United States
Environmental Protection
Agency
Municipal Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-81-201 Nov. 1982
Project Summary
Development of
Methods for the
Stabilization of Pyrolytic Oils
M. B. Polk and M. Phingbodhippakkiya
In this study, capillary gas chroma-
tographic, liquid chromatographic,
and gas chromatographic mass spectro-
metric procedures were developed for
analyzing pyrolytic oils. The major
components of the oils and the chemi-
cal reactions that cause polymeriza-
tion were identified. Some of the
major components identified in pyro-
lytic oils were ethanol, 1-butanol,
guaiacol, naphthalene, eugenol, acet-
aldehyde, and 4-hydroxy-3-methoxy-
styrene.
This Project Summary was devel-
oped by EPA's Municipal Environ-
mental Research Laboratory. Cincin-
nati. OH, to announce key findings of
the research project that is fully
documented in a separate report of the
same title (see Project Report ordering
information at back}.
Introduction
Annually, large amounts of agri-
cultural waste are produced in the
United States. The disposal of this
waste material is becoming an increas-
ingly more difficult and expensive
matter. Agricultural wastes are largely
lignocellulosic in chemical nature.
Pyrolysis is one approach for converting
agricultural, forestry, and municipal
wastes to useful energy of chemical
forms.
The products resulting from the
pyrolysis of the organic fraction of solid
wastes include noncondensable gases,
liquids, and a solid residue of carbona-
ceous material or char. Analysis of the
evolved pyrolytic gas stream indicates
the presence of hydrogen, carbon
dioxide, carbon monoxide, methane,
ethane, and ethylene. The individual
gas compositions very with pyrolysis
conditions. The solid material remaining
after pyrolysis is an impure carbon and
ash. The liquid fraction of pyrolytic oil
contains organics and water.
The pyrolytic oils are mixtures of
neutral compounds and strong and
weak acids. The oils are viscous, sticky
liquids at room temperature. The
pyrolytic oils appear to oxidize and/or
polymerize on standing. During this
study, methods were developed for
determining the chemical composition
of the pyrolytic oils, and attempts were
made to stabilize the pyrolytic oils
against whatever changes they undergo.
Methods and Results
The pyrolytic oil distillate was analyzed
on an Aerograph 1440 gas chromatog-
raph with a flame ionization detector.
The conditions were: a 10-ft by 1/8-in.
stainless steel column packed with 2%
OV-210on 100/120 mesh Supelcoport
F-01409*; oven temperature program,
50° to 225° at 10°C per min; helium
flow rate, 30 ml/min. Peak identifica-
tions were made by noting the en-
hancement of peak size when known
substances were chromatographed
with the distillate. Peak assignments
are given in Table 1.
•Mention of trade names or commercial products
does not constitute endorsement or recommenda-
tion for use.
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The oil distillate was also analyzed on
the Varian 3740 capillary gas chroma-
tog raph under the same conditions.
Stabilization studies were conducted
to determine mechanisms that lead to
polymerization of pyrolytic oils. When a
chromatogram of a pyrolytic oil sample
was compared with one made 9 months
later, the observation was that iso-
eugenol and 4-hydroxy-3-methoxy-
styrene peaks disappear on aging of the
oil. This finding substantiates our
suggestion that cationic, chain-reaction
polymerization or oligomerization is
responsible for substantial increases in
viscosity of the pyrolytic oils on aging.
Also discussed is the potential of the
pyrolytic oils as a source of chemicals.
The full report lists chemicals present in
pyrolytic oil and their prices as reported
in Chemical Marketing Reporter.
In an earlier EPA-supported study,
"Pyrolytic Oils" (EPA-600/2-80-122),
methods were developed to separate
oils into fractions containing phenolics,
polyhydroxy neutral compounds, neutral
compounds of a high degree of aromat-
icity, and volatile acidic compounds. The
results of these methods will be useful
in determining full potential of pyrolysis
for production of chemicals and fuels.
The full report was submitted in
fulfillment of Grants Nos. R-804440010
and R-804440020 by Atlanta University,
Atlanta, GA, under the sponsorship of
the U.S. Environmental Protection
Agency.
Table 1. Typical Pyrolytic Oil Distillates
Sample
m/e (Relative Intensity %)
1 -Heptanol
2,3-Dimethylphenol
2,4-Dimethylphenol
2,6-Dimethylphenol
Naphthalene
2-Methoxy-4-methyl phenol
Veratrole
29(38). 31(251. 41(96). 42(56). 43(68). 54(68).
55(100), 56(30). 69/56). 70(96). 73(66). 84(25).
99(7). 100(8)
31(11). 36(30). 43(17), 45(12). 54(14), 56(10).
79(17). 80(11). 81(17).93(17). 107(75). 122(100)
31(2). 94(10), 107(60). 121(30), 122(100)
36(6). 43(8). 55(6). 80(25), 82(22), 94(20),
107(40), 122(100)
36(13), 43(25), 54(6). 67(5). 104(7), 128(100)
31(16), 35(44). 45(41). 54(14). 55(30), 56(14),
57(14). 59(30). 68(20). 69(20), 7O(30). 80(22).
81(18). 95(58), 123(100). 138(100)
29(4). 41(18), 52(12), 63(10), 64(12), 65(12),
93(38). 123(100). 138(97). 139(10)
M. B. Polk and M. Phingbodhippakkiya are with Atlanta University, Atlanta, GA
30314.
C. J. Rogers was the EPA Project Officer (see below for contact).
The complete report, entitled "Development of Methods for the Stabilization of
Pyrolytic Oils." (Order No. PB 82-108 150; Cost: $9.50. subject to change) will
be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
For information contact N. B. Schomaker at:
Municipal Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati. OH 45268
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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