1°973 Environmental Protection Technology Series
The Disposal of
Cattle Feedlot Wastes
by Pyrolysis
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
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EPA-R2-73-096
January 1973
THE DISPOSAL OF CATTLE FEEDLOT WASTES BY PYROLYSIS
by
Dr. William Garner
Dr. Ivan C. Smith
Project No. 13040 EGH
Contract No. 14-12-850
Project Officer
Mr. Ronald R. Ritter
Environmental Protection Agency, Region VII
Kansas City, Missouri 64108
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402
Price $1.25 domestic postpaid or $1 OPO Bookstore
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EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents
necessarily reflect the views and policies of the
Environmental Protection Agency, nor does mention
of trade names or commercial products constitute
endorsement or recommendation for use.
il
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ABSTRACT
Steer manure was obtained from a source that was generally free
from extraneous mineral contaminants. This material was dried at 100°C and
pulverized. Three types of laboratory scale pyrolysis reactors were used in
a study of reaction conditions and of the characteristics of the materials
that were produced.
Replicate batch pyrolyses were carried out in stainless steel
vessels equipped with devices to scrub the exhaust in an ice-cooled trap and
a solid carbon dioxide-cooled trap. There was also provision to sample the
noncondensable gases. These pyrolyses were carried out with carefully con-
trolled heating regimen and at atmospheric and low pressures. Optimum op-
erating conditions were established by the criteria of maximizing yield of
liquid organic products and minimizing the yield of carbonaceous solid res-
idue. Low pressure and a maximum temperature of 400°-500°C were optimum.
A rotating glass device was used to prepare larger batches of
pyrolysate. These runs, however, were not quantitative as it was not possi-
ble to completely remove condensables from the exhaust stream. Materials
from these runs and the runs described above were used for one scheme of
qualitative analysis of the organics.
A third pyrolysis study was carried out in a long iron tube that
was progressively heated to 500°C along -its length while the heated contents
were swept with a slow stream of helium. Multiple condensate traps and
scrubbers were used to collect condensate from the exhaust stream. This
setup approximated a continuous run. The material from this run was ana-
lyzed by a classical organic separation scheme.
The yields of the long tube run were, based on dry weight:
Char 35.7$
Ash 9.2
Carbonaceous residue 26.5 (by difference)
Low-boiling organics 7.3
Tarry volatile organics 14.2
Reaction water 16.7
Noncondensable gases 26.1 (by difference)
Under comparable conditions, other runs had yielded a noncondens-
able mixture of 8.6$ H^, 10.9$ Ng, 16.0$ CO, 38.9$ C02, 12.9$ CH4, 0.3$
C2H4, and 1.8$ CpHg. The yield of this combustable mixture is equivalent
to 2 - 3 million Btu/ton of dry manure.
iii
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The liquid pyrolysates contained a wide variety of alcohols, al-
dehydes, ketones, acids, amines and phenols as well as polyfunctional com-
pounds. This complex mixture of organic compounds is valued at 1 to 2^/lb
based on the current prices for crude petroleum and coal tar obtained from
coking operations.
Economic analysis of a proposed pyrolysis unit for a 40,000-head
beef cattle feedlot shows the cost of pyrolysis with benefit of sale of py-
rolysis products to be $5.60/ton of 80$ moisture manure. This would place
a liability of $25.30 on each market beef in addition to usual manure hand-
ling costs but less the cost of field disposal. Break-even pyrolysis econ-
omics will be achieved only if the pyrolysis product has a value of 8^/lb.
iv
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TABIE OF COHTEETS
Section Page
Abstract ±±±
I Conclusions 1
II Recommendations 3
III Introduction 5
IV A Literature Review of Pyrolysis of Natural Products. . . 7
Pyrolysis of Cellulose 9
Pyrolysis of Hemicellulose and Lignin 13
Pyrolysis of Wood. 13
Analytical Systems for Pyrolysates 15
V Experimental Procedures 17
Raw Material 17
Pyrolysis and Collection Equipment 18
Separation and Analysis of Pyrolysate 18
ATI Quantitative Results of Pyrolysis Experiments 23
VII Separation and Characterization of Organic Compounds
Produced by Pyrolysis 33
Preliminary Separation and Analysis 33
Characterization of Pyrolysates by Classical Methods
of Separation 37
Discussion 53
VIII Economic Considerations 55
Balance Sheet 58
IX References 59
X Acknowledgements 61
Appendix A - Evolutionary Operation Applied to Experimental
Manure Pyrolyses 53
v
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TABLE OF CONTENTS (Continued)
Page
Appendix B - Infrared Spectra of Significant Materials Separated
From Cattle Manure Pyrolysates by Scheme I ....
Appendix C - Infrared Spectra of Significant Materials Separated
From Cattle Manure Pyrolysates by Scheme II. ... 85
Appendix D - Waste Production as Eelated to Animal Feed
93
List of Tables
Table Title Page
1 Manure Samples Used for Pyrolysis 17
2 Isothermal Pyrolysis of Manure in a Nitrogen
*? f\
Atmosphere
3 Results of Pyrolysis Experiments 29
09
4 Composition of Noncondensibles
5 Extraction of Chloroform- and Water-Soluble
Pyrolysates 35
37
6 Elemental Analyses - Pyrolysate Fractions
A-l Pyrolysis Conditions
A-2 Verified Trends 75
D-l Potential Quality and Quantity of Waste from Selected
Feeds 97
vi
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TABLE OF CONTENTS (Concluded)
List of Figures
Figure Title Page
1?
1 Bomb Pyrolysis Unit
20
2 Long Tube Pyrolysis
3 Manure Weight Loss as a Function of Temperature. . . 24
25
4 Manure Weight Loss as a Function of Heating Rate . .
27
5 Typical Readout from Thermal Differential Analysis .
38
6 Extraction Procedure Used for Bomb Pyrolysate. . . .
7 Scheme II for Separation of Condensible Pyrolysis
43
Products
8 Material and Energy Balance in Pyrolysis Processing
of Cattle Feedlot Wastes 57
66
A-l Phase 1
67
A-2 Phase 2
68
A-3 Phase 3
69
A-4 Phase 4
70
A-5 Phase 5
71
A-6 Phase 6
73
A-7 Response Surfaces: Manure "A"
74
A-8 Response Surfaces: Manure "B"
VI1
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SECTION I
CONCLUSIONS
The vast quantity of manure produced as a by-product of the
cattle feeding industry is both an economic burden on the industry and
a potential environmental hazard to air, water and land quality. An
attractive solution to these problems is the development of processes
that would use the manure either as a fuel, or a source of basic raw
materials for the chemical industry. Pyrolysis is possibly such a
process.
Laboratory scale pyrolyses were conducted to determine the
optimum pyrolysis conditions and the characteristic of the materials
that were produced. The criterion for optimization was the yield of
liquid organic compounds which were produced as water-soluble and water-
insoluble oils and tars. Maximum yields were obtained with pyrolysis
temperatures of 400°-500°C and low pressures. The liquid pyrolysate
contains a wide variety of alcohols, aldehydes, ketones, acids, amines
and phenols as well as polyfunctional compounds. Within the scope of
the study, it was possible to completely characterize only a few of these
compounds. In view of the complexity of this mixture, and the attendant
cost of separation into components, its value must be placed at no more
than 1 - 2^/lb, the current price range of crude petroleum and coke oven
tars.
Under optimum conditions the pyrolysis of unadulterated manure
produced a char that contained about one-third ash. This char was
difficult to burn in the open air. It had some properties as an adsor-
bent .
The pyrolysis produced a combustible gas with a fuel content
of 300 - 400 Btu/ft3 that contained EQ, CH4, CO, C02, and N2 with traces
of C2H4 and Cglfe. Approximately 2-3 million Btu/ton of dry manure,
20-30$ of the fuel value of the dry raw manure, was recovered in the gas
mixture.
Differential thermal analysis indicated that a portion of the
reaction would proceed exothermically at 250°-300°C. The exothermic
reaction yielded a mixture of gases and condensibles that could not be
completely separated.
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The pyrolysis process applied to cattle feedlot wastes Is uneco-
nomical in relation to simple incineration, as the cost of equipment to
separate potentially valuable materials from the exhaust stream is not
offset by the market value of these materials. The fuel oil that would
be used to fire a predryer is probably more valuable than the pyrolysate.
If materials isolated from the pyrolysate are merely used as fuels, the
pyrolysis process becomes in essence a multistage incinerator with no
particular advantage over simple burning.
Economic pyrolysis might be feasible if the fresh manure were
allowed to dry in an arid climate. In such a case, however, the whole
premise of rapid manure disposal to prevent the accumulation of an envi-
ronmental hazard is defeated.
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SECTION II
EECCMMEKDATIOWS
The results of this study do not encourage the immediate
development of a pilot or large scale program to pyrolyze cattle wastes
as a means of disposal.
Additional research can "be done in anticipation of some of the
possible trends in our economy. A long-term, low-level stucly could more
fully characterize the exact nature of the pyrolysis products. This would
permit more exact design of the pyrolysate separation units. Such a
research program might well be conducted at a university where a by-
product would be well-trained environmental scientists.
One economic trend that might bring pyrolysis into favor would
be a steep rise in the price of feed grains. This would bring rough
fodder back in use as a main dietary energy source, causing production
of a bulkier, drier manure. Also, as oil and other fossil sources of
carbon become scarce, manure pyrolysate may become competitive with crude
petroleum and coal tar.
The pyrolysis process has its own environmental liabilities.
pyrolyzing manure has a distinct odor, somewhat like popular barbecue
sauces. Some of the low boiling fractions on standing developed a
particularly objectionable smell. If pyrolysis is to be developed into
a usable process, devices for complete scrubbing of exhausts will need to
be developed.
Coal tar, soot, and fumes of broiling meat are all reported to
carry cancer producing agents. There is sound rationale in suspecting
that the manure pyrolysates would also be carcinogenic. Adequate research
should be conducted on this subject before an environmental hazard to
aquatic wildlife is traded off for a real hazard to humans.
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SECTION III
INTRODUCTION
The cattle feeding industry is experiencing two trends: growth
in numbers of cattle fed and marketed annually; and growth in the size of
the individual operations. Feedlots with 50,000 head are no longer unique.
Since each animal produces from 40 to 60 Ib. of manure daily, handling and
disposal of the manure is a major operating task for the industry. With
the competition of chemical fertilizers, the value of manure in most areas
is below handling costs. On the other hand, there is a potential hazard
to the environment, especially the natural watershed, from large quantities
of impounded manure. The BOD load, high ammonia content, and suspended
solids of manure have been responsible for specific fish kills and general
degradation of aqueous bodies. Any economically attractive alternative
to piling or concentrated field spreading should be investigated.
Pyrolysis, a common chemical process, is, in concept, an attrac-
tive solution for manure disposal. The dry animal manure produced in the
USA is equal in mass to coal or oil production. Thus, manure could rival
the fossil fuels as a source of carbonaceous material. A 60,000-head
cattle feedlot produces daily, on a dry weight basis, some 300 tons of
dry organic material of fairly uniform composition. Preliminary quali-
tative studies of manure pyrolysates indicated the presence of many common
commercial organic chemicals.
Pyrolysis is thermal decomposition that can be achieved by
heating in an inert atmosphere or by partial combustion. The process
equipment must include a burner or heat sources, a pyrolysis chamber and
a system for separating the condensable pyrolysate. A good benchmark for
estimation of capital and operating costs of such a process would be
incineration of municipal refuse. The pyrolysis process would thus require
equipment at least as expensive as incineration and the process could be
economically attractive in relation to incineration if there were a market
for the products of the process.
Based on the above background, a program was conducted to
determine if it is economically feasible to pyrolyze feedlot wastes as
a method of volume reduction, stabilization and production of marketable
by-products.
Preliminary to any cost analysis of the pyrolysis process was
an iterative analysis of the process in terms of (l) type of product,
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(2) yield of product, and (3) reaction conditions for producing this
product. The assumption was made that the most valuable products would
be liquid organics that contained either oxygen or nitrogen, that is,
the alcohols, ketones, acids, and amines that might be used as either
special solvents or synthesis intermediates.
Process parameters were first approximately established by
small scale instrumental methods analyses. The thermodynamic character
of manure pyrolysis was established by Differential Thermal Analysis
(DTA). Weight loss in relation to time and temperature was established
by Thermogravimetric Analysis (TGA).
Next, replicate small scale pyrolyses were made using samples
containing approximately 30 g of dry manure. The condensable portion of
the pyrolysate was collected in two sequential traps cooled to 0°C and
-78°C. The mixture of tarry distillate and aqueous liquor that collected
in the 0°C trap was extracted with chloroform. The chloroform extract
and the aqueous layer were evaporated separately to yield two fractions
plus the low boilers that condensed out in the -78°C trap.
The range of optimum conditions was established by use of
Evolutionary Operation (EVOP). The techniques of EVDP are given in
Appendix A. A maximum yield of the three fractions described above was
sought, as well as minimization of the residue of carbonaceous material
that remained in the pyrolysis vessel. Principal parameters studied were
temperature, pressure and mineral content of the manure.
At this point, the need for a more definitive analysis of the
liquid pyrolysis product was apparent. The pyrolysate was partially
characterized by two versions of a standard qualitative analysis scheme.
A wide variety of compounds were isolated. It was concluded that the
pyrolysate was of low value by virtue of its complexity and the attendant
cost of separation. Further, the pyrolysate contained no single unique
or high valued compound that could be gleaned from the mixture to offset
process costs.
