the HDO performed on guaiacol leads to demethoxylation, the
2
C-balance is given relative to the C -ring products.
6
strated the ability to retain ArꢀOH bonds, while selectively
of the intermediate phenol was reduced with longer reaction
times (entries 3 and 4). A compromise between the degree of
HDO and the phenol yield must, therefore, be found by
adjustment of reaction time.
cleaving the other oxygen-containing functional groups.
Aliphatic CꢀO bonds (i.e. in 1-octanol and cyclohexanol)
were cleaved within 2 hours of reaction. HDO reactions on
model compounds incorporating diphenyl ether, phenyl alkyl
ether, and benzofuran moieties (entries 7, 9, and 11) primarily
resulted in the corresponding phenol and alkoxy-(alkyl-
To demonstrate the feasibility of the strategy, MoC /C-
x
catalyzed SHDO reactions on a pyrolysis bio-oil obtained
from oak wood were performed (H pressure 5 bar, 3008C).
2
)
2
phenol species. Although conversions were low within
hours of reaction time, an extension to 8 hours led to an
To ensure a high degree of HDO, reactions were carried out
for a duration of 8 hours at 3008C, and were expected to lead
to a somewhat increased arene yield instead of the targeted
phenol products. Two-dimensional (2D) GC ꢀ GC images
increase in conversion, and the promising selectivity towards
the targeted product(s) was still observed. However, the yield
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from each stage of the process are shown in Figure 2. The 2D
GC ꢀ GC image of untreated bio-oil (prior to SHDO)
demonstrates that the oil consisted of furan species, alde-
hydes, ketones, and lignin-derived phenolic compounds (Fig-
[
13]
ure 2a).
Similar to the reactions performed on model
compounds, SHDO brought about cleavage of aliphatic CꢀO
bonds of the bio-oil to form alkanes. Likewise, hydrodeox-
ygenation at ArꢀOR and ArꢀOꢀAr bonds took place
selectively without saturation of the aromatic ring. By
contrast, hydrogenolysis of stronger ArꢀOH bonds was
disfavored under the reaction conditions. The identified
compounds were mainly phenol, 4-(alkyl)phenols, and hydro-
carbons (Figure 2b). A product mass yield of 38% was
obtained after SHDO, corresponding to a total carbon yield of
approximately 68%.
Given the high selectivity of the SHDO reaction, the
product mixture was subsequently separated nonthermally
using a short-path flash silica gel column, exploiting the
differences in polarity of the aliphatic and phenol derivatives.
Hydrocarbons were extracted by eluting with n-hexane
(
Figure 2d), followed by extraction of the phenolic species
using ethyl acetate (Figure 2c). The n-hexane solution of
hydrocarbons may be recycled as the solvent for a second
SHDO reaction cycle. Alternatively, the reclaimed n-hexane
and ethyl acetate solvents could be used for subsequent
separation of SHDO product mixtures. In this manner, the
requirement for input of solvents is minimized, and the
targeted phenol (and aliphatic) products may be concen-
trated, thus enhancing the efficiency and economy of the
process. Since no compounds of higher polarity than phenol-
(
s) were present (Figure 2b), all compounds were washed out
by either n-hexane or ethyl acetate. Therefore, no compounds
were lost as a result of reversible adsorption on the silica
column during separation.
A 2D GC ꢀ GC analysis of the ethyl acetate fraction after
nonthermal separation demonstrated that the solution pre-
dominantly contained the desired alkylphenol/phenol prod-
ucts (Figure 2c). The overall yields (calculated from starting
pyrolysis bio-oil) of alkylphenols and phenol were 2.5 and
1
.0%, respectively (see Table S3 in the Supporting Informa-
tion). Considering the total mass yield is 38%, the yield of
other compounds, hydrocarbons, remains as 35 wt%. One
may always argue that these yields appear to be too low to be
industrially relevant. However, vanillin, a specialty chemical
produced on a scale of 70000 ton per year, is obtained at
comparable yields by current industrial processes based on
[4a]
oxidation of lignosulfonates. Moreover, the overall yield of
.5% of high-value-added, isolated phenolic compounds
3
nears the current market distribution of chemicals and fuels
obtained from petroleum. Furthermore, the yield could be
expected to increase by either applying a feedstock with
higher lignin content or an even more selective catalyst.
In addition to the target products, minor quantities of
oxygenated species (e.g., guaiacol, 4-methylguaiacols,
Figure 2. GCꢁGC-FID traces highlighting volatile products obtained at
different stages of the process. a) Starting pyrolysis bio-oil from oak
wood. b) After selective HDO reaction with MoC /C. c) Content of the
x
ethyl acetate fraction. d) Content of n-hexane fraction, after chromato-
graphic separation using n-hexane and ethyl acetate eluents (smeared-
out tail at high retention time in the first column results from
impurities in the n-hexane).
4
-ethylguaiacols) were detected (see Table S3; Figure 2c).
Our approach renders 4-alkylphenols as the primary com-
[
14]
pounds of the final product mixture. The para isomers are
known to boil at temperatures 10–208C higher than analo-
gous ortho compounds, which would likely facilitate separa-
4
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15]
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3
[
16]
strategy to obtain high purity phenol.
In conclusion, we have demonstrated a new strategy,
consisting of pyrolysis of LC biomass, SHDO, and nonthermal
separation, thus rendering high-value alkylphenols and
hydrocarbons as isolated fractions. Instead of the pre-
separation of lignin and holocellulose, the low-cost non-
thermal separation of the product mixture can easily be
undertaken in our system to afford the desired alkylphenols
from lignin, thus serving as an important potential feedstock
for industry. The integrated procedure could offer significant
economic benefits relative to a simple biomass-to-fuel
strategy, on account of both the decreased hydrogen con-
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Conflict of interest
The authors declare no conflict of interest.
Keywords: biomass · gas chromatography · hydrocarbons ·
molybdenum · phenols
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Manuscript received: October 24, 2016
Revised: December 6, 2016
2000.
Final Article published: && &&, &&&&
6
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ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2017, 56, 1 – 7
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Biomass
Out of the woods: Selective hydrodeox-
ygenation of lignocellulose-derived pyrol-
Z. Cao, J. Engelhardt, M. Dierks,
M. T. Clough, G.-H. Wang, E. Heracleous,
A. Lappas, R. Rinaldi,*
ysis bio-oil, catalyzed by MoC /C, affords
x
value-added alkylphenol (and phenol)
products and hydrocarbons. The strategy
requires no prior fractionation of the
lignocellulosic biomass, no further syn-
thetic steps, and no input of additional
petrochemical platform molecules.
F. Schꢁth*
&&& — &&&
Catalysis Meets Nonthermal Separation
for the Production of (Alkyl)phenols and
Hydrocarbons from Pyrolysis Oil
Angew. Chem. Int. Ed. 2017, 56, 1 – 7
ꢀ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
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These are not the final page numbers!