Fuel 148 (2015) 226230

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Catalytic oxygen atom transfer from lignin to cellulose

and hemicellulose and its importance in biorening
Zuolin Zhu a,b,, Jonathan Zhu a
a
b

Sun Pharmaceuticals, Inc., San Diego, CA 92128, USA

China Fuel (Huaibei) Bioenergy Technology Development Co., Ltd., Anhui 235000, China

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Oxygen atom transfer from lignin to

cellulose is proposed and conrmed.

 All polymers of biomass are

hydrolyzed into small molecules in

one-pot reaction.
 Lignin is converted quantitatively
into small molecular aromatics.
 Cellulose and hemicellulose are
transferred quantitatively into small
organic acids.
 Small molecular aromatics can be
converted into diesel blends in onestep.

a r t i c l e

i n f o

Article history:
Received 2 December 2014
Received in revised form 24 January 2015
Accepted 29 January 2015
Available online 11 February 2015
Keywords:
Oxygen atom transfer
Biomass
Diesel
Small molecular aromatics
Small organic acids

a b s t r a c t
A novel approach for biorening is proposed and the proof of concept is accomplished. Catalytic oxygen
atom transfer from non-oxidant lignin to cellulose or hemicellulose by organic chemicals is reported. As
expected, the catalytic reaction is a novel method for the selective and quantitative hydrolytic depolymerization of lignocelluloses into liquid products in a one-pot reaction. Lignin is converted quantitatively
into small molecular aromatics, simultaneously, cellulose and hemicellulose are converted quantitatively
into small organic acids with lactic acid up to 50%. Small molecular aromatics can be converted into diesel
blend via one-step methylation. Neither black tar formation nor gasication is observed in the catalytic
oxygen atom transfer reactions, conversion of biomass to products is quantitative.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Highly selective depolymerization of lignocellulose for decent
yields of small molecular organics using the fewest number of
steps is the key for economically producing fuels or chemicals
from biomass [1]. Small molecular organics function as excellent
Corresponding author at: Sun Pharmaceuticals, Inc., San Diego, CA 92128, USA.
E-mail address: zuolinzhu@yahoo.com (Z. Zhu).
URL: http://www.ussunpharm.com (Z. Zhu).
http://dx.doi.org/10.1016/j.fuel.2015.01.109
0016-2361/ 2015 Elsevier Ltd. All rights reserved.

intermediates for fuels or chemical products based on current

technologies [2,3]. Many well-known methods for the depolymerization of lignocelluloses, or its pure components, have been
proved to be commercially impractical due to a high operation
cost. Thermal-chemical methods, such as liquefaction and pyrolysis, show no product selectivity. These methods always result in
the formation of black tar and low yields of liquid products [4].
Separation/isolation and purication of components rst, followed by depolymerization, such as hydrolysis of cellulose into

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Z. Zhu, J. Zhu / Fuel 148 (2015) 226230

Fig. 1. Designed one-pot catalytic depolymerization of lignocelluloses. Through oxygen atom transfer, lignin will be converted into small molecular aromatics, and cellulose
is transferred into small carboxylic acids.

Table 1
The results of catalyst screening tests at 250 C. 1 l stainless steel, 750 ml of distilled water, 112 g of dried pinewood, 60 g of sodium, 2 g of catalyst.
Catalyst

Gas (%)

Tar (%)

Residue (%)

Catalyst

Gas (%)

Tar (%)

Residue (%)

No
PPh3
PMe2Ph
PEtPh2
PEt3
RuO2
CeO2
ZrO2
OsO2
Cr2O3
MnO2
Fe
Zn

6.2
6.1
5.3
5.3
5.1
9.8
11
8.2
9.9
11
10.3
10.2
11

11
13
11
10.5
11
7.5
6.8
6.6
7.2
5.5
6.2
7.8
8.1

23
25
22.8
23.5
24.2
28.5
30.2
27.6
27.6
30
26.9
25.5
26.2

AQ
NaSO3AQ
Pyridine
N-Me morpholine
Et3N
Me2S
H5PV2Mo10O40
MeReO3
Ti(O-iPr)4
VO(acac)2
Cr(TPP)Cl
Mn(TPP)Cl
Fe(TPP)Cl

0
0
4.2
3.8
5.8
5.4
8.6
10.5
7.6
7.3
9.2
8.9
10

0
0
16
16
15
12.6
9.2
7.6
12
11
7.3
7.2
9.2

0.2
0
25
24.6
23.8
24.1
15.3
21.2
15.5
16.3
20.2
20.7
25.1

TPP: tetra phenyl porphyry.