The remainder of this report discusses the chemistry of the
pyrolysis reaction, details of the experimental studies, and presents
an economic analysis of a tentative process. Infrared spectra of
isolated pyrolysis fractions are included as Appendices B and C. Waste
production by cattle is discussed in Appendix D.
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SECTION IV
A LITERATURE REVIEW OF PYROLYSIS OF NATURAL PRODUCTS
A preliminary literature survey disclosed no studies concerning
the pyrolysis of cattle manure. The following is a review of literature
related to such a pyrolysis study. The review covers the chemistry and
composition of the manure; the pyrolysis of the polysaccharides — cellulose
and hemicellulose—and of lignin; the pyrolysis of wood and possible re-
lations to manure pyrolysis; the systems for analysis of cellulose pyrol-
ysis products, and the application of these systems to manure pyrolysis
products.
Cattle manure is largely a mixture of polysaccharides and long
chain aromatic polymers usually found in the cell walls of plants.
Grub—/ describes cattle manure as a combination of undigested
food, unabsorbed digestive juices, cells and mucous from the digestive
tract, and waste minerals. Fresh manure contains 80-85% water. Dry matter
consists largely of undigested cellulose, hemicellulose, lignin, and ligno-
protein complexes.
Cellulose is a homopolysaccharide containing glucose units linked
together by 1-4-p-glucosidic bonds. The sugar formed by two glucose units
is cellobiose.
Cellulose
CHgOH
r< n
H/H \,—0-
C C
HO\OH H/H
r r*
H OH
H OH
P — r<
-[/OH HN
H\H
r1 n
tn2oH
CHgOH
C
H/H
C
-V
C OH
^c"
H
-r/
c
H\
n
H
p
/ OH
\?
r*
CHgO
OH
1
f-"t
U
H\
/
f\
E
^
C
Cellobiose
Hemicelluloses include heteropolysaccharides and uronic acids.
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Hemi celluloses
-0-
Pentosans
H
t
H/H
0
1\ OH H /
V, A/
Hexosans
•0-
H
n
n
Pentosans include xylan and araban, while the hexosans may be
mannan, glucan, galactan and others.
Uronic Acids
CHO
H-90H
HO-C-H
H-C-OH
H-C-OH
COOH
CHO
H-i-OH
HO-G-H
HO-C-H
H-C-OH
COOH
D-Glucuronic Acid
D-Galacturonic Acid
Although Pigman^ suggests that the composition and genesis of
lignin is unsettled, Mkitin5/ believes that lignin is composed of polymers
containing the following units:
C-C-C-,
CH30
HO
and HO
c-c-c-
OCH3
Ligno-protein complexes are highly stable humus-like compounds which are
produced in the digestive tract of the ruminant by the reaction of lignin
with bacterial protein. Grubi/ believes these compounds may comprise up to
25$ of the total dry weight of the feces.
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Pyrolysis of Cellulose
When dry cellulose is heated slowly to 120°C in the presence of
air, water, vacuum or in various liquids, the molecule begins to depoly-
merize and changes occur in viscosity, a-cellulose content, strength, sol-
ubility in alkali, and copper number.—1—' An aqueous distillate begins to
form at 200°C, and tar and gases at 230-240°C. The reaction becomes exo-
thermic at 270°C and extensive decomposition results with formation of sol-
id, gaseous, and liquid products. Between 270-350°C the rate of production
of gases is greatest, while above 350°C the rate of production of gas is
constant until it is complete at 470°C.
The char resembles natural coal. Heuserl/ states that Bergius'
experiments showed natural anthracite could be formed from plants rich in
cellulose and poor in lignin. He also cites the conflicting opinion of
Fisher, who believed that in the natural process the cellulose would be en-
tirely destroyed by bacteria before the coalification could be completed.
Contrary to both these arguments, Heuser himself believed the exposure of
the mixture of cellulose, lignin and their biological decomposition products
to heat produced a natural coal.
The aqueous distillate from cellulose pyrolysis contains small
amounts of acetic and formic acids, acetone, methyl ethyl ketone and other
ketones, while the tar is chiefly composed of phenols and undecomposed levo-
glucosan. The gases include CO, COg, hydrocarbons and Hg.
The nature of these pyrolysis products depends on the temperature
and duration of heating, the presence of impurities and the surrounding at-
mosphere during pyrolysis. Coppick-' observed that the amount of the flam-
mable tarry compounds increased with an increase of the final pyrolysis temp-
erature. Heuser^/ points out that cellulose loses much more of its tensile
strength and Qf-cellulose at lower temperatures and longer periods of heating
than at higher temperatures and shorter heating times.
Studies on the effect of impurities on cellulose pyrolysis have
led to a mechanism involving the intermediate, levoglucosan. Shafizadeh-/
suggests that at high temperatures the following reactions take place:
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cellulose
glowing ignition
combustile
volatiles
flaming combustion
He cites the works of Martin, and Glassner and Pierce to prove that these
secondary reactions occurred from the thermal degradation of the levo-
glucosan. Martin proved that flash pyrolysis produced a large percentage
of levoglucosan. Under longer duration heating, the amount of levoglu-
cosan decreased due to formation of secondary products. Glassner and Pierce
compared cellulose pyrolysis and levoglucosan pyrolysis at isothermal con-
ditions between 170-360°C. The secondary products from these pyrolyses
were essentially the same.
Shafizadeh cites several mechanisms for the secondary reactions.
The secondary products could be formed in a way similar to the acid-
catalyzed degradation of D-glucose residues:
10
-------
n IT
• y--h
HCOH
j
HOCH
HCOH
H-C-O
H-COH
|
HgO HCOgH
+ +
H-C=0 C02H
HOCH HC=CV CH2
i X i ^
> HflOK ^
HCOH H(
-0-CHp CH2OH
* 5-(H;
0 > CHp -
/ \ d
: —c / c=o
CHp OH CH^
\
yrdr oxymethyl J -
C02
+
CH3
^> CHp
c=o
CH3
2-Butanone
Levoglucosan/ Glucose
t.
E'-OCH
H(j:OH
HOCH
HCOR
HCO
2-f-oraldehyde Levulinic
I Acid
HUMIN
Char
o
II 2
CH
cro
CH3
3-Buten-2-one
Levoglucosan could also degrade through free radical formation
and molecular rearrangement:
r9H
HCOH
HCKJIH
HCOH
HCO—
-OCH2
— >
— CHO' CHO
HCOH HCOH
HCXJIH HOCH
HCOH > -COH
HC • CHp
i i '-
l— OCH2 -OCH2
C
:HO
H-C-OH
HO-C
^ i
> fi
:H
:-OH
CHp
H
i —
CH20
Levoglucosan Forme
CH2OH
HC=0 <
HCOH KG OK
|| HOCH + CHO \
ildehyde
/
HOCH < C=0 ^^--^^ CHO CHO
1 + OH*; ^^^ HCOH CHO
p ~i i
^ 1 .n-n HOCH ^ Glvoxal
•CHp OH
C_
•CHO
CH, / (
•r
1 ^ CHO ^X'' CH3 CH2OH
HCOH
i
HO-CH v
1 C=0
1
+ CHO Hydroxyacetone
•c=o
_tH3.
CH2OH
Glycoladehyde
CHO
c=o
CH3
Pyruvicaldehyde
11
-------
Shafizadeh cites another possible route for this degradation pro-
posed "by Byrne, Gardiner, and Holmes that would proceed through a carbonium
ion intermediate:
& ( "\
R'O-CH
HCOH
HOCH
HCOR
HCO— '
(
fT^ "
COH
HOC)-H
HCOR
HC^-R HC=O
:H2OH CH2OH HC) @ »- HC
/CH,OH CH,
C,
CH
HCOH
HOCH
HCOR
HCO-'
r
R"OH
CcH
II O
HC— OH
O=CH
j
*~ HC— OR
HC— O —
t
CH
HCOH
O=CH
H-7-COR
' HC— 0-'
I^H
JH.UH | 1
CH2OH CHjOH
1 1
' 0 HOCH HC=0
HCOR*
1
HCOH
1
HOCH
HCOR
HCO —
1 II II »- 1 .
C— H HCOH CH,OH
1
HC=O +
+ 0=CH
O=CH COR
1 Hr rH II
J HC Hk \-,n HC
CH,OH HC HC\0^CH CHjOH
CH.OH
3/
Nikitin suggests that polysaccharides hydrolyze at low temp-
eratures and isomerize, decompose, condense and polymerize with increased
heating. However, Shafizadeh believes that the pyrolysis of cellulose in-
volves oxidation, hydrolysis, degradation, and decomposition at low temp-
eratures, while thermal degradation occurs with an increase in temperature
and duration of heating.
Some impurities in cellulose act as flame retardants by inhibiting
the formation of levoglucosan and increasing the production of char, water
12
-------
7 ,8;
and gas. Several workers have used impurities such as water-soluble salts9—1—'
and organophosphorous compounds—' as flame retardants.
Several pyrolysis experiments have been performed on cellulose in
vacuum: Vann,—' Madorsky,—' Golova,* Pakhomov,* and Epshtein.* The vacuum
prevents decomposition of levoglucosan "by minimizing the secondary decompo-
sition reactions of this tar. The vacuum removes as formed such oxidizing
agents as CO, COg, HgO, and 02. Schwenker and Becki^/ have proposed that the
same products are obtained in either nitrogen, air, or helium atmosphere.
They suggested, therefore, that most secondary products were produced by a
nonoxidative process.
Pyrolysis of Hemicellulose and Lignin
Not many generalizations can be made concerning pyrolysis of lig-
nin or hemicellulose since, as Shafizadeh£/ explains, few experiments on such
pyrolyses are reported. One reason for the lack of research may be the dif-
ficulty in separating these two constituents from one another in wood.
Nikitin£/ states that it is not possible to completely extract either lignin
or carbohydrate from wood without contamination of the other. He has, how-
ever, noted (from the temperature curves in the data of Heuser, Skioldebrand,
and Hagglund* and also from Heuser and Bretz*) that acidified lignin from
spruce exothermally decomposes at a higher temperature range (350-450°C) than
the cellulose. The pyrolysis of this lignin yielded more carbon and tar and
less aqueous distillate than cellulose pyrolysis. Mishin* observed that hemi-
cellulose must begin to decompose around 250°C, below the decomposition point
of cellulose which is 270°C.
Pyrolysis of Wood
Nikitin^-/ provides a comprehensive review of wood pyrolysis. Wood
begins to decompose considerably above 150°C. He cites the work of Violett*
that shows the weight loss due to volatilization increases by 60.9$ between
160 °C and 270 °C. Nikitin concluded from data of Klason* that the exothermal
decomposition of wood begins at about 270-280°C. Large amounts of CO and C02,
acetic acid and liquid distillate are produced, followed by production of
light and heavy tars. By further heating to 380-400°C, heavy tars, plus C02,
CO and hydrocarbon gases, were formed. The residue was carbon with adsorbed
impurities.
References cited by Nikitin.
13
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The final pyrolysis products from charring depend on the type of
wood, the final reaction temperature and duration of the heating. Klason*
heated various woods to 400 °C for 8 hr and obtained 32-38$ carbon, 45-50/0
liquid, and 15-20$ gas (including loss). Water accounted for 21-23$ of the
liquid distillate. Between 250-350°C more volatile products were liberated
than in the final range of 350-450°C. As the heating duration increased,
the yield of tars decreased and the yield of carbon increased.
The various constituents of wood are believed to decompose se-
quentially. Above 150°C and up to 270°C hemicellulose is almost completely
decomposed, while cellulose decomposition is initiated and a small amount of
lignin is lost. A large amount of gas is produced along with the aqueous
distillate and tars. At 270-280°C, the cellulose decomposition becomes ex-
othermic with some decomposition of lignin to produce the liquids, hydrocar-
bon gases, and tars. From 380°C to completion at 470°C, the lignin decom-
poses completely to light and heavy tars and hydrocarbon gases.
Charcoal from wood pyrolysis is not pure carbon, but contains
volatile products. Bergstrom* reports that the amount of volatile products
is a function of the final pyrolysis temperature. As this temperature was
increased from 300-500°C, methoxy group content in charcoal decreased from
5.7 to 0.2$. Long heating periods also lead to an increase in the carbon
content of the charcoal.
Although the liquid distillate may contain 60 organic compounds,
the predominant compounds are acetic acid, methanol, methyl acetate and
acetone. The liquid fraction also contains "soluble" tars. These tars
contain condensation products of phenols and aldehydes, soluble acids, al-
cohols, and ketones. The work of Wacek, Tichcheuko, and Bobrov* confirms
the production of the soluble tars as the pyrolysis of carbohydrates and
cleavage of sugars.
The "settled" tar is composed of water-insoluble volatile products,
nonvolatile products, and some water-soluble volatile products. The most
important components of this tar include phenol, pyrocatechol, pyrogallol
and their homologs (10-20$). Hydroxy acids also make up 20$ or more of the
tars.
The gases are noncondensed vapors saturated with volatile compounds
trapped as droplets. Yvon* showed that only water vapor, C02 and CO are elim-
inated up to 280°C; hydrocarbons begin to be produced at 280°C and reach a
maximum production between 380°C end 500°C, while hydrogen appears between
700-900°C.
* References cited by Nikitin.
