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Ist International Conference on New Frontiers in Biofuels, DTU

January 18-19, 2010, New Delhi

ID: 2010/NFIB/004
High Energy Furane based Biofuel from Cellulose
Y. P. Chauhan*, Ankit Singh and Anoop Meshram
Department of Chemical Engineering, College of Engineering & Technology, Akola, Maharashtra
*E mail ID: yp_chauhan@yahoo.co.in

ABSTRACT
Today world is marveling at the technological revolution, this has helped the human race but
mismanagement has led to various problems. One of the burning issues is fuel crisis. The
consumption of fuels is increasing by leaps and bounds which ultimately leads to price hike. The
present day fuels are the product of natural changes in organic matter over millennia, has
accumulated beneath the earths surface. The exploitation of these reservoirs are very high, due
to this these reservoirs are going to be over sooner or later. Thus there is need of promising
alternative fuel for future. Today population of world is increasing consequently the consumption
of petroleum products is also increasing. Sources of petroleum are going to be exhausted one
day. Then what will be scenario of world? Imagination only causes threat but answer to this
question is Bio-fuels. Cellulose is the most abundant organic compound with the formula
(C6H10O5)n. On globe approximately 1015 Kg/yr is synthesized and degraded and is found in plenty
in nature in the form of cotton, hemp, jute, flax etc. Chloromethylfurfural (CMF) is a promising
alternative fuel manufactured from cellulose. The cellulose itself, is converted into furanic
products in isolated yields of greater than 80% by conversion mainly into 5-(Chloromethyl)furfural
(CMF), a hydrophobic molecule which is easily sequestered into organic solvents in a two-phase
reaction medium. Thus, microcrystalline cellulose was added to a stirred solution of lithium
chloride (5 wt %) in concentrated hydrochloric acid to give a homogeneous mixture, which was
introduced into a reaction chamber containing the solvent and extraction has been done. The
combined organic extracts were distilled to recover the solvent, and the residual liquid was
chromatographed for isolation of Chloromethyl furfural (CMF). While CMF is itself not a biofuel
candidate, it is converted into ethoxymethylfurfural (EMF) in nearly quantitative yield by stirring it
in ethanol solution at room temperature, which is a promising biofuel.
Keywords: Biofuel, Cellulose, Chloromethylfurfural (CMF), Extraction, Lithium chloride,
Hydrochloric acid, Ethoxymethyl furfural (EMF)

1. INTRODUCTION
Today world is marveling at the technological revolution, this has helped the human race but
mismanagement has led to various problems. One of the burning issues is fuel crisis. The
consumption of fuels is increasing by leaps and bounds which ultimately leads to price hike. The
present day fuels are the product of natural changes in organic matter over millennia, has
accumulated beneath the earths surface. The exploitation of these reservoirs are very high, due
to this these reservoirs are going to be over sooner or later. Thus there is need of promising
alternative fuel for future. Today population of world is increasing consequently the consumption
of petroleum products is also increasing. Sources of petroleum are going to be exhausted one
day. Then what will be scenario of world? Imagination only causes threat but answer to this
question is Bio-fuels.
These are days of great incentive in the field of bioenergy research. The stakes, of course, are
immense economic independence from politically unstable, petroleum-exporting countries, the
remediation of greenhouse gas levels in the atmosphere and their potential effect on the climate,
and mitigation of the economic consequences of our imminent arrival at the peak oil point,
particularly in light of the pace of industrialization of emerging economic superpowers in Asia. It
may be said that the final answer to the global energy issue will lie most credibly in ultraclean
technologies based on hydrogen and solar energy. However, few would deny a more immediate
future to carbon-based fuels, in view of the prevailing automotive infrastructure based on the
internal combustion engine, as well as the fact that the chemical industry will always require
feedstock for the production of organic materials and chemicals, regardless of what is being used
for energy. The challenge to a new carbon-based fuel economy, as it emerges, is twofold: First,

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Ist International Conference on New Frontiers in Biofuels, DTU