Table 2
The results of catalytic oxygen atom transfer with different temperatures. 1 l stainless
steel, 750 ml of distilled water, 112 g of dried pinewood, 60 g of sodium, 2 g of
catalyst.

Table 3
The results of catalytic oxygen atom transfer with different catalyst loadings. 1 l
stainless steel, 750 ml of distilled water, 112 g of dried pinewood, 60 g of sodium.

Temperature (C)

Gas (%)

Tar (%)

Residue (%)

Catalyst loading (wt%)

Gas (%)

Tar (%)

Residue (%)

200
210
220
230
240
250
260
270
280
290
300

0
0
0
0
0
0
0
0
0.2
0.5
1

1
1
0.5
0.7
0
0
0
0
0
0
0.5

11
8
5
1.5
0.3
0
0
0
0
0
0.5

10
5
2
1
0.5
0.2
0.1
0.05
0.02
0.01
0.005

0
0
0
0
0
0
0
Trace
Trace
0.2
0.3

0
0
0
0
0
0
0
0
0
0.7
0.7

0
0
0
0
0
0
0.5
0.5
0.6
1.3
1.5

glucose [5], or depolymerization of lignin into small molecular

aromatics [6,7], show a huge loss of organic carbon in percentage.
One-pot co-depolymerization of cellulose, lignin, and hemicellulose with high product selectivity is possible. Lignin is a complex
polymer of aromatics with oxygen content up to 37% [8]. The ideal
products from lignin are small molecular aromatics with reduced

oxygen content. Meanwhile, cellulose and hemicellulose are

oxygen acceptors and will be converted into small organic acids.
Catalytic atom transfer reactions are preferred by industrial processes because these kinds of reactions have good to high product
selectivity and atom economy [9].

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Z. Zhu, J. Zhu / Fuel 148 (2015) 226230

Small molecular aromatics are important components in liquid

transportation fuels, and starting materials for high performance
polymers. With the increased yields of shale gas and methane
hydrate that contain no aromatic components, the cost of producing aromatics is expected to increase [10]. Organic acids are important commodity products with broad applications in many areas.
For example, esters are better solvents for paints and ink than
alkane-based organic solvents, because esters are biodegradable
and have excellent dissolving power [11]. Esters are also effective
liquid fuels, possessing a higher or similar heat of combustion,
and better anhydrous product yields, than that of ethanol. Additionally, they are non-toxic and, unlike ethanol, non-corrosive.
Organic acids can also be converted into many useful chemicals.
For example, lactic acid can be converted into n-propanol, 1,2-propanediol, acrylic acid, propanoic acid, etc. Until now there is no
cost effective method for making small organic acids from biomass.
Alkaline hydrothermal methods produce a mixture of products
containing more than a hundred different chemicals. Another
problem regarding the disproportionation reaction is that it has
no specicity in terms of products; the product mixture contains
more than 25 monocarboxylic acids, 22 dicarboxylic acids, and several cyclopentyl chemicals [12]. With oxidation methods [13]
strong oxidants have to be used at elevated temperatures, such
as concentrated hydrogen peroxide [14,15] and nitric acid [16].
There are safety issues using strong oxidants with these processes.
Additionally, multi-hydroxyl organic acids, such as tartaric acid,
glucaric acid, gluconic acid, and threonic acid, are formed. Multihydroxyl organic acids are difcult to isolate and purify, therefore,
their use is limited.
Here we report a novel method for a catalytic one-pot hydrolytic depolymerization of all natural organic polymers (CoDOP
method), with good product selectivity, via catalytic oxygen atom
transfer from lignin to cellulose or hemicellulose mediated by
organic molecules. Catalytic oxygen atom transfer reaction from
non-oxidant organic chemicals facilitated by organic molecules
has not been reported before.

2. Experimental
The organic acids are analyzed using HPLC method. All volatile
products such as phenols are analyzed using GCMS. LCMS method
is used for the analysis of molecular mass of small molecular