14
-------
With an increase of pressure, the yield of soluble tar decreases
and settled tar yield remains fairly constant. In a stream of reducing
hydrogen the amount of these soluble tars increases while the secondary re-
actions decrease. Superheated steam is also another deterrent to secondary
reactions by providing more uniform heating and continuous removal of vol-
atile products. Liquid hydrocarbons can also be used as the reaction med-
dium to avoid producing dilute aqueous solutions. Pyrolysis in these media
also lowers the exothermal decomposition point, which reaches a maximum rate
of heat liberation between 260-270°C. Above this temperature, wood will al-
most entirely dissolve by a mechanism of thermal dissolution. Continuous
circulation ovens also produce effects on the pyrolysis of wood similar to
those produced ±n vacuo.
Analytical Systems for Fyrolysates
Systems for the analysis of pyrolysis products have been mostly
developed through the study of cellulose pyrolysis. Swenker and Pascu— /
used paper and partition chromatography for identification of nonvolatile
acids and levoglucosan. Madorsky and co-workers used mass and infrared
spectroscopy to identify vacuum pyrolysis products from cellulose—/ as well
as products from derivatized cellulose.^/ Lindsey— / suggests the use of
elution chromatography for the identification of pyrolysis products.
~\ C /
Greenwood, Knox and Milne—' suggested the use of gas chromatography to
identify the unidentified trace components found by conventional, IR, and
mass spectrometry. Schwenker and Beck-Li/ used pyrolysis gas chromatography
and found 37 different volatiles in contrast to the 8 to 18 products found
by other workers. LincolniZ/ employed flash pyrolysis in which the reac-
tant was exposed to a very short and intense impulse of heat. Only the
light absorbing cellulose was heated, while the transparent container stayed
cool. Under these conditions, there was complete volatilization of the sam-
ple. Lincoln adapted his apparatus to feed directly to a gas chromatograph
or to a mass spectrometer. With these techniques he found that cellulose
did not decompose below 600°C as compared to decomposition at 300°C by slow-
er heating. Martin and Ramstad-*-,8/ used coupled gas chromatographic columns,
attached directly to the flash pyrolysis unit, to measure separately the high
molecular weight products and the fixed gases.
* References cited by Nikitin.
15
-------
SECTION V
EXPERIMENTAL PROCEDURES
This section of the report describes the collection and handling
of the raw material, contains a description of the pyrolysis and collection
equipment used and an outline of the separation procedures and analytical
techniques used to identify pyrolysis products.
Raw Material
Manure from two sources was used for this study. Manure used in
early studies was obtained through the courtesy of Mr. Don Elfson, Farm
Manager for Reorganized Church of Jesus Christ of the Latter Day Saints
(RLDS). Manure from this source was from three Holstein yearling steers
being maintained on a whole corn plus protein supplement diet. Manure
from the RLDS farm proved to be of variable nature and contained up to
40$ ash, largely Si02. This material is designated Sample "A" through-
out this report.
Four yearling steers were subsequently purchased by MRI and kept
on a partially covered concrete pad. These animals were fed a finishing
ration. Two composite batches of manure collected from these steers were
used as pyrolysis samples. These batches are identified as Samples "B"
and "D".
Samples were dried for 24 hr at 212°F. This reduced the moisture
level to approximately 7%, The material was then passed through a Wiley
Mill using a 3/32 screen. Finely divided material prepared in this manner
was used for all pyrolysis studies. Table 1 shows the ash and moisture con-
tent of the various samples.
TABLE 1
MANURE SAMPLES USED FOR PYROLYSIS
Sample % Moisture % Ash Source
V' 10.8 40 RLDS Farm
"B" 6.3 8.65 MRI Feedlot
"D" 2.7 8.95 MRI Feedlot
17
-------
Pyrolysis and Collection Equipment
Pyrolysis is the process of thermal decomposition in an inert
or controlled atmosphere. Three pyrolysis procedures vere employed in
this research program.
The first unit developed and constructed for pyrolysis of manure
consisted of a furnace designed to accommodate six 75-ml pressure bombs.
Each bomb was connected in series to two pyrolysate collecting traps: the
first at 0°C (ice) and the second at -78°C (dry ice). The sample collection
train also contained a gas collection bulb that enabled sampling and anal-
ysis of noncondensables. The total volume of noncondensables was measured
with a wet test meter. Approximately 30 g of dried manure was pyrolyzed
in each bomb per run. The pyrolyses were conducted under vacuum and at
atmospheric pressure. The unit is shown in Figure 1.
A second pyrolysis device was constructed from a 1.5 in. diameter
black iron pipe 3 ft long._ This pyrolysis tube simulated a unit which
could be operated continuously. It enabled the pyrolysis of 350-g batches
of dry manure.
Helium was used to maintain a nonoxidizing atmosphere. Heating
burners were lit sequentially at 15-min intervals. After lighting all
burners, heating was continued for an additional 67 min. Air input to the
burners was adjusted to produce a sooty yellow flame. A thermocouple
attached to the surface of the tube read 500°C - 25°C. A schematic of
this unit is shown in Figure 2.
A rotary glass device was also used to prepare several batches
of tarry condensate. It was not possible, however, to get quantitative
recovery with this system.
Separation and Analysis of Pyrolysajte
Two extraction procedures were used to separate the pyrolysate
into fractions having different solubility characteristics and into different
types of compounds. Schematics of the two separation procedures are shown
in Section VII as Figures 6 and 7.
Figure 6 shows the schematic of the separation procedure that
was developed specifically for this complex mixture of materials. It
was designed, partially through trial and error, to separate products
collected from the bomb pyrolysis studies. Also shown on this schematic
are the types and yields of compounds found in various fractions.
18
-------
Figure 1 - Bomb Pyrolysis Unit
-------
I '
'
TUBE CHAR
COUPLING PACKING
SLOW HELIUM
GAS STREAM-
DRY MANURE PACKING
\ \
1st TRAP
BURNERS LIT SUCCESSIVELY IN THIS DIRECTION
GLASS BEAD
FILLED TOWER
2nd TRAP - 78°C TRAP SCRUBBER
Figure 2 - Long Tube Pyrolysis
WET TEST METER
-------
Figure 7 shows the schematic of the classical separation procedure
taken from Cheronis and Entrikin's text "Semimicro Qualitative Organic
Analysis."i^/ This separation scheme was slightly modified for this
separation task.
A variety of identification and other separation procedures were
used in analysis of the components of the pyrolysate. These procedures
were patterned after methods used in structural investigations of wood
pulp, lignins, coal tar pitch, humic acids and other similar materials.
Vacuum sublimation, gas chromatography, thin-layer chromatography
(TLC), paper chromatography, and distillation were used in addition to
extraction to separate and isolate components.
Infrared (IR), nuclear magnetic resonance (MR), electron spin
resonance (ESR), and ultraviolet (UV) spectroscopies, mass spectrometry,
gas chromatography and elemental analysis were used to partially characterize
the tar fractions.
21
-------
SECTION VI
QUALITATIVE RESULTS OF PYROLYSIS EXPERIMENTS
Pyrolyses of bovine waste were conducted over a range of
temperatures and at two pressures using the three pyrolysis units pre-
viously described. This section of the report contains a tabulation
of the results of all pyrolyses conducted including yields for the various
fractions of the distillate (tar, water, volatiles, noncondensables, and
char).
Prior to initiating pyrolysis studies, preliminary investigations
were conducted using thermogravimetric analysis (TGA) and differential
thermal analysis (DTA) to identify a temperature range for conducting the
pyrolyses. Thermogravimetric analysis of Sample "A" was obtained using
a Perkin Elmer TGS-1 instrument. Five-milligram samples of the manure
were placed in a nickel sample cell. Five thermograms were obtained from
samples maintained in a nitrogen atmosphere and one thermogram from a
sample at 10~3 torr. Heating rates of 5°, 10°, 20° and 40°C/min were used.
Figure 3 shows percent weight loss as a function of temperature
under a vacuum of 10 torr and at 1 atm. under nitrogen, both obtained
using a heating rate of 5°C/min. Rapid weight loss began to occur in the
temperature range of 200°-250°C for the sample maintained under a nitrogen
atmosphere. A first derivative of this curve would show a maximum at about
300°C. Figure 4 shows weight loss at heating rates of 5°C/min and 40°C/min.
The curves have essentially the same configuration; however, the curve
obtained using the higher heating rate is displaced toward a higher temper-
ature by 25°-30°C. This displacement may be attributed to inefficient
heat transfer and hence to temperature lag in the sample.
The major difference observed was between the sample heated under
vacuum and an identical sample heated under a nitrogen atmosphere. The
temperature where rapid weight loss began to occur for the evacuated sample
was at 350°-400°C, or approximately 150°C higher than for the sample under
nitrogen. The maximum rate of weight loss occurred at approximately 450°C.
The only obvious explanation for this difference is that some constituent
of the manure, perhaps water, promotes degradation. If this constituent
is removed under vacuum it is not available for hydrolytic decomposition
of the manure.
Isothermal TGA studies were also conducted at two temperatures,
250°C and 325°C. The results of these studies are shown in Table 2 .-
23
-------
O
0
10
20
30
40
50
60
70
80
90
100
J
a
\
5°C/Min - Vacuum (10"3 Torr)
5°C/Min - 1 Atm. Nitrogen
_L
_L
100 200 300 400 500
TEMPERATURE (°C)
600
700
800
Figure 3 - Manure Weight Loss as a Function of Temperature
-------
NJ
V/i
(/I
o
0
10
20
30
40
50
ULJ
-------
TABLE 2
ISOTHERMAL PYROLYSIS OF MAMJEE IN A NITROGEN ATMOSPHERE
Weight LossSy in Heating Period
Temperature
18 Min. 90 Min.
250°C 18$ 29$
325°C 38$ 39$
a/ A maximum of 59$ of the sample could be volatilized by heating to
constant veight at 600°C in air.
This study clearly demonstrated that a substantial portion of the volatiles
was lost within 18 min. at 325°C.
Differential thermal analyses were conducted on this same sample
of manure. A Du Pont 900 thermal analyzer was used for these measurements.
Five thermal analyses were conducted over the temperature range 25°-800°C
using heating rates of 5°, 15° and 30°C/min.
The general patterns of all the DTA curves were similar. Each
demonstrated an endotherm, exotherm, endotherm, exotherm sequence. The
temperature ranges were not completely uniform, even on curves repeated
at the same heating rate. The lack of reproducibility was possibly due
to variations in the samples. The change in the pattern from endothermic
to exothermic is indicative of a multicomponent mixture in which the
components pyrolyze or volatilize independently. The similar patterns
exhibited at all heating rates seem to demonstrate that change of heating
rate within this range does not change the reaction significantly. A
typical tracing of the instrument readout is shown in Figure 5.
TGA and DTA studies showed clearly that little or no pyrolysis
occurred below 200°C and that no advantage was realized by pyrolyzing at
temperatures above 600°C. High temperatures could also be expected to
cause second order reactions and a larger number of pyrolysis products.
The results of these experiments provided certain guidelines for
process development. Slow heating is preferred to fast heating; 300°C seems
a minimum temperature, and very high temperatures have no advantage. These
guidelines agree with the results obtained by other workers who are investi-
PO PI/ P?/
gating the pyrolysis of refuse,^^-V tires,_' etc.
26
-------
ho
o
x
LLJ
i
-------
As a consequence of these studies, samples of manure pyrolyzed
in the "bomb apparatus were rapidly heated to 200°C (~10°C/min). The
temperature program (heating rate, temperature, time) was then varied
"between 200°C and 600°C to determine what effect temperature and time
had on the amounts of pyrolysate and char. Results from these experi-
ments are shown in Table 3. Also contained in this table are the results
of studies in which portland cement, sodium bisulfate monohydrate and
sodium carbonate were added to the manure. These materials were evaluated
as potential pyrolysis catalysts. They are inexpensive, readily available,
and had been evaluated previously as catalysts for pyrolysis of other
organic materials .£^7
Table 4 shows the composition of the noncondensable gases that
were obtained from these batch pyrolyses.
The results of large-scale (350-g) pyrolyses are presented in
Table 3 as experiments 11 to 15.
28
-------
TABLE 3
RESULTS OF PYROLYSIS EXPERIMENTS
Experimon t
No. Sample
5 "A"
"B"
t .
50
50
50
50
50
50
51
50
50
50
50
50
50
50
50
50
50
50
50
50
20
33
33
33
33
33
33
Wt.
. i&A
44.6
44.6
44.6
44.6
44.6
44.6
45.5
44.6
44.6
44.6
44.6
44.6
44.6
44.6
44.6
44.6
44.6
44.6
44.6
44.6
18.7
30.9
30.9
30.9
30.9
30.9
30.9
25"C > 200°C Fast
200°C - 30 Min.
200°C ——-'3rjO°C at l°/Min
350°C -j>500°C Fast
25°C > 200"C at 10°/Min
200°C >400°C ;it WMin
400"C - 140 Min.
25"C >200°C Fast
200°C > 300"C at l°/Min
300°C - 120 Min.
25°C > 200°G at 10°/Min
200°C » 600°C at 5° /Min
600'C - 100 Min.
25°C— >300°C Fast
300"C - 1«0 Min,
300"C >500"C Fast
500'C - 75 Min.
25°C 5> 200°C at 10"/Min
200"C > 500°C at 5"/Min
500*0 - 120 Min.
Pyrolysis
I'yro lysis
Procedure
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Romb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Pressure
(Atm
< 0.
< 0.
•=' 0.
1.
1.
1.
1.
< 0.
< 0.
< 0.
1.
1.
1.
1.
< 0.
< 0.
< 0.
I.
1.
1.
1.
< 0.
< 0.