January 18-19, 2010, New Delhi

the carbon source must ultimately be atmospheric carbon dioxide, which is most practically
harvested by the photosynthetic production of cellulose, hemicellulose, starch, and simple sugars,
and second, these saccharides must be efficiently converted into molecules which are ambient
temperature liquids of low volatility and high energy content. To some extent, the above challenge
is currently being met by the production of ethanol from either starch-derived glucose or cane
sugar, but this has largely been an issue of expediency, making use of mature technologies
(agriculture and brewery/distillery) that were established long before energy became an issue,
and the approach is now considered by many to be transitional.
Cellulose is the most abundant organic compound with the formula (C6H10O5)n. On globe
15
approximately 10 Kg/yr is synthesized and degraded and is found in plenty in nature in the form
of cotton, hemp, jute, flax etc. Also a good percentage of wood consists of cellulose. Cellulose
has an extremely high degree of crystallinity and this is due to the formation of several hydrogen
bonds originating from its hydroxyl groups. Its high stereo-regularity is also a contributory factor
for its high crystallinity. Pure cellulose also known as - cellulose is that material insoluble in 17.5
% NaOH. -cellulose and -cellulose are not true cellulose. cellulose beloved to be degraded,
low degree of polymerization cellulose, is insoluble in 17.5 % NaOH; -cellulose is completely
soluble at any pH and is though to be the hemicelluloses such as xylans, mannas, galactans etc.
Since cellulose is by far the major form of photosynthetically fixed carbon, it can be argued that it
should be the principal focus of any emerging carbon-fuel technology. The difficulty, from the
point of view of ethanol production, is that fermentable sugars are not easily liberated from this
material. The current model for cellulose utilization involves saccharification with immobilized
enzymes, but despite recent advancements, this remains a slow and expensive process. The
carbon economy of glucose fermentation is poor; during production of 10gm of ethanol 9.6 gm
CO2 is released. Thus production of ethanol has some contribution to global warming.
Researchers have developed a new simpler process for conversion of cellulosic biomass in to
furanics- high energy, furan based organic liquids. These furanics are mainly furfural which can
be used as fuel when blended with ethanol.
Furfural has an aromatic odor reminiscent of almonds. Its exceptional physical properties make
from this hetero-aromaticaldehyde a selective solvent for refining lubricating oils. In the
manufacture of resin-bonded grinding wheels and refractory materials this biomass based
chemical is used at the same time as a reactive chemical and as solvent. Furfural is the sole
industrial source for furfuryl alcohol, tetrahydrofurfuryl alcohol, furoic acid, furfurylamine,
methylfuran and furan. The furfuryl alcohol is its principal derivative. Since the sixties and
seventies furfuryl alcohol resins replace oil based binders in the foundry industry.

2. EXPERIMENTAL SETUP
2.1. REAGENTS AND CHEMICALS
Microcrystalline cellulose (MCC) was taken as prepared by final year students of Chemical
engineering in their project. 1, 2-Dichloroethane, lithium chloride, hydrochloric acid, sodium
sulfate was of analytical reagent grade supplied by S. D. Fine Chemicals (INDIA). These chemical
were used as received without further purification.

2.2. METHODOLOGY
Chloromethylfurfural (CMF) is a promising alternative fuel manufactured from cellulose. The
cellulose itself, is converted into furanic products in isolated yields of greater than 80% by
conversion mainly into 5-(Chloromethyl) furfural (CMF, 2), a hydrophobic molecule which is easily
sequestered into organic solvents in a two-phase reaction medium. The experimental setup used
for this purpose is a standard apparatus for continuous extraction of an aqueous solution with a
solvent of greater density than water.
1,2-Dichloroethane (500 mL) was introduced into the extraction chamber of a standard apparatus
for continuous extraction with a solvent heavier than water. A homogeneous suspension of
microcrystalline cellulose (2.05 g, 5% water by mass) was prepared in a solution of lithium

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Ist International Conference on New Frontiers in Biofuels, DTU


January 18-19, 2010, New Delhi

chloride (10 g) in concentrated hydrochloric acid (150 mL), and this was added to the extraction
chamber. A boiling flask containing 1,2-dichloroethane (150 mL) and anhydrous sodium sulfate
was attached to the apparatus and the solvent was heated to reflux. The aqueous slurry was
heated at 650 C with continuous mechanical stirring and subjected to continuous extraction for 18
h. At this point, further LiCl (5 g) in concentrated hydrochloric acid (75 mL) was added to the
extraction chamber and extraction was continued for another 12 h. During the extraction the
boiling flask was emptied every 6 h and replaced with fresh 1,2-dichloroethane (150 mL). The
combined organic extracts were distilled to recover the solvent, and the residual oil (1.469 g) was
chromatographed