Lignin
OH

O
O

O
OH

H OH

aromatics. Gasication of the reaction is measured via gas product

analysis (see Supplementary data for details).
Screening tests are carried out using a 1 l stainless steel autoclave equipped with mechanical stirrer. 750 ml of distilled water
is used as solvent, 112 g of dried pine wood particles (2 mm size,
contains cellulose: 40%, lignin: 30%, hemicellulose: 28%, ash: 1%,
the carbon content is 51%), 60 g of sodium hydroxide is used to
neutralize small organic acids, and 2 g of catalyst is used (the background is the reaction without using any proposed catalyst). The
temperature screened is 150, 170, 190, 210, 230, 250, 270, 290,
and 310 C. The screening procedure is: the autoclave is sealed
after all materials are loaded, purged with nitrogen three times,
then lled with a positive nitrogen pressure P0, heated to designed
reaction temperature at a rate of 5 C/min and maintain at this
temperature for 60 min. After cooling to room temperature, the
nal pressure Pf is recorded and compared with P0. Gas product
is collected and sampled for gas analysis. The liquid mixture
obtained is worked out for non-reacted biomass, black tar, and
hydrolysis yield (see Supplementary data for details).
3. Results and discussion
3.1. Screening tests
For catalytic oxygen-atom transfer from lignin to cellulose and
hemicellulose, there will only be two kinds of products of small
organic chemicals from biomass depolymerization: organic acids
and small molecular aromatics, shown by Fig. 1. Lignin is not considered as an oxidant in current chemistry. In order to show the
proof of concept, many chemicals that have the ability to accept
oxygen atoms were selected for the screening tests. These chemicals include pure metal powder such as Fe and Zn; metal oxides
such as BaO, RuO2, CeO2, ZrO2, RuO2, OsO2, MnO2, and Cr2O3;
metal complexes such as Ti(O-iPr)4, VO(acac)2, Cr(TPP)Cl,
Mn(TPP)Cl, Fe(TPP)Cl, and MeReO3; phosphines such as PPh3,
PEt2Ph, PEtPh2, and PMe2Ph; polyoxometalates such as
H5PV2Mo10O40; organics such as pyridine, N-methylmorpholine,
triethylamine, dimethyl sulde, anthraquinone, and sodium
anthraquinone-2-sulfate. The results of screening tests show that
gasication (10%) and large quantities of solid residue (2030%)
are observed for all the reactions when transition metals are present in catalysts. Phosphines, amines, and sulde have no effect on
the designed reaction (compared with background reaction that
did not use any catalyst). Anthraquinone and sodium anthraquinone-2-sulfate give expected results, there is almost no solid residue after reaction, and no gasication detected. Because the
designed oxygen-atom transfer reaction will produce only small
molecular aromatics and small organic acids, these two kinds of
products are soluble in solution in reaction media. There should
be neither gaseous molecules that contain carbon nor solid residue after reaction. Table 1 contains the results of a screening test
that was carried out at 250 C. This data is the average of three
experiments. Gas is the carbon molar percentage of the starting
material, calculated by measuring the total carbon in gaseous
product (CO, CO2, and CH4), then dividing by the total molar carbon in starting materials. Residue is the solid left after reaction.
Tar is the methanol soluble part of the residue. Both of them
are reported as weight percentage to starting material.
3.2. The results of catalytic oxygen atom transfer

O
Fig. 2. Possible catalytic oxygen transfer pathways for the catalytic one-pot
hydrolytic depolymerization of lignocellulose.

Two parameters are chosen for the optimization of catalytic

oxygen atom transfer, they are temperature and loading of catalyst
(weight percentage to biomass). The results of these experiments
are tabulated in Tables 2 and 3.

Z. Zhu, J. Zhu / Fuel 148 (2015) 226230

229

Lignocelluloses
Catalytic One-pot Quantitative Hydrolysis
100%

Small Organic Molecules

Extraction

Aqueous Layers
~100%

Small Molecular Aromatics

>99%

1. Removal of water at pH=10

2. Extraction with ether/HCl gas

Small Organic Acids

Fig. 3. Biorening scheme for the catalytic one-pot hydrolytic depolymerization of lignocellulose via oxygen atom transfer. (The yield of small molecular aromatics is
calculated based on the percentage content of lignin in biomass used. The yield of small organic acids is calculated based on the percentage content of cellulose and
hemicellulose in biomass used.)