< 0.
1 .
1.
1.
.)
1
1
1
0
0
0
0
1
1
1
0
0
0
0
1
1
1
0
0
0
0
1
1
1
0
0
0
Water
late
9,
8.
10.
8.
8.
9.
8.
8.
9.
10.
9.
10.
9.
9.
10.
10.
9.
10.
10.
10.
5.
10.
8.
9.
9.
8.
8.
r Soluble
3
1
3
9
9
0
5
8
9
1
9
2
7
7
3
2
5
2
2
2
8
8
9
3
1
5
9
2
2
2
1
1
1
1
0
1
0
1
1
0
0,
0
0.
0
0.
0.
0
0
0
0.
0.
0.
0.
0
.5
.2
.4
. 3
.6
.8
.2
.7
.0
.5
. 5
.3
,8
.2
.5
,7
.5
,3
.3
.3
9
.4
/,
.6
.3
. 3
, 3
Volatilcs*5/ Tar
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
,2
.2
.3
.5
.6
.6
-
-
-
-
-
-
-
.5
. 5
.4
.5
.8
.9
.2
J
.1
.2
.4
.4
, /,
7
7
7
3
2
3
5
3
3
3
:i
3
2
0
5
3
5
1
1
1
1
1
~>
2
1
1
0
.5
.6
. 1
.9
.9
.2
. 3
.7
. 2
.1
.2
r
.4
.5
.3
.9
.1
.8
2
.1
_7
.5
. 1
. 5
.8
t ?
ij
Non -
condfnsib lc£/ Cliar
3
5.
3
8
a
9.
12
8.
9.
9.
h.
6.
8,
3,
10,
10.
10.
1 j .
11,
10,
6
8,
11,
10.
9.
1 1 .
11
,5
,9
.9
. 4
.5
.0
.0
. 4
, 7
,4
,5
5
,4
.3
,4
.7
,2
0
,3
,3
.6
,8
2
2
,8
]
.3
27
26
26
27
27
26
24
28
26.
26.
28
28,
28.
36
23
24
24
26.
26
27
6
11
10
10
11
11
11
.0
.0
.0
.0
. 5
.5
.0
,4
.5
.9
.9
.5
,7
.3
.7
.0
.3
.2
.3
_2
.0
.3
2
2
.6
. 5
i 2
'•' Yi
eldi!/
Tar
16
17
15
8.
6
7.
11
8,
7.
7 .
7.
7,
5.
1,
11,
8.
11 .
4.
•?
9
6
4.
6
8
5
3.
2
.8
,0
.9
. 7
.5
.2
.7
3
2
0
2
9
4
1
,9
.8
. 4
.0
. 7
, 5
.4
,9
.8
. 1
8
.9
.9
-------
TABLE 3 (Continued)
Co
O
Sample
Experiment
No. Sample
8 "B"
9 "B"
10 "B"
11 "B"
12 "D"!/
13 "D"
14 "B"
15 "D"
16 "B'VPort-
Wt.
(K.)
33
33
33
33
33
33
33
33
33
33
33
33
33
33
150
150
398
331
30
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.5
.0
.0
Dry
Wt.
IfiJL
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
30.9
145.9
145.9
373.5
321.8
22.5
17
18
land Cement
80/20
"B"/NaHS04- 33.0 27.9
H0 90/10
"B"/NaHS200°C at 10°/Mln
200°C—>400'C at 5°/Min
400°C - 140 Min.
25°C =>200°C at lO'/Min
200°C —>600°C at 5°/Min
600°C - 100 Min.
Pyrolysis
Pyrolysis Pressure
Pyrolysis Products (a.)
Yellow Flame (~ 500°C) 120 Min.
Yellow Flame (~ 500°C) 120 Min.
Yellow Flame (- 500°C) 120 Min.
Yellow Flame <~ 500°C) 120 Min.
•~ 500"C - 277 Min.
- 500°0
25°C ->300°C at 10"/Mln,
300°C - 60 Min.
300°C—>450°C at 10°/Min,
450»C - 120 Min.
450°C—> 500°C at 10"/Min,
500°C - 150 Min.
25°C >200°C at 10°/Mln
200°C—>400°C at 5°/Min
400°C - 140 Min.
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Rotovac
Rotovac
Rotovac
Rotovac
TubeS/
Bomb
Bomb
< 0.1
< 0.1
< 0.1
1.0
1.0
1.0
< 0.1
< 0. 1
< 0.1
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
Water Non-
Water Soluble Volatiles"/ Tar condensibleS/ Char
8.7
8.5
8.2
8.0
8.9
7.8
.
9.9
9.4
9.8
9.6
8.8
8.3
8.3
34.8
35.4
-
62.3
6.4
0.5
0.5
.
0.3 0.3
0.4 0.2
0.2 0.2
.
0.6
0.6
0.3 0.6
0.3 0.6
0.2 0.6
0.6
0.3
6.2
2.6 0.6
-
23.5
0.2
2.2
2.2
2.2
0.8
1.0
0,7
_
3.2
3.3
0.8
1.0
1.2
3.3
1.8
8.1
8.2
17.6
45.9
1.7
8.7
8.6
9,6
10.0
9.4
10.6
_
9.3
10. 1
10.6
10.7
11.8
11.6
9.9
33.9
37.9
-
84.3
8.7
12.9
13.2
13.0
13.6
13.1
13.5
10.2
10.0
9.6
10.9
10.8
10.4
9.2
12.7
67.0
65.3
165.0
115.0
13.0
-/.. Yiel
Tar
7.1
7.1
7.1
2.6
3.2
2.3
_
10.3
10.7
2.6
3.2
3.9
10.7
5.8
5.6
5.6
4.9
14.3
5.2
10.0
1.0
2.2
10.8
10.0
7.9
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
< 0.1
< 0.1
< 0.1
1.0
3.0
1.0
10.4
10.6
9.5
10.3
10.2
10.5
0.2
0.3 0.3
0.6 0.3
0.3
0.3
0.4
0.9
1.1
2.8
1.5
0.9
1.3
8.4
8.3
8.6
8.6
8.9
8.7
16.1
15.4
14. 1
15.3
15.7
15. 1
2.9
3.6
9.0
4.6
2.9
4.2
-------
TABLE 3 (Concluded)
Ex?
a./
b/
£./
I/
£/
£/
eriment We. Wt. Temperature
No. Samplo (fi.) (s 0 Program
].<> "B"/N,iH.SO/(- 5.0 4.3 25'C > 200'C at
H-,0 11/1 10,0 8.6 200°C — > 400°C at
15.0 12.9 400°C - 140 Min
20.0 17.2
25.0 21.5
30.0 26.8
20 "B"/NallS04- 36.0 30.9 25°C — >200°Cat
H20 11/1 36.0 30.9 200°C — > 500"C at
36.0 30.9 500°C - 120 Min.
36.0 30.9
36.0 30.9
36.0 30.9
21 "B'VNaHSO*,- 36.0 30.9 25°C — > 200"C at
H20 11/1 36.0 30,9 200°C — > 600°C at
35.T 30.9 600"C - 100 Min.
36,0 30.9
3b.O 30.9
36.0 30.9
22 "B"/NapCO-3 30.0 27,8 25"C — > 200°C at
99/1 " 30.0 27.8 200°C >500°C at
30.0 27,8 500°C - 120 Min.
10°/Kin
5° /Min
10°/Min
5° Min
10°/Min
5° /Min
10° /Min
5° /Min
All "A" samples contained 10.87. moisture and 40% ash.
Water insoluble volatiles, condensed at -78°C.
Calculated by difference.
Calculation base on dry weight of sample.
All "B" samples contained 6.37. moisture and 8.657. ash.
All "D" samples contained 2.77. moisture and 8.957. ash.
Pyrolysis run under helium atmosphere.
Pvrolvsis
Pyrolysis
Procedure
Bomb
Bomb
Bomb
Bomb
Borrsb
Bomb
Borah
Bomb
Borah
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Pressure
(atm, )
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
< 0.
1,
1.
1 .
< 0.
< 0
< 0
1
1
1
1
1
1
1
1
1
1
1
1
J
,1
1
0
0
.0
.1
.1
.1
.0
.0
.0
.0
.0
.0
Pvrolvsis Pi
•oducts ($•)
Water Non-
Uat-Pt- Soluble Volatilesbl' Tar condensible£/ Char
0.
0.
-
3.
5.
6.
9.
9.
9.
11.
11.
10.
9.
9.
a
9.
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8.
8.
9.
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9.
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7, YielciS.
Tar
3.3
3. 5
-
4. 1
5.1
6.0
5.5
6.0
6.0
4.)
4.9
4.2
7.3
R.I
7.5
5.7
6.2
5.8
3.6
2.7
3.2
-------
TABU 4
COMPOSITION OF NONCONDENSIBLES
Dry
Experiment Ut.
No. Sample (R.)
7 "B" 92.7
92.7
8 "B" 92.7
92.7
9 "B" 92.7
92.7
OJ
IV)
19 "B"/NaHS04-H20 86.0
11/1
20 "B"/NaHS04-H20 88.5
H/l
21 "B"/NaHS04-H20 88.5
11/1
Temperature
25"C
200"C —
500°C -
25"C
200 °C —
400°C -
25"C
200°C —
600°C -
25 °C
200°C —
400'C -
25"C
200°C —
500°C -
25"C
200°C —
Program
^ 200°C at
->500°C at
120 Min.
-> 200°C at
->400"C at
140 Min.
-> 200"C at
->600°C at
100 Min.
-> 200°C at
->400°C at
140 Min.
-> 200 "C at
->500°C at
120 Min.
-» 200°C at
-> 600°C at
10"/Min
5"/Min
10°/Mln
5°/Mln
10°/Min
5° /Min
10°/Min
5°/Min
10°/Min
5°/Min
10°/Min
5°/Min
Pyrolysis
Pressure
(atm.J^
< 0.1
1.0
< 0.1
1.0
< 0.1
1.0
< 0.1
< 0.1
1.0
< 0.1
1.0
Pyrolysis
Procedure
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Bomb
Composition (volume 7.J
H2 N2
40.
8.6 10.
43.
14.
17.0 23.
16.4 7.
27.
3.6 19.
2.2 27.
n.o 15.
6.5 19.
02
2 12.2
9
8 10.8
0
8 7.6
0
1 17.5
2
9
8
4
CO
12.6
16.0
17.0
23.6
14,2
16.7
-
26.4
19.8
28.3
21.6
C02
24.9
38.9
32.4
49.6
27.3
37.2
43.0
38.8
34.8
31.2
34.0
CH4 C2H4 C2H6
6
12,
3
3.
8,
15,
3
9,
11
13.
15,
.0
.9 0.3
.7
.2
.8 0.3
.5 0.4
.0
.2 0.6
.0 0.6
.? 0.8
.4 0.5
O.i
1.8
.
0.4
0.8
1.7
-
1.4
2. I
1.6
1.9
-------
SECTION VII
SEPARATION AM) CHARACTERIZATION OF ORGANIC
COMPOUNDS PRODUCED BY PYROLYSIS
Prior to proceeding -with detailed fractionation and separation,
the tar from the pyrolysis had been extracted with water and then with
chloroform. The combination of water and chloroform dissolved all of the
pyrolysate. These solvents were used to primarily remove the tar from the
condenser traps and to clean the lines "between the pyrolysis cell and the
traps. These two extracts were then evaporated to dryness at 100°C. The
resultant residues were designated as "Tar H," an H^O-soluble material;
and "Tar C," the CHCl^-soluble material. The water-soluble fraction
amounted to 25 - 30$ of the pyrolysate condensables, excluding water.
Preliminary Separation and Analysis
Samples of Tar C and Tar H were subjected to a variety of
separation procedures that had previously been used in structural in-
vestigations of wood pulp lignins, coal tar pitch, humic acids and
similar materials.
Vacuum sublimation, thin-layer chromatography (TLC), paper
chromatography, and extraction (liquid-liquid and Soxhlet) experiments
were performed in order to isolate major constitutents from either the
water or chloroform-soluble tars. Infrared (ffi), nuclear magnetic
resonance (MR), electron spin resonance (ESR), and ultraviolet (UV)
spectroscopies, and elemental analysis were used to characterize the tar
fractions.
Procedures and Results
a. Vacuum sublimation; Samples of Tar C and Tar H (0.5 g)
were placed in a standard vacuum sublimation apparatus and evacuated
(~ 0.1 torr) for 30-60 min at room temperature. The temperature was then
raised to 180°C by means of an oil bath.
A trace of yellow oil condensed on the cold finger from
the chloroform-soluble material (Tar C) at 80°-100°C. A majority of the
sample remained (~ 98$) as residue under these conditions. The infrared
spectra of the residue before and after loss of the oil were essentially
the same. Both tars lost water and entrapped gases that were not condensed
33
-------
on the cold finger. Thus, vacuum sublimation resulted only in the isolation
of a minor component of the chloroform-soluble tar, and was useful for
removal of entrapped gases and water prior to other analyses.
b. Thin-layer chromatography: Silica Gel G chromatographic
plates and a chloroform-ethyl acetate-formic acid solvent mixture (50-40-10)
were used in an attempt to separate the HpO-soluble material. The plates
were sprayed with Fast Blue Salt B-NaOH (Reagent 61). This system has been
used to separate various phenolic carboxylic acid mixtures (e.g., pyrolgallol,
gallic acid, etc .)._/
The entire sample moved with the solvent front and no
separation of component?; of the water-soluble tar fraction was observed
by this method.
c. Paper chromatography: Whatman No. 54 paper was used
as the support. The solvent system consisted of butanol-water-ethyl
alcohol (50-40-10). This system had been used by others in an attempt
to separate levoglucosan and organic acid components——/
As with TLC, the entire sample migrated with the solvent
front.
d. Extraction studies : Each tar fraction was extracted
with solvents. The results of these experiments are given in Table 5.