3. RESULTS
The chromatographic analysis (silica gel, CH 2Cl 2 :Et2 O, 2:1 gradated to CH 2Cl 2 :MeOH, 95:5)
gives 5-(chloromethyl)furfural (2) (1.233 g, 71 %), 1H NMR (CDCl 3 ) 4.36 (s, 2H), 6.32 (d, 1H),
6.95 (d, 1H), 9.25 (s, 1H), 13C NMR (CDCl 3) 36.1, 111.6,122.1, 152.2, 155.3, 177.1; 2-(21
hydroxyacetyl) furan (3) (0.116 g, 8 %), H NMR (CDCl 3 ) 3.26 (brs, 1H), 4.71 (s, 2H), 6.56 (t,
13
1H), 7.26 (d, 1H), 7.60 (d, 1H), C NMR (CDCl 3) : 65.2, 112.7, 118.02, 147.2, 150.3, 187.8; 5(hydroxymethyl) furfural (1) (0.082 g, 5 %), 1H NMR (CDCl 3) 3.51 (brs, 1H), 4.66 (s, 2H), 6.50
(d, 1H), 7.21 (d, 1H), 9.51 (s, 1H), 13C NMR (CDCl 3) d: 56.9, 110.1, 123.9, 151.8, 162.0, 178.1;
and levulinic acid (4) (0.011 g, 1%), 1H NMR (CDCl 3) d 2.17 (s, 3H), 2.59 (t, 2H), 2.73 (t, 2H), 13C
NMR (CDCl 3) d: 27.9, 29.9, 37.8, 178.2, 207.0. Filtration of the remaining aqueous layer gave a
fine, black humic material (0.10 g).

4. DISCUSSION
The following products were isolated: 5-(chloromethyl) furfural (71%), 2-(2-hydroxyacetyl) furan
(8%), 5-(hydroxymethyl) furfural (5%), and levulinic acid (1%). Filtration of the remaining aqueous
layer gave a small quantity of fine, black, humic material (5% by mass). The total, isolated yield of
simple organics is thus a remarkable 85%. Applying the same reaction conditions to glucose gave
(71%), (7%), (8%), (3%), and humic material (4% by mass), for a total organic yield of 89%.
Finally, we were also interested in applying this method to sucrose, since it is currently the
principal raw material used globally to produce bioethanol. Here isolation of (76%); (6%); (4%);
(5%), and humic material (3% by mass), for a total organic yield of 91%. Systematic variations of
the time, temperature, and LiCl concentration of the reaction have shown that these parameters
are very nearly optimal for glucose, sucrose, and cellulose using the present experimental setup.
The quantity of HCl/LiCl solution and dichloroethane solvent used was a matter of convenient
handling and has not been optimized.
Conversion of glucose into furanic products.
Using the general procedure described above, glucose (2.01 g) gave crude product (1.425 g)
which was chromatographed to give 5- (chloromethyl) furfural (2) (1.145 g, 71%), 2-(2hydroxyacetyl) furan (3) (0.103 g, 7%), 5-(hydroxymethyl)furfural (1) (0.116 g, 8%), levulinic acid
(4) (0.032 g, 3%), and humic material (0.090 g).
Conversion of sucrose into furanic products.
Using the general procedure described above, sucrose (2.06 g) gave crude product (1.543 g)
which was chromatographed to give 5- (chloromethyl)furfural (2) (1.322 g, 76%), 2-(2hydroxyacetyl)furan (3) (0.090 g, 6%), 5- (hydroxymethyl)furfural (1) (0.055 g, 4%), levulinic acid
(4) (0.064 g, 5%), and humic material (0.070 g).

5. MATERIAL AND ENERGY BALANCE


5.1. ANALYSIS FOR FLOW THROUGH REACTOR
Background
We will take as our reactor a well-mixed CSFR (continuously stirred flow through reactor). We
consider two input streams and one exit stream as shown in the following flow sheet.

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Ist International Conference on New Frontiers in Biofuels, DTU


January 18-19, 2010, New Delhi

Stream # 1 contains HCl (species A), cellulose (C6H10O5, species B), water (H2O, species C) and
LiCl (species D), which does not react. Stream # 2 contains a pure solvent stream (C2H2Cl2
species E) which also does not react. The exit stream #3 contains H2O, C6H10O5, C6H5ClO2
(species F, also known as CMF), HCl, LiCl and C2H4Cl2.

5.2. MATERIAL BALANCE


The species balance for any species i for the above reactor shown in figure 1 is
- (Mi)1 - (Mi)2 + (Mi)3 = Ri,
i = A, B,F(1)
Here Ri is the rate of production of species i. The notation (Mi)j is the molar flow rate of species i
in the jth stream. Based on experimental data we conservatively estimate that the fractional
conversion of cellulose (species B) is

...(2)
The constraints on the stoichiometry are given by

.......................................................................................(3)
where Nji is the composition matrix for the reacting species given by