The results show that a suitable reaction temperature is in the

range of 230270 C in a one hour reaction time. Below 230 C,
unreacted starting material is obvious. Gasication is observed
for the reaction with temperature above 280 C. Considering the
loading of catalyst (sodium anthraquinone-2-sulfate), 0.1 wt% of
catalyst to biomass is enough as it still gives completed hydrolysis
of biomass. Unreacted starting material biomass is isolated and
gasication is observed for the reaction with catalyst loading
below 0.05 wt%.
3.3. Scale up, product separation and identication: catalytic one-pot,
selective, hydrolytic depolymerization of lignocelluloses
Scale up is carried out in a 10 l stainless steel autoclave
equipped with mechanical stirrer using modied screening procedure. 1120 g of pinewood is used, and the ratio of solid biomass to
solvent is 1:7. The catalyst (sodium anthraquinone-2-sulfate) loading is 1.12 g (0.1 wt%). The autoclave is sealed, purged with nitrogen three times, then lled with nitrogen at a positive pressure,
heated to 250 C, and stirred at this temperature for 60 min. After
cooling to a temperature below 50 C, a brown colored solution is
obtained. This color is similar to the color of the biomass (pinewood) used, which suggests that there is no black tar formation.
The color darkens after the mixture is exposed to air, which suggests that some phenols are formed and oxidized to quinones once
contact with air. Filtration shows no signs of solid residue in the
product solution, concluding that the percentage of hydrolytic
depolymerization is about 100%. The reaction mixture is collected
and the autoclave is washed with a small amount of 1% NaOH
aqueous solution, 910 ml liquid is obtained.
HPLC analysis of the solution shows that only several small
organic acids are formed, such as formic acid, glycolic acid, acetic
acid, lactic acid and succinic acid. It contains 399 g of lactic acid
(>50% of cellulose plus hemicellulose), 138.5 g of glycolic acid,
151 g of formic acid, 19.8 g of acetic acid, 38 g of succinic acid,
and the rest are 2-hydroxyl isobutyric acid, fumaric acid, etc.
Fig. S1 illustrates the product distribution of small organic acids
for this scale up of catalytic one-pot hydrolytic depolymerization
of lignocellulose.
The reaction solution is mixed with equal volumes of benzyl
alcohol and acidied with hydrochloric acid to pH = 4.2. The
organic phase is separated and washed once with a half volume
of water. HPLC analysis shows there is no organic acid in organic
solution. The benzyl alcohol is carefully removed under reduced
pressure to obtain 293 g of sticky products. GC analysis shows it

contains 4.9% benzyl alcohol. The weight of the small aromatics

obtained is 278.6 g-its yield is 100% based on lignin weight. Molecular mass analysis shows they are mixtures (Fig. S2), most with a
molecular weight between 162 and 340. Elemental analysis shows
that the oxygen content of this product is 18%, far below the oxygen content of lignin (36%). This result suggests that more than
50% of oxygen atoms are transferred from lignin to cellulose or
hemicellulose, because this 18% of oxygen in small molecular aromatics includes some oxygen incorporated from water via lignin
hydrolysis reaction.
Methylated small molecular aromatics are obtained as
described in experimental section. 1H NMR of this aromatic
product shows that the ratio of aliphatic hydrogen to aromatic
hydrogen is 4.8:1 (Fig. S3), a ratio of the current diesels.
3.4. Possible catalytic pathways
Based on the results of our experiments, dioxirane intermediate
is proposed as a potential key catalytic substance, as shown in
Fig. 2.
First, the ether linkage of lignin is broken by a hydroxide anion
to form a alkoxide anion; then the alkoxide (or phenoxide) anion
attacks the carbonyl group of anthraquinone, the formed anthraquinone anion intermediate rearrange to kick off alkyl (or phenyl)
group and produce dioxirane intermediate, meanwhile, alkyl (or
phenyl) group abstract hydrogen from water to yield smaller
molecular aromatic with reduced oxygen content. The ether linkage of smaller molecular aromatics can be used for further reactions until there is no ether linkage inside the molecules. These
kinds of molecules are the expected products of small molecular
aromatics. Dioxirane is known to be good oxidant for oxidizing primary alcohols to carboxylic acids [17] and secondary alcohols to
alpha-hydroxy ketones [18]. Monosaccharide units of cellulose
and hemicellulose contain many secondary alcohols, and are oxidized by dioxirane to ketone intermediates. Then these ketone
intermediates go on rearrangement [19] to form carboxylic acid
such as formic acid, lactic acid and acetic acids. These small organic
acids are the another kind of expected products.
4. Conclusions
Catalytic oxygen atom transfer from lignin to cellulose and
hemicellulose is proved to be possible. Quantitative conversion of
lignocellulose into small organic molecules is achieved. This novel

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Z. Zhu, J. Zhu / Fuel 148 (2015) 226230

approach has very high product selectivity as there are only two
kinds of products formed (Fig. 3). Lignin is converted into small
molecular aromatics with reduced oxygen content. Meanwhile,
cellulose and hemicellulose are oxidized into small organic acids
with lactic acid up to 50%. Small molecular aromatics can be converted into diesel blend via one-step methylation. This novel
method for biorening has the huge potential to make liquid fuels
and chemicals with a lower cost than that of the products from
petro-chemical process. Our current study is focused on a novel
method for stabilizing small organic acids other than neutralization with base, in the hope to further lower process cost.
Acknowledgments
This research was supported by grants from the Key Project of
the National 863 Program of China (2010AA10Z404). We acknowledge the nancial support from Huaibei Mining Group.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.fuel.2015.01.109.
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