With one exception, the solvent extraction experiments
resulted only in partitioning or dissolution of the entire sample. The
one exception was hexane extraction of the chloroform-soluble tar.
Approximately 10$ of this tar was insoluble in hexane. No difference
was observed between the UV spectra of the two fractions.
e. Infrared analyses; Infrared analyses were made on thin
films of both tars deposited from chloroform and other solvents used in
extractions. Spectra of the water-soluble tars were also obtained from
KBr pellets. Infrared spectra of the dried water-soluble and chloroform-
soluble fractions revealed several significant structural differences.
The most significant were: (l) greater 0-H and/or N-H content of the
water-soluble fraction as indicated by the stronger bands present at 3
and 6 M., (2) the absence of a strong C=0 absorption in the chloroform-
soluble sample; and (3) the absorption, at 7.3 M-, of the chloroform-soluble
material indicating CHg chains of length greater than four carbons. The
ratio of 0-H to C-H absorption indicates that the water-soluble material
may contain hydroxyquinone; the C=0 absorption is of course typical of
carboxylic acid type structures; and the pH of a saturated solution of the
34
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TABLE 5
EXTRACTION OF CHLOROFORM- AND WATER-SOLUBLE PYROLYSATES
Tar
Chloroform-
soluble
pyrolysate
Solvent
Benzene
Ethyl acetate
Carbon tetrachloride
70% sulfuric acid
Hexane
Result
50 mg. solid dissolved in 5 ml.
50 mg. solid dissolved in 5 ml.
50 rag. solid dissolved in 5 ml.
50 mg. solid dissolved in 5 ml.
(test for lignin neg.)
50 mg. in 5 ml. was 80-90$ soluble.
Subjected extract and CHC13 solution
of residue to UV analysis. At-
tempted to separate hydrocarbons
from aromatic carbonyl (observed
in IR), but residue showed no UV
maxima at 280 m|ju
Water-soluble
pyrolysate
Methano1
50 mg. solid dissolved in 5 ml.
Ethanol
EMSO
Benzene
Hexane (goxhlet)
50 mg. solid dissolved in 5 ml.
50 mg. solid dissolved in 5 ml.
Insoluble.
Somewhat soluble but infrared of
extract and residue indicated
partitioning rather than separation.
35
-------
HpO-soluble material "was 5, consistent with carboxylic acid structures.
The IR spectra of water-soluble tars show a close similarity to those
2fi /
of sodium salts of humic acids —-'
f. Nuclear magnetic resonance analyses: The IMR spectra
of the chloroform-soluble fraction were obtained from carbon tetrachloride
solutions. A singlet was observed at a T value of 8.7 and a second peak
with an intensity of less than 10$ of the first occurred at 9.1. The peak
at 8.7 T is characteristic of methylene groups; the lesser peak at 9.1 T
indicates the possible presence of a few methyl groups.
The spectra of the water-soluble tar were obtained in IkO
and acetone. The sample was run in a nondeuterated solvent because no
proton resonance was observed in E^O. It was thought that the absence
of resonance may have been due to exchange of the OH and NH protons with
EgO. Eesonance was also not observed in the nondeuterated solvent; this
could be due to unpaired electron broadening of the resonance or a shifting
of the resonance to T values greater than 10 if the protons are positioned
above the plane of a polyaromatic ring system.
The conclusions drawn from the IR spectra complement the
results of the MR experiments. The water-soluble material showed no
proton resonance in deuterated and nondeuterated solvents, indicating
a highly substituted structure similar to that proposed by Flaig—2/for
the humic acid formed from lignin. The chloroform-soluble fractions showed
sharp resonance at 8.7 T with no splitting. The spectrum of this fraction
indicated that the majority of protons were in long chain CE^ groups.
g. Electron spin resonance analyses: Humic acid and
related model compounds have been shown to have a stable free-radical
content. For this reason, electron spin resonance spectra of both fractions
were obtained. Both samples gave a single line spectrum at "g" values
near 2.0. The intensity of the signal was approximately 1017 spins/g of
the water-soluble material. A spin density of 10 spins/g was observed
in EPR studies of soil humic acids.— These results indicate the simi-
larity of this pyrolysate to soil humic acids.
h. Ultraviolet analyses: Ultraviolet analyses of the tar
samples on the Beckman DK showed the water-soluble material to have an
absorption maximum at 281 mp,. The chloroform-soluble material showed
no UV absorption maxima above 240 mix. The quinone moiety has an absorp-
tion maximum at 280 mM-
i. Elemental analyses: Elemental analyses were performed
on a standard, F&M C, H, & N Analyzer. Table 6 shows the results of
36
-------
elemental analysis of the dried tar samples and also literature values
2fi/
for humic acids extracted from straw '
TABLE 6
ELEMENTAL ANALYSES - FYROLYSATE FRACTIONS
C H N 0 (by difference)
CHCl3-soluble 71.7% 9.8
-------
SCHEME I FOR SEPARATION OF PYROLYSATE TARS
Dilute H2SO4 extraction
Soluble Fraction (B)
Insoluble Solids
Ether/Water Partition
Water-Soluble Ether-Soluble
I
Ether Extraction
Insoluble Solids
Soluble Solids (A)
NaOH-Soluble
pH-
Ether-Soluble
— 5 HCI
Neutra
ization
Acetone
Solid Residue (D)
Me t ha no 1
Extraction Acetone Extraction
Soluble (C) Soluble Solids Insoluble Solids
Soluble Solid| Insoluble
1
Ethanol
Recrystollize
Precipitated Solids Sold Oil
joiid
— B- -2 B-l-l A-VI-I
i .j i
Occurrence (Estimates) T
' 10%
Eva
sorate
A-VI-2
,
20%
Identity Amino Acids Amines Alcohol Alcohol (?) Acid (?)
Components (Estimated) ? 2-4 + 2-3
2-3
Fractional Cr
ysral lizations
Acetone
Soluble Residues
1, Crystallization
Efher/rVater Hexane Acf*
Partition (A-lll-1)
NoOH
Soluble Ether '
| (A-IV-l)
Acidifx (A-IV-2)
1 Vacuum Distillation
Ether/Water
Partition
NaHCO3
Soluble NaHCOjj Soluble Ether BP/2 mm
jne
| 95-125 A-IV-1A M.S. No. 1
Hexane 125-150 A-IV-1B M.S. No. 2
| 150-180 A-IV-1C M.S. No. 3
Soluble [ Insoluble 180-200 A-IV-ID M.S. No. 4
|| Pot A-IV-IE M.S. Pot
— A-il-1 A-ll-2 A-il-3 A-V-1 A-V-2 A-V-3 A-l-1
i j , ,i -> ^ ' i •
5% 50% 5% 5% 5%
Alcohol (?) Stearic Stearic Stearic Lower Higher Phenols Alcohols Ketone
Acid Acid Acid Acids Acids
2-4 + + 1+ 2-3 2* 2-4 4-10 1+
Figure 6 - Extraction Procedure Used for Bomb Pyrolysate
-------
Separation by Scheme I
A composite sample of Tar C and Tar H was subjected to the
procedure shown in Figure 6.
The primary separation step involved extracting the mixture twice
•with warm dilute 119804 (pH *— l). This separated water-soluble material and
amine sulfates from the main product which remained as an unctuous black
mass. The solubles are designated as Fraction "B".
The remaining material was then extracted three times with ether
to dissolve the major portion of the organic materials. This fraction
is designated as Fraction "A". A pasty black mass remained.
Two acetone extractions resolved this latter fraction into a
soluble Fraction "C" and a friable, powdery black mass, Fraction "D".
The Fractions "A", "B", "C", and "D" were further resolved into
component products as outlined in Figure 6.
Ether extractives (A): Solids obtained by evaporating
Fraction "A" dissolved partially in cold acetone.
a. Two successive recrystallizations of the acetone-
insoluble material from cold acetone yielded a fairly pure product. The
IE spectrum (A-I-l) suggests that it was an aliphatic ketone.
b. The cold acetone extract was slowly evaporated.
Successive crystal crops give solids which through further recrystalli-
zation from acetone provided fairly pure materials: A-II-1, A-II-2,
A-II-3. These fractions, which constituted approximately 50$ of the
pyrolysate, were found to be largely stearic acid although minor dif-
ferences in the IR absorbance bands indicate them to be incompletely
separated from other components.
c. The combined acetone raffinates from these recrystal-
lization experiments when concentrated yielded a fourth crop consisting
primarily of stearic acid.
d. A portion of the acetone raffinate, after removal of
the solvent, dissolved incompletely in n-hexane. Heating to dissolve
the mixture followed by cooling gave a very minor amount of crystalline
material. The IR spectrum (A-III-l) suggests stearic acid, although
some difference in specific absorbances was noted.
39
-------
e. The major portion of the comMned acetone raffinates,
after evaporation of solvent, was further resolved in acid and neutral
fractions by partitioning between ether and aqueous alkali. At this
stage in the separation scheme the soaps of the residual fatty acids
do not interfere greatly with separation of the ether and aqueous layers.
Evaporation of the ether layer gave an appreciable quantity
of a liquid product whose IE spectrum (A-IV-l) indicates a keto-alcohol
This material was separated by vacuum distillation (~ 2 mm. Hg) into five
major fractions. Cuts were taken arbitrarily according to the following
schedule.
Fraction Temperature IR
1 95°-120° A-IV-IA
2 120°-150° A-IV-1B
3 150°-180° A-IV-1C
4 180°-200° A-IV-ID
Pot > 200° A-IV-1E
Infrared analyses of each fraction indicated them to be
primarily alcohols; however, a strong carbonyl absorption appeared in
all fractions.
The fractions were subjected to mass-spectrometrie analysis
Numerous molecular species were evident in each of the spectrograms, but
the differences of molecular weight suggested by the different boiling
ranges were quite evident. The analysis of the pot fraction indicated
materials of mass ~ 400. This finding suggests the possible presence
of steroids in the pyrolysate. The inherent stability of the steroid
nucleus to chemical attack and the generation of steroids in the animals'
digestive processes make it seem highly probable that these materials
could be obtained from pyrolysis of manure.
f. The basic aqueous layer was acidified and extracted
with ether. The ether layer gave an appreciable quantity of semi-solid
upon evaporation. This solid dissolved in warm acetone and gave a
semi-solid precipitate when cooled. The IR spectrum corresponded fairly
closely with that for oleic acid. However, a second recrystallization
from acetone gave a solid whose IR pattern corresponded to that for
stearic acid. The raffinate upon evaporation of the solvent again
yielded an IR spectrum (A-TV-2) suggestive of that for oleic acid.
g. The balance of the base soluble fraction from the
acetone raffinate was then resolved into a carboxylic acid and phenolic
40
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fraction "by partitioning between NaHC03 solution and ether. This procedure
gave an appreciable quantity of KaHCOs-insoluble acids, material A-V-1,
after acidification. The NaHCO^-insoluble acids contained in the ether
layer after evaporation of the solvent were further separated into two
fractions by hexane extraction. The hexane-soluble fraction (A-V-2) was
recovered as a semi-solid whose IR absorption spectrum resembles that
of oleic acid. The IR spectrum of the hexane-insoluble fraction (A-V-3)
closely resembles that of a substituted phenol.
Aqueous acid extractives (E):
a. The dilute acid extract of the pyrolysis products
contained a very small quantity of ether extractable liquid material
whose IR spectrum (B-I-l) after solvent removal indicated the presence
of alcoholic hydroxy groups.
b. Ether extraction of the aqueous phase when it had
been strongly alkalinized with sodium hydroxide gave a small quantity of
amines recoverable from the ether solvent as hydrochloride salts. These
products were judged to contain lower aliphatic amines because the dried
salts were appreciably soluble in methanol. However, treatment with
acetone dissolved part of the HCl-salt mixture. After removal of the
acetone this portion gave an IR spectrum (B-I-2) corresponding roughly
to that of an amine-HCl salt.
Ether-insoluble, acetone solubles (c); Evaporation of
the acetone extracts from the ether-insoluble residue gave a small quantity
of black solid material. This material was soluble in methanol. It was
also partially soluble in ethanol indicating the presence of several
materials. Wo clean-cut separations have been obtained. IR spectra
obtained from samples of the material are very indistinct although a
strong hydroxyl or amine absorption is observed.
The small quantity of recovered materials in this fraction
did not warrant further study.
Ether-insoluble, acetone-insoluble solid residue (D); The
relatively large quantity of black material remaining after the successive
ether and acetone extractions prompted a further investigation of its
composition. It was found to be almost completely dissolved by multiple
extraction with methanol. Stepwise evaporative concentration of the
methanol extracts allowed the recovery of small quantities of black
solids from each succeeding concentrate until the entire concentrate
gelled on cooling. The gel was warmed, further methanol evaporated,
and recooled. Two layers now formed, which permitted removal of the
residual solvent layer.
41
-------
The bulk of the black solids, combined with the precipitates
from each previous methanol concentration step, was then dissolved in hot
ethanol. On cooling the solution gelled but on standing produced a crys-
talline solid (A-rV-l) that was recovered by filtration. Attempted re-
crystallization of this from solution in hot ethanol resulted in a gelled
mixture that could not be filtered.
The ethanolic mother liquor on evaporation gave a solid
material (A-IV-2).
Infrared spectra of the two materials suggest that A-IV-1
is primarily an alcohol and that the solid residue A-IV-2 is primarily a
carboxylic acid. The evidence obtained in this investigation suggests
that the pyrolysis products were largely functional derivatives of long
chain aliphatic compounds, small amounts of steroidal or benzene nuclei,
and a small quantity of lower aliphatic amines. Very little evidence
was obtained to indicate the presence of significant quantities of prod-
ucts that were derived from the pyranose structure present in cellulesic
components of dried manure.
These findings, therefore, suggest that the conditions
employed resulted in a combination of distillation, thermal decomposition
and accompanying interaction of reactive materials in the vapor phase
developed within the heated reaction chamber.
Infrared spectra of the various fractions obtained using
Scheme I are contained in Appendix A.
Characterization, by Scheme II, of Products of _Pyr_olysis in
Iron Tube
A pyrolysis experiment was conducted by filling a 4 ft long,
2 in. diameter iron pipe with manure. Additionally, the exhaust end of
the tube was filled with a 2-in. layer of char from previous pyrolyses,
and a 3-in. layer of ceramic packing. The char and the packing were
preheated and then the tube was progressively heated along its length
with a sooty yellow flame (500°C). The char was added to improve the
opportunity for secondary reaction. The ceramic packing was put in to
prevent flow-over of unreacted manure.
The exhaust from the pyrolyzer tube was passed through two
water-cooled condensers, then through a solid carbon dioxide-cooled
condenser, through a scrubber tower and finally through a wet test meter.
Throughout the experiment, a slow stream of helium was passed through
the apparatus. This setup is shown in Figure 2.
42
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Mixture of Pyrolysis Products
Distill the Water and Volatile Compounds
II Extract with Ether
Distillate
Insoluble
Extract with Water
Soluble
I
(Evaporate the Ether)
V Extract with Water
Insoluble
W
IV
Insoluble
(Dissolve in Ether)
Extract with Methanol
VI
Extract with 10% HCI
Insoluble
Soluble
Ether Solution
VII
Solids
F
Extract with 10% NaOH
Ether Solution
VIII
Distill Ether
Solids
G
Aqueous Solution
H
Aqueous Solution
Neutralize to pH 6 and Extract with Ether
M, S, and 1
Ether Solution
Aqueous Solution
Distill Ether
Neutralize to pH 3 and Extract with Ether
Ether Solution
Aqueous Solution
Distill Ether
Negatively Substituted
Phenols and
Intermediate Acids
A1
Acidify to pH = 1
Extract with Ether
Strong Acids
A
Figure 7 -
Scheme II for Separation of Condensable Pyrolysis Products
43
-------
The tube vas charged with 331 g of manure "D" (2.7$ moisture,
8.95$ ash) and 3 hr were taken to "bring the entire length to maximum
temperature. The mass balance for the study vas as follows:
Tube loading
Dry manure 331 g
Char plug 25 g
356 g
Char recovered 140 g
Char plug 25 g
New char produced H5 g
Manure charge 331 g
New char 115 g
Loss on pyrolysis 216 g
Net gas generated 2.576 ft3
Net gas generated 72.942 liters
Assume density of 1.2 g/liter 87.53 g
Contents of first trap
Water 62.3 g
Organics boiling below 100°C 8.6 g
Organics boiling above 100°C 45.9 g
Total 116.8 g
Contents of second trap 7.1 g
Contents of -78°C condenser 7.6 g
Total condensate 131.5 g
Total of char, gas and condensate 334 g
Error in mass balance 1$
44
-------
The mixture of water and organics from the first trap was
separated according to the classical scheme for separation of organic
mixtures with further separation of the fractions "by selective solubility.
The scheme used is shown in Figure 7. It has "been designated as Scheme
II.
The initial step (l) was to distill the contents of the first
trap so that the pot temperature did not exceed 115°C. In this manner,
the low boilers and the water were separated from the main bulk of the
pyrolysate.
The distillate from Step I (70.9 g.) was redistilled in an
attempt to identify the organic components; 1.3 g of material boiled
at less than 100°C. Wo sharp boiling points were observed, and gas
chromatographic separation of this fraction indicated the presence of
at least 10 different compounds, none in high enough concentration to
warrant further separation. Water (62.3 g.) was then distilled out
leaving 7.3 g. of liquid residue boiling at greater than 100°C. This
residue was later shown by GC to contain at least 14 different compounds;
again, none was of high enough concentration to warrant further separation.
The residue from Step I was extracted with ether (Step II).
The ether-insoluble material was then extracted as follows:
Ether Insoluble Material from Step II
III
Extract with cool water
Soluble
Insoluble
Extract with hot water
1
Soluble
Wh
1
Soluble
K
1
Soluble
L
1
Soluble
D
Ins
Ins
Ins
Ins
oluble
Extract
aluble
Extract
oluble
Extract
oluble
_B
with cool methanol
with hot methanol
with chloroform
45
-------
The ether-insoluble, cool water-soluble material is designated "Wc." The
Molisch test for carbohydrates on this portion was essentially negative,
as was the test for amine salts.
¥ was distilled at atmospheric pressure and yielded fractions
toiling at 68°, 70°, 73°, 80°, 80°-120°, and 145°C. The nitrochromic
acid test for -OH was positive for all but the last distillate fraction.
It was negative for the fraction boiling at 145°C, and for the pot residue.
The ferric hydroxamate test for -C02H was positive for the residue and the
fraction boiling at 80°-120°C; it is probable that it would have also been
positive for the higher boiling fraction. The fraction boiling at 68°C
appeared from its IR spectrum to be mostly methanol. The IR spectra of
the fraction boiling at 145°C and of the residue showed strong absorptions
indicative of a carboxylic acid. The UV spectrum of the Wc material taken
prior to distillation indicated the presence of an aromatic structure.
Maximum absorbance in ethanol occurred around 230 tap, with a lesser peak
at 276.5 mu.. Benzoic acid in water gives a primary peak at 230 mjj, (e max.
11,600) and a secondary peak at 273 mp, (e max. 970). The specific class
tests together with the IR and UV spectra indicated that a component of
Vc was an aromatic carboxylic acid.
The residue from Step III was then extracted with hot water.
The soluble material was designated "W^." The IR spectrum of W^ was
nearly identical with that of Vc, indicating little, if any, separation.
The material which was insoluble in ether and in water was
extracted with cool methanol, followed by extraction with hot methanol,
yielding fractions "K" and "L", respectively. The residue from this
latter extraction was extracted with chloroform, yielding "D", which
is soluble in chloroform; and "B", which is not. The ferric hydroxamate
test for -COOH and the nitrochromic acid test for -OH are negative for
each of the above fractions. The IR spectra for K and for L indicate
strong methylene absorption (2925, 2870 and 1460 cm"1) and strong
absorption indicative of a primary amine (1690, 1600 cm"1).
The ether solution from Step II was evaporated to remove the
ether, then extracted with water (Step V). The soluble material was
designated "E." The aqueous mixture has a pH of 4.5; it was neutralized
to pH 7, then steam-distilled until the distillate was colorless. The
distillate was extracted with ether; the ether was then removed to yield
fraction "E-l." The test on this fraction for -COOH was negative; tests
for -OH and -CHO or =CO were positive. The UV spectrum indicated the
presence of an aromatic structure (major peak at or near 215 mp,, secondary
peak at 266.6 mp.)- The material E-l was then further separated by the
following scheme:
46
-------
E-l
take up in CC14, then extract
with water
CC14 soluble
E-l-a
ether soluble
E-l-b
I
Water soluble
Extract with ether
aq.
E-l-c
The portion of E remaining after steam distillation was separated as
follows:
soluble
E-2
soluble
E-3
soluble
E-4-a
soluble
E-4-b
E Residue
1. remove water
2. extract with ether
insoluble
extract with chloroform
insoluble
extract with benzene
insoluble
extract with acetone
insoluble
E-4-c
47
-------
The test for -COOH indicated that it was absent in E-2 and E-3
but present in E-4-c. The test for -CHO and =CO was positive for E-2 and
negative for E-3 and E-4-a. The test for -OH was marginally positive for
E-2 and E-4-a and negative for E-3, E-4-b and E-4-c. The IR spectra for "
E-2, E-3, and E-4-a were quite similar, and indicate the presence of an
aromatic amide or an alcohol.
The IR spectrum of E-4-c suggested a salt of a carboxylic acid.
Elemental analysis of this material gave the following: C - 37.61$, H - 4.19$,
N - 0.5$. The values for sodium adipate most nearly approximate the observed
values for C and H: Ccalcd. 37.9$, Cobs. 37.61$; Hcaicd. 4.2$, Hobs. 4.19$.
The extracted material decomposed around 340°C. The melting point or de-
composition temperature of sodium adipate has not been recorded in the
literature. Dibasic acid salts will, in general, decompose rather than
melt; this, together with the class tests, the IR spectrum and the elemental
analysis, strongly suggest sodium adipate.
The water-insoluble material from Step V was dissolved in ether
and extracted with 10$ HC1. A solid formed during the extraction was
filtered off and set aside. The acidified aqueous portion was designated
"H." Separation of H proceeded as follows:
48
-------
Aqueous solution of H
Steam distill
Distillate
Aq. residue
Extract with ether
Ether soln.
Aq. so In
Extract with ether
Ether soln.
Remove ether
H-l
Extract with
chloroform
Aq. soln.
Remove ether
H-3
Chloroform Aq. residue
soln.
Remove
chloroform
H-2
Chloroform
soln.
Extract with
chloroform
Remove
chloroform
H-4
Aq. soln.
EtOAc soln.
Remove water and extract
with ethyl acetate
Insoluble
Remove EtOAc
H-5
Benzene soluble
Remove
benzene
H-6-a
Extract with benzene
Insoluble
Extract with acetone
Acetone
soluble
Insoluble
I
H-6-b-2
Remove
acetone
H-6-b-l
49
-------
The H group of compounds primarily contained amines or amino
acids. Tests for -GOOH were negative. The UV spectrum of H-4 showed
no aromaticity. The IE spectra of several of the H group showed relatively
strong absorptions in the ranges 3300-2200 cm'1' and 2100-1800 cm"1' which
are indicative of an amine hydrochloride.
"F."
The solid which formed during extraction (Step VI) was designated
It was separated as follows:
Extract with CC14
Soluble
Insoluble
1. remove
2. extract with ether
Extract with MeOH
Soluble
F-l
Insoluble
F-2
Soluble
F-3
Insoluble
F-4
The IR spectra for the F group indicate a carboxyl salt rather
than an amine salt; however, the tests for -COOH were negative. Ho further
work was done with this fraction.
The ether solution from Step VI was extracted with 10$ EfaOH
(Step VII). A solid that separated during the extraction was designated
"G." The ether solution should have contained groups M, S, and I.
The aqueous solution from Step VII was acidified to pH 6, then
extracted with ether. The ether extract contained compounds of Group C.
The aqueous solution was further acidified to pH 5, then extracted with
ether to get compounds of Group A'. The aqueous solution was finally
acidified to pH 1 and extracted with ether to get compounds of Group A.
The fractions A, A' and C were quite small and were analyzed
only "by infrared. The spectrum of A indicated that it was largely
comprised of silicone lubricant, a probable contaminant. The IE spectrum
of A' indicated the presence of one or more carboxylic acids. The
spectrum of C suggested one or more aromatic amino acids, not necessar-
ily an o'-amino acid of natural origin.
The ether solution containing M, S and I from Step VII was
distilled to remove the ether, then extracted with absolute ethanol to
50
-------
remove a substituent, later Identified as silicone lubricant. The total
mass, M-S-I, gave a positive test for -CHO or =CO, a negative test for
-OH and -COOH. The IR spectrum indicated both a ketone and a secondary
amide; however, the ferric hydroxamate test for -CONH^ was negative.
The mixture M-S-I incompletely dissolved in concentrated sul-
fur ic acid., indicating the presence of hydrocarbons which could have been
both saturated acyclic and cyclic. The mixture dissolved incompletely
in 85$ phosphoric acid indicating the presence of hydrocarbons having
more than 8 carbon atoms per molecule. The UV spectrum indicated an
absence of aromatic compounds in this mixture.
The solid G was separated as follows:
G
1. extract with ethanol
2. extract with ether
ether solution
remove ether
extract with CC14
Insoluble
G-l-a
Soluble
G-l-b
ethanol solution
1. decolorize with
charcoal and filter
2. Crystallize
G-2
The fraction G-2 consisted mostly of the sodium salt of stearic
acid as shown by IR spectra. The IR spectrum of G-l-a also indicated the
presence of another organic acid salt.
The IR spectrum of G-l-b was very similar to the spectrum M-S-I
It is probable that a portion of the group of M-S-I was occluded in solid
G.
The mass balance of the above fractionatlon by Scheme II is
as follows:
51
-------
Total organic material 45.9 g
Material insoluble in ether 10.7 g
W - soluble in cold water
W^ - soluble in hot water
K + L - soluble in methanol
D - soluble in chloroform
B - insoluble in organic solvents
Material soluble in ether, soluble in water - E 6.9 g
Material soluble in ether, insoluble in water,
soluble in 10% hydrochloric acid - H 4.0 g
Material soluble in ether, insoluble in
water and dilute acid, soluble in 10$ sodium
hydroxide - C, A + A' 1.2 g
Material soluble in ether, insoluble in
water, acid or base - M-S-I 7.9 g
Solid G - Sodium salts of long chain
fatty acids 13.4 g
Solid F - Amine salts 1.8 g
Total 45.9 g
Infrared spectra of the significant fractionated products
separated by this scheme are shown in Appendix B.
The condensate of the second water-cooled trap was a mixture
of water and organic compounds. It was felt that the quantity of the
organics was too small to justify separation and fractionation.
The condensate in the dry-ice trap was a mixture of materials,
including carbon dioxide, acetaldehyde, propionaldehyde, iso-butyraldehyde,
n-butyraldehyde, and other uncharacterized compounds as determined by
gas chromatography.
52
-------
Discussion
The types of pyrolysis products recoverable from the combined
tars are representative of compounds that could be obtained from full
scale commercial thermal decomposition of cattle manure. Since the
samples of tars used in the initial test and Scheme I separation were
composites of products obtained in several pyrolytic experiments which
had been evaporated to apparent dryness both by heating and subsequent
air-drying, some of the low-boiling fractions originally present in the
condensates must have been lost.
Although some preliminary estimates of the quantitative
proportions of type components in the products have been made, the
number of ingredients in the composite tar sample and the varied
techniques involved in their separation and classification precluded
the derivation of highly quantitative measures of their abundance.
Clearly, a large number of compounds are present in the pyrolysate.
It must be recognized that the relative proportions of the components
could vary with both the source of the manure and the reaction con-
ditions for conducting its pyrolysis. These variations, however, are
not expected to be large.
Stearic acid was the only significant fraction of the pyrolysate
recovered in pure enough form to enable positive identification. The
small quantities available and the presence of more than one component
in each major fraction were limiting factors. In most instances,
several compounds endowed with the same general functionality were
present in each fraction. Further separation into pure components
was not warranted in this phase of the program.
53
-------
SECTION VIII
ECONOMIC CONSIDERATIONS
The economic evaluation of a potential process cannot be made in-
dependently of alternative approaches. Thus, pyrolysis as a method of ma-
nure stabilization and disposal must be viewed in relation to alternate pro-
cesses to accomplish this end. The simplest approach to manure management
is to establish a stocking rate sufficiently low that the manure is sta-
bilized in the feedlot. In such a case, the only processing costs would be
provision for runoff retention and runoff disposal.
One may progress from this low level of sophistication up through
a variety of physical, chemical, and biological processes, that have been
designed to stabilize similar wastes. The sophisticated processes hopefully
would produce a greater degree of environmental protection at no greater
fraction of operating cost than for the simplest case cited above.
There is, however, insufficient information available to construct
a very accurate table of cost/benefit ratios. A rather subjective list of
approaches to manure disposal is presented in increasing order of both tech-
nical sophistication and, hopefully, higher degree of environmental protec-
tion:
1. On-lot stabilization of manure.
2. Lot scraping and field disposal of manure.
3. Partial stabilization of solid waste to abate odor.
This assumes a system of manure collection as well.
4. Complete biological stabilization of all waste by (a) wet
biological treatment such as activated sludge, (b) "dry"
biological treatment such as composting, or (c) heat dry-
ing to the point where no further biological activity can
occur.
5. Incineration.
6. Pyrolysis.
7. Wet oxidation of a manure slurry by Zimmerman process.
In actual practice, any one of these approaches could be the best
one. The choice can be made intelligently only after a thorough engineering
study of the particular site, the surrounding environment and prevailing
economic conditions. (Any consideration of environmental management on
feedlots must recognize the problem of runoff. Runoff is more simply man-
aged by containment, followed by subsequent evaporation or use as irrigation
water. Other systems for disposal of runoff include partial or complete
stabilization without or with simultaneous treatment of solid waste.)
55
-------
A preliminary cost analysis of pyrolysis can be made on the "basis
of literature values and the data obtained in the experimental portion of
this study. The pyrolysis process itself is depicted in Figure 8, which
gives both the energy and material balances of the processes. The value
most susceptible to criticism is the 400 Btu/lb pyrolysis energy, but if
this were to vary by 100$, it would still have little effect on the over-
all analysis.
The process itself must consist of (l) drying, (2) thermal de-
composition of manure, (3) separation of decomposition products, and (4)
combustion of a portion of the pyrolysis products (char, gases, or liquids)
with auxiliary fuel.
The estimated cost/ton of pyrolyzing manure (80$ moisture) in a
feedlot of 40,000 head capacity is $5.60. Cost/market animal is $25. De-
tails of the estimate are presented below. Particularly worthy of note is
the fact that fuel oil costs (2.26/ton) are more than the value of recover-
able tars and oils (l.29/ton). This comparison makes it quite clear that py-
rolysis cannot pay its way, and that a useful fuel—oil, gas, or coal—must
be sacrificed to yield a product of presently questionable commercial value.
ECONOMIC EVALUATION OF PYROLYZER FOR MANURE
FROM A 40,OOP-HEAD BEEF CATTLE FEEDLOT
Assumptions:
1. Manure production - 50 Ib/day/head; 80$ moisture, 2$ ash.
2. 65$ thermal efficiency on predryer and pyrolyzer.
3. 1,135 Btu/lb for moisture removal.
4. 400 Btu/lb pyrolysis activation energy.
5. Capital costs - dryer $2,000/ton*
pyrolyzer $10,000/ton**
separator $30,000/ton***
6. Amortization - 10 years.
7. Delivered fuel oil at $40/ton; 13,000 Btu/lb.
8. Lot occupancy - 360 days = 2 x 180-day cycle.
* Prevailing cost for similar equipment.
** Low estimate based on 1971 costs of municipal refuse incinerators.
*** Estimated as 1/5 the cost of petroleum refinery costs reported in
"Hydrocarbon Processing" February 1971, and adjusted by 6/10 factor.
56
-------
2,000 Lb. Fresh Manure
80% Moisture, 2% Ash"
1,816,000
Btu A°n —
for Drying
160,000 Btu
for Pyrolysis
At 65% Thermal Efficiency
3,040,000 Btu
PYROLYSIS
PROCESS
Heat
Balance
Char - 143 Lb.
Ash -36.8 Lb
Carbon - 103 Lb.
l,133,OOOBtu (11,000 Btu/Lb)
Low Boilers - 29.2 Lb.
292,000 Btu (10,000 Btu/Lb)
Tarry Volatiles - 56.8
739,000 Btu (13,000 Btu/Lb)
Evaporated Moisture - 1,600 Lb.
Reaction Water - 66.8 Lb.
Exhaust Gases - 104.4 Lb.
H2, N2, CO, CO2, CH4, C2H4/
438, 000 Btu (4, 200 Btu/Lb)
2,602,000 Btu Total
1,571,000 Btu Less Liquids
Figure 8 - Material and Energy Balance in Pyrolysis Processing
of Cattle Feedlot Wastes
57
-------
BALANCE SHEET
Capital costs
Dryer $2,000 x 1,000 - $ 2,000,000
Pyrolyzer $10,000 x 200 = 2,000,000
Recovery unit $30,000 x 50 - 1,500,000
Total capital cost $ 5,500,000
Operating costs
Depreciation at K# $ 550,000
Capital charges at 6$ 330,000
Taxes and insurance at 5$ 275,000
Maintenance at 4# 220,000
Labor (18 men: 4/shift plus 5 relief
plus 1 supervisor at $5/hr) 180,000
Fuel at $40/ton ^»°°°
Miscellaneous at 2$ 110,000
Total $ 2,477,000
Credit for pyrolysate at 1.50/lb 464»OQO
$ 2,013,000
Cost per ton manure at 80$ moisture = $ 5.60
Cost per market steer = $ 25.30
58
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SECTION IX
1. Grub, W., R. C. Albin, D. M. Wells, and R. Z. Wheaton, Animal
Waste Management: Cornell University Conference on Animal Waste
Management, Ithaca, New York, 217-224 (1969).
2. PIgman, W.W., Chemistry of the Carbohydrates, Academic Press, New York,
602-647 (1948).
3. Nikitin, N. I., Chemistry of Cellulose and Wood, Davey: New York,
417-442 (1966).
4. Heuser, E., Ohe Chemistry of Cellulose, Wiley: New York., 541-558
(1944).
5. Coppick, S., "Degradation of Cellulose" in R. W. Little, ed. Flame-
proofing Textile Fabrics, Reinhold; New York, 13-75 (1947).
6. Shafizadeh, F. "Pyrolysis and Combustion of Cellulosic Materials" in
Advances in Carbohydrate Chemistry, 23j 419-74 Academic: New York
(1968).
7. Coppick, S., in R. W. Little, Flameproofing Textile Fabrics, Reinhold:
New York, 41-75 (1947).
8. Tfeunaru, K., Bulletin of the Chemical Society of Japan, 24:164-8 (1951).
9. Parks, W. G., Michael Antoni, A. E. Petrarca, and A. R. Pitochelli,
Textile Research Journal, 95:729-96 (1955).
10. Venn, H. J. P., Journal of the Textile Institute, 15JT414-8 (1924).
11. Madorsky, S. L., V..E. Hart, and S. Straus, Journal of the National
Bureau of Standards, 5£:343-354 (1956).
12. Madorsky, S. L., V. E. Hart, and S. Straus, Journal of the National
Bureau of Standards, 6£:343-9 (1958).
13. Schwenker, R. F., and L. R. Beck, Journal of Polymer Science, 2j331-340
(1963).
14. Schwenker, R. F., Jr., and E. Pascu, Chemical Engineering Data,
2:83-88 (1957).
59
-------
15. Lindsey, A. J., "The Spectrophotometric Polycyclic Aromatic hydro-
carbons", Analytica Chimica Acta, 20:179 (1959).
16. Greenwood, C. T., J. H. Knox, and E. Milne, Chemistry and Industry,
(London), 1878 (1961).
17. Lincoln, K. A., Pyrodynamics, 2:133-43 (1965).
18. Martin and Ramstad, Analytical Chemistry, 33J.982-5 (1961).
19. Cheronis, N. D., and J. B. Entrikin, Semimicro Qualitative Organic
Analysis, Interscience Publishers, Inc., New York (1958).
20. "Pyrolysis of Solid Municipal Wastes," A Summary Report of Batch Retort
Research obtained from D. A. Hoffman, Technical Studies Coordinator,
Utilities Department, City of San Diego, San Diego, California, July
1967.
21. "Conversion of Municipal and Industrial Refuse into Useful Materials by
Pyrolysis," Bureau of Mines Report of Investigations RI 7428, authored
by W. S. Banner, C. Ortuglio, J. G. Walters and D. E. Wolfson.
22. "Destructive Distillation of Scrap Tires," Bureau of Mines Report of
Investigations RI 7302 authored by D. E. Wolfson, J. A. Beckman,
J. G. Walters, and D. T. Bennett.
23. "The Chemistry of Heterocyclic Compounds," by A. A. Morton, McGraw-Hill,
New York, 1946.
24. E. Stahl, Thin-Layer Ghromatography, Academic Press, Inc., New York.
25. C. Steeling, "EPR Studies of Humic Acid and Related Model Compounds,"
in Coal Science, R. F. Gould, ed. Avd. in Chemistry Series, 55, ACS,
Washington, D. C. 1966.
26. W. Flaig, "chemistry of Humic Substances in Relation to Coalification,"
in Coal Scien-ce_.
27. Friedel, R. A., and J. A. Queiser, Anal. Chem., 28, 22 (1956).
60
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SECTION X
ACKNOWLEDGEMENTS
This report was written by Dr. William Garner and Dr. Ivan C.
Smith. The research program was conducted under the technical direction of
Dr. Garner with assistance "by Mr. Charles Bricker, Mr. Wesley Wiegand, Dr.
James Spigarelli, Mr. Eon Townsend, and Mr. Gene Moeller. Dr. James J.
Downs designed the Evolutionary Operation Computer Program that is presen-
ted in Appendix A. Mr. Tom Ferguson assisted in the economic analysis.
Dr. A. D. McElroy was administratively responsible for the program that was
conducted in the Physical Sciences Division, Dr. H. M. Hubbard, Director.
The advice and assistance of Mr. Jeffrey Denit, Chief Agricultural
Waste Research, EPA/ORM>and Mr. Ronald Hitter, Technical Project Officer,
Vllth Regional Office, EPA/ORM?is gratefully acknowledged. The program was
conducted under Contract 14-12-850 between the Environmental Protection
Agency and the Midwest Research Institute.
61
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APPENDIX A
EVOLUTIONARY OPERATION APPLIED TO
EXPERIMENTAL MANURE PYROLYSES
I. Introduction
The experimental manure pyrolyses on this program have been per-
formed using a set of experimental conditions, and a relatively new exper-
imental design system called Evolutionary Operation.—' The objective of
this system is to determine optimum process conditions for manure pyrolysis
using a minimum number of experiments.
Evolutionary Operation (EVOP) is an experimental method using fac-
torial design for experimental conditions. It differs from standard factor-
ial design experiments, which tend to be large and complicated, in that it
limits the number of experimental conditions being investigated at any one
time. Using EVOP, many experimental conditions maybe investigated, but
only a certain number at any one time. The advantages of this method of op-
eration are that less experimental measurements are needed to find an op-
timum set of conditions; the freedom to add new experimental conditions is
not restricted, and the results of one run may be used to indicate a set of
conditions nearer the optimum, for the next run.
In the terminology of EVOP, an experimental test is called a pjia_s_e.
A phase consists of sets of four or eight experimental runs of predetermined
combinations of two levels of experimental conditions. A cycle is a repli-
cate test on the same phase. In the factorial design terminology, the phase
design is either 2^ or 2^ factorial design.
II. Fyrolysis Conditions
The experimental test conditions for manure pyrolyses were made up
of combinations of pyrolysis temperatures and pressures, and two kinds of ma-
nure. The first manure (manure A) was a farm lot sample from cattle fed on
corn and alfalfa. The second manure (manure B) was a concrete pad sample
from cattle fed on cracked corn with a diet supplement. The combinations
of these experimental factors, with their phase numbers, are given in Table
A-l. Three cycles of each phase were run.
I/ "Evolutionary Operation" G.E.P. Box and N.R. Draper, John Wiley and
Sons. New York, 1969.
63
-------
TABLE A-l
PYROLYSIS CONDITIONS
Phase
1
2
3
4
5
6
Temperature
Levels
(°c)
400/500
500/600
400/500
500/600
400/500
500/600
Pressure
Levels
(atm)
0/1
0/1
0/1
0/1
0/1
0/1
Manure
Component(s)
(A or B)
A
A
B
B
A/B
A/B
Factorial
De s ign
2"
a2
>-\
22
o
22
«2*
23
23
III. Experimental Goals
The experimental results are expressed as percentages of the weight
of volatile^/ material charged to the reactor. Pyrolysis components were
determined as:
PCT.(PIC) - The weight percent of material condensed in the dry
ice trap,
PCT.(TAR-H) - The weight percent of distillable tar, soluble in
water,
PCT.(TAR-C) - The weight percent of distillable tar, soluble in
chloroform, and
PCT.(CHAR) - The weight percent of residue remaining in the reac-
tor, minus the determined percentage of ash in the original manure.
The experimental goals were to adjust conditions to maximize PCT.
) and PCT.(TAR-C) and minimize PCT.(CHAR).
IV. Experimental Results
The experimental results were analyzed using a computer program
written for use in a time-shared computer. The program name is EVOP, and it
is written in the Extended Basic Language for use on United Computer Services'
GE-265 computer system.
2/ Volatiles = loss on ignition at 600°C,
64
-------
Computer outputs of the experimental results are shown in Figures
A-l to A-6. Each figure represents a phase of experimentation shown in Table
A-l. In the figures, the following items may be noted reading down the page
(the reference is Figure A-l):
Phase:
Factors:
Results:
Latest Results:
Latest Average:
Standard Error:
2S.E. Limits:
Number.
High and low level experimental conditions.
Kind of data.
Factorial analysis of the experimental data
(converted to percentage) at Cycle 3.
First, the factorial analysis of experimental
data averaged over three cycles; second,
the averages, once three cycles, of the ex-
perimental data at each level (H or L) of
temperature (l) and pressure (P).
The estimated standard deviation of the ex-
perimental results, often three cycles.
The estimated limit for real means and ef-
fects in the factorial analysis. Means
and effects larger than the 2S.E. Limit may
be counted as real at approximately the 90fo
confidence level.
V. Interpretation of Results
The interpretation of factorial analysis results depends on the
various averages of combinations of factor levels. With reference to Figure
1 (22 design), the Mean is the average around the cycle of all four experi-
mental readings for each percentage. T, the temperature effect, is the av-
erage change in percentage, going from low to high temperature, for each per-
centage. P, the pressure effect, is the average change in percentage, going
from low to high pressure, for each percentage. TP, the interaction effect,
measures the curvature of the percentage response to changing conditions. If
the square, bounded by TLPL3 TH?L> TLPH> and THPH is consldered to be a Pla"
nar surface, the TP interaction introduces a curvature which can show the con-
tours of the response surface for each kind of percentage measured experimen-
tally. Such a contour map of the experimental area points out clearly the
ways to adjust experimental conditions to approach optimum yields.
The general run of the results is as follows:
• At Phase 1, high temperature decreases char and increases tar,
with similar effects for low pressure. Therefore, Phase 2 was run at a higher
set of temperature conditions (500 and 600°C).
65
-------
EACTQPJAL ANALYSIS
PHASE: 1
FACTORS:
HI LEVEL LO LEVEL
TErtFEPATTFE: 5PP Af'V
PPESS-1'PE: 1 P
VOL A TILES:
LATEST PESt'LT:
CYCLE: 3
EFFECT FCI.(DIC) PCT.(IAP-H) FCT.(IAF-C) PCT.(CHAP)
t'.EAN * 2.82 4. f p> 12.58 23. <*3
1 1.P5 4.8P 6.85 -5.15
P ' -1.<45 -.5P -6.45 3.R5
TP -1.P5 -1.5? -*. 15 -2. 15
LATEST AVEPACE:
CY CL E : 3
EFFECT PCI.(LID PCI.(TAP-H) PC7.(TAt5-C) FCT.(CHAP)
M F AN " 2. <*R
1 * ' .63 ^
F ' -.7P
TP -,?P
LiSItM ^
T F PCT.(DIC)
L L ?. 57
HI -r •* f
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67
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68
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69
-------
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70
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Figure A-6 - Phase 6
71
-------
• At Phase 2, high temperature decreases char slightly, but
decreases tar greatly. Low pressure is still advantageous. Optimum run con-
ditions have been located near 500 °C, and Phase 3 was run using different
manure.
* At Phase 5, char is lower at high temperature, and low pres-
sure is still advantageous. Therefore, Phase 4 was run at higher tempera-
ture conditions (500 and 600°C).
* At Phase 4, tars are increased at high temperature and char
continues to decrease, indicating an optimum at even higher temperature con-
ditions .
' Phase 5 is a recapitulation of results from Phase 1 and
Phase 3 showing the effects of changing manure on experimental conditions in
the range 400-500°C.
* Phase 6 is a recapitulation of results from Phase 2 and
Phase 4 showing the results of changing manure experimental conditions in
the range 500-600°C.
A comparison of the results of Phase 5 and Phase 6 against the
goals of decreased char and increased tar shows clearly that the type of
manure used is the overriding experimental factor in the pyrolyses.
Another view of the experimental process situation is shown in
Figures A-7 and A-8, which give response contour surfaces for the exper-
imental data. Percentages are shown on contour lines across the entire ex-
perimental region for manure A and manure B. The optimum regions for tar
production using manure A can be easily seen in Figure A-7. For manure B,
these optimums are absent except at the highest temperatures, where an op-
timal region is indicated. A rule that char decreases at high temperature
can be made from both figures.
From an economic point of view, manure A would seem the most ad-
vantageous for processing because of the lower temperature optimums. Thus,
we must isolate the characteristic of manure A that produces this effect.
Vacuum conditions are not economically prohibitive.
Finally, sequential significance tests were made to compare ex-
perimental treatments of the two kinds of manure, and establish the validity
of the indicated trends between them. After three cycles of experimental
measurement, the validity of most of these trends is established at the 95^
confidence level, and no more experimental runs to verify these trends are
needed. The verified trends in going from manure A to manure B in Phase 1
and Phase 3 are shown in Table A-2.
72
-------
MANURE "A"
600-
i
550-
500-
450-
400-
0 0.5 I
PRESSURE (ATM)
%
TAR-H
0 0.5
PRESSURE (ATM)
%
TAR-C
/ /
14 /
,20
-22-
•34-
.26-
,28
0 0.5
PRESSURE (ATM)
CHAR
Figure A-'- Response Surfaces: Manure "A1
-------
MANURE "B"
•
•
600-
550-
500-
450-
400
0.5
PRESSURE (ATM)
%
TAR-H
6
, \
H
0 0.5
PRESSURE (ATM)
TAR-C
—26
28
36.
0.5
PRESSURE (ATM)
CHAR
•i ;uri - Response Surfaces: Manure "BT
-------
Design
POT. (DIG)
TABLE A-2
VERIFIED TRENDS
Manure A to Manure B
POT. (TAR-H)
PCT. (TAR-C)
FCT. (CHAE)
LL
HL
LH
HH
Effects
Mean
T
P
TP
Increase
Increase
-
-
Increase
Decrease
Decrease
Increase
-
Decrease
Decrease
Decrease
Decrease
Decrease
-
Increase
Decrease
Decrease
Decrease
Decrease
Decrease
Decrease
-
Increase
Increase
Increase
Increase
Increase
Increase
Decrease
—
-
VI. Conclusions
Factorial analysis on experimental measurements showed that the
type of manure processed is the single most important factor in manure py-
rolyses.
Of the experimental manures used, the feed lot manure sample
showed more desiratle process conditions than the concrete pad manure sample.
Three cycles (replicates) of each experimental run are sufficient
to verify experimental trends.
-------
APPENDIX B
INFRARED SPECTRA OF SIGNIFICANT MATERIALS SEPARATED
FROM CATTLE MANURE PYROLYSATES BY SCHEME I
77
-------
4000 3000
_l_
?000
1500
CM' 1000 900 800 700
:
7 8 9 10 11
WAVELENGTH (MICRONS
12 13
-
Material A-I-1
<000
100
S 9 10
WAVELENGTH MICRONS
12 U 14 15
4000 ?OOC
100
Material A-II-1
CM '000 900 ECO 70C
8 9 10 11
WAVELENGTH MICRONS
12 13 14 15
Material A-II-2
78
-------
4000 3000
100
1500
800
700
1
l\
-
7 8 9 10 11 12
WAVELENGTH ^MICRONS
14 15
Material A-II-3
4000 3000
CM1
1000 WO
SOO
700
7 6 9 iO n
WAVELENGTH MICRONS
1? 1.
Material A-III-1
3000
2000
1580 CM 1000 900 800
700
7 S 9 10
WAVELENGTH :MICRONS
Material A-IV-1
-------
700
jitiflQ
7 8 9 10 11 12 13 14 15
WAVELENGTH (MICRONS!
Material A-IV-1A
4000 3000
2000
1500
CM'1
1000 900 800
700
7 8 9 10 11 12 13
WAVELENGTH (MICRONS;
Material A-IV-IB
4000 3000
100
2000
700
8 9 10
WAVELENGTH (MICRONS)
Material A-IV-1C
80
-------
4000 3000
2000
1500
CM'1
1000 900 800
700
7 8 9 10
WAVELENGTH (MICRONS)
12
13 14 i;
Material A-IV-ID
4000 3000
100
7000
1500
CM'
1000 900
800
700
7 8 9 10 11
WAVELENGTH IMICRONSj
12 13 14 15
Material A-IV-IE
4000 3000
100
7000
1500
CM-'
1000 900
800
700
7 8 9 10
WAVELENGTH 1MICRONS)
13 14
15
Material A-IV-2
-------
4000 3000
2000
1500
CM'
1000 900 800
700
7 8 9 10 11
WAVELENGTH (MICRONS)
12 13 14
Material A-V-1
4000 3000
1000 900
800
700
7 8 9 10 11
WAVELENGTH (MICRONS;
12 13 14 15
Material A-V-2
4000 3000
100
?000
1500
CM'
1000 900
800
100
B<
7 8 9 10
WAVELENGTH (MICRONS
12 13
••—ID
14 15
Material A-V-3
-
-------
4000 3000 2000 1500 CM'1 1000 900 800 700
6 7 8 9 10 11 12 13 14
WAVELENGTH (MICRONS)
Material A-VI-1
4000 3000
2000
1500
CM'1
1000 900 800
700
9 10 11 12 13 14 15
Material A-VI-2
I
4000 3000 200C
100
CM'1 1000 900 800
700
3 4
7 8 9 10 11
WAVELENGTH (MICRONS!
12 13 14 li
Material B-I-1
83
-------
K
7 8 9 10
WAVELENGTH (MICRONS)
11 12 13 14 15
Material B-I-2
-------
APPENDIX C
INFRARED SPECTRA OF SIGNIFICANT MATERIALS SEPARATED
FROM CATTLE MANURE PYROLYSATES BY SCHEME II
85
-------
VELENGTH (
10 13 14 15
4000 3000 2000 1500 1200 1000 900
700
.
WAVELENGTH (MICRONS
6 7 8 9 10
12 13 14
4000 3000
2000
1500
1200
CM
1000 900
800
700
Wc Distillate Fraction I, b.p. 68°C
WAVELENGTH [MICRONS
7 9 11 12 13 14
1500 1200 1000 900 800
4000 3000
Wc Distillate Fraction VI, b.p. 145°C
:.
-------
WAVELENGTH (MICRONS)
6 7 8 9 1.0 1.1
12 13
-
:
4000 3000
2000
1500
1200
CM'
1000 900
800
700
Wc Residue After Distillation
WAVELENGTH (MICRONS:
6 78 9 10 11 12 13
4000 3000
700
10»f
WAVELENGTH MICRONS.
10 11 12 13 U
4000 3000
700
:
-------
100
WAVELENGTH (MICRONS!
- 10 11 12 14
40003000 2CXX 5500 1200 1000 900
700
WAVELENGTH (MICRONS)
14
4000 3000
700
E-l-b GC Distillate Fraction III
WAVELENGTH fMICRONS
10 14
700
E-l-b GC Distillate Fraction IV
88
-------
WAVELENGTH [MICRONS)
10 11 12 13 14
4000 3000
E-l-b GC Distillate Fraction V
6 WAVELENGTH ^MICRONS)
-
4000 3000
2000
1500
1200 1000 900 800
CM'
E-4-a
WAVELENGTH jMiCRONSj
12 1.3
100
4000 3000
2000
1500
1200
1000
CM1
E-4-c
-------
WAVELENGTH (MICRONS