....(4)
The columns represent species A, B, C, F; the rows represent atomic species C, H, O, Cl.
Solving Eq. 3 we get the constraints on the production rates Ri which are
RA = - RF
RB = - RF
RC = 3 RF .......(5)
The molar flow rates per unit time entering to the reactor are specified as follows
C6H10O5
: 1.5/162
= 0.00925926
HCl
: 98.235/36.46 = 2.69432
: 167.28/18
= 9.29333
H2O
LiCl
: 15.42.39
= 0.353857 ...(6)
The total molar flow rate is (MT)1 =12.350766 mol/time.
For our calculation we will assume basis for the inlet flow rate of 100 mol/hr. We can readily solve
the species balances Eq. 6 in conjunction with Eq. 5 to obtain the following composition for
stream #3
(MA)3 = 21.7655 mol/hr
(MA)3 = 0.025489 mol/hr
(MA)3 = 75.3914 mol/hr
(MA)3 = 2.865 mol/hr
(MA)3=0.0494787mol/hr (7)
The species rates of production are
RF = 0.04948 mol/hr, RA = RB = - RF
RC=0.146436mol/hr ..(8)

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Ist International Conference on New Frontiers in Biofuels, DTU


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5.3. ENERGY BALANCE


For our reactor we can write the following energy balance

...(9)
Here (Hij) is the partial molar enthalpy of the ith species in the jth stream and -Q is the net rate of
heat input into the reactor. Now the last term of the LHS of the energy balance can be rearranged
using the species balances (see Eq. 1) to obtain

. (10)
For simplicity we assume that all streams behave ideally and that the temperature of the streams
is T=65C. Thus the energy balance becomes
- Hrxn RF = - Q .(11)
Here Hrxn is the heat of reaction evaluated at T=65C. To determine the heat of reaction we use
the following heats of formation at standard conditions and ideal heat capacities at standard
conditions.
Heats of formation
HCl
C6H12O6
H2O
C6H5O2Cl

:
:
:
:

HA0 (T = 25 0C) = - 167.2 kJ/mol


0
0
HB (T = 25 C) = - 1267.8 kJ/mol
0
HC (T = 25 0C) = - 285.8 kJ/mol
HF0 (T = 25 0C) = - 227.05 kJ/mol (12)

To determine the heat of reaction at T=65C, we use


Hrxn = H0rxn + Cp (65 - 25)
Cp = (-CPA - CPB + 3 CPC + CPF) .(13)
Ideal heat capacities
HCl
C6H12O6
H2O
C6H5O2Cl
O2
CO2

:
:
:
:
:
:

CP,A
CP,B
CP,C
CP,F
CP,O2
CP,CO2

= 29.56 J/mol K
= 198.2 J/mol K
= 33.65 J/mol K
= 132.95 J/mol K
= 29.36 J/mol K
= 39.41J/mol K .(14)

Note: because of the uncertainty in determining the heat of formation for cellulose we have used
glucose as a substitute for cellulose in the energy calculations.
From the energy balance Eq. 11, we find
Q = 18.6596 kJ/hr ...(15)
Thus from the heat balance gives
Q = 18.6596 kJ/hr ...(16)
Since Q > 0, this means that the reaction is endothermic and we need to supply heat to the
reaction to maintain isothermal operation. It is of interest to determine if heat of combustion of the
CMF in stream #3 exceeds this value, and if so by how much.
The heat of combustion of species F in stream #3 is given by
C6H5O2Cl (l) + 6 O2 (g)
6 CO2 (g) + 2 H2O (l) + HCl (l) .(17)
H0C, CMF = 6 H0F, CO2 + 2 H0F, H2O + H0F, HCl - H0F, CMF ..(18)

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Ist International Conference on New Frontiers in Biofuels, DTU


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Substituting in the heats of formation we find


H65 deg.C C, CMF = H0C, CMF + Cp (65 - 25) = - 2871.78 kJ/mol ...(19)
And based on our material balance the molar flow rate of CMF is
(MF)3=0.0494787mol/hr ...(20)
Thus the potential thermodynamic energy in the form of CMF produced by the reaction is
65deg.C
H
C,CMF(MF)3=-142.092 kj/hr .(21)
Note a negative heat of combustion implies that energy is produced by the combustion reaction.
The ratio of heat added to the reactor to energy potential of CMF is therefore
Thermodynamic energy of CMF
142.092
Energy supplied to the reactor
= 18.6 = 7.6393 .(22)

6. CONCLUSION
The nearly identical results obtained for cellulose and glucose suggest that the rate-limiting
component of the process is not the hydrolysis of cellulose, but the dehydration of glucose or the
drop wise extraction of the furan products. A more aggressive extraction protocol would almost
certainly reduce the reaction times. While CMF is itself not a biofuel candidate, it is converted into
ethoxymethylfurfural (EMF) in nearly quantitative yield by stirring it in ethanol solution at room
temperature. Interestingly, EMF a liquid with a boiling point of 2350C, is already considered to be
a promising alternative fuel, the energy density of which is reported to be 8.7 kWhL_1,
substantially higher than that of ethanol (6.1 kWhL_1), and comparable to that of standard
gasoline (8.8 kWhL_1) and diesel fuel (9.7 kWhL_1).EMF has been tested in blends with diesel
fuel by Avantium Technologies, a spin-off of Royal Dutch Shell, who noted that the test yielded
positive results for all blends tested. The engine ran smoothly for several hours. Exhaust analysis
uncovered a significant reduction of soot.

REFERENCES
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Journal of Angew. Chem.,Int. Ed. 2008; 47: 79247926.
2. Binder Joseph B. and Raines Ronald T. Simple Chemical Transformation of Lignocellulosic
Biomass into Furans for Fuels and Chemicals. J. Am. Chem. Soc., 2009; 131 (5):1979-1985.
3. Process for producing a furan derivative, U.S Patent Documents: 4076733, Inventors:
Hamada; Kazuhiko (Ibaraki, JP),Nagase; Tsuneyuki (Takatsuki, JP),Suzukamo; Gohu
(Ibaraki, JP)
4. Lewis NS and DG Nocera. Proc. Natl. Acad. Sci. USA. 2006;103: 15729.
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8. Doerfler J, Amorim HV, Zuckerindustrie 2007; 132: 694.
9. In practice this may not be a crucial parameter. Since the only reagent consumed in this
process is hydrogen chloride, a flow reactor could be envisaged where the saccharide is
continuously introduced, 14 are continuously removed, and the concentration of HCl is held
constant by introduction of the gas into the reactor. A preliminary modeling study of this
process is included in the Supporting Information.
10. Gruter GJM, Dautzenberg F, Eur. Pat. Appl, 2007;1834950A1
11. Avantium Technologies press release: http://www.avantium. com/index.php?p = 115&n = 2.
12. Hamada K, Suzukamo G and Fujisawa K. The literature yield for this reaction is up to 95 %,
depending on which solvent is used. Eur. Pat. Appl.1982; 44186A1.

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January 18-19, 2010, New Delhi

13. Jap. P. 58013576, 1983.


14. A reviewer brought the importance of processing these materials to negligible halogen levels
to our attention. To this end, we have determined that no residual solvent or CMF (2) is
1

13

present in the istillates to the detection limits of H and C NMR, and analysis by ASTM
D4208 (oxygen bomb combustion selective electrode method) shows that the chlorine content
is < 0.5%.
15. de Man JM, Principles of Food Chemistry, 3rd ed., Springer, Heidelberg, 1999.
16. Michail K, Matzi V, Maier A, Herwig R, Greilberger J, Juan H, Kunert O and Wintersteiger R,
Anal. Bioanal. Chem. 2007; 387: 2801.
17. Fenton HJH. and Gostling M. J. Chem. Soc. Trans. 1901; 79: 807.
18. Hibbert H and Hill HSJ. Am. Chem. Soc. 1923; 45:176.
19. Sanda K, Rigal L and Gaset A. J. Chem. Technol. Biotechnol. 1992; 55: 139.
20. Kuster BFM and Van der Steen HJC.,Staerke 1977, 29, 99. HMF and CMF are also readily
interconvertable: a) K. Sanda, L. Rigal, A. Gaset, Carbohydr. Res. 1989, 187,15; b) W. N.
Haworth, W. G. M. Jones, J. Chem. Soc. 1944, 667.
21. 2-(2-Hydroxyacetyl) furan (3) is a well-known aroma component of several natural
substances, for example, toasted oak in wine barrels: I. Cutzach, P. Chatonnet, R. Henry, D.
Dubourdieu, J. Agric. Food Chem. 1999, 47, 1663.
22. Levulinic acid is a well-studied derivative of cellulosic biomass and is considered a promising
building block for bio-derived polymers and fuel additives; see: BiorefineriesIndustrial
Processes and Products: Status Quo and Future Directions (Eds.: B. Kamm, P. R. Gruber, M.
Kamm), Wiley-VCH, Weinheim, 2007.
23. Thermodynamic data used in the above calculations was taken from several sources:
Reklaitis (1983), Sandler (2006), and the software package ChemDraw. The calculations
described above are routine in chemical engineering and are described by Sandler (2006).
24. Reklaitis G V, Introduction to Material and Energy Balances, John Wiley & Sons, 1983 S. I.
Sandler, Chemical, Biochemical and Engineering Thermodynamics, John Wiley & Sons, 2006

Figure 1. Reactor flow sheet

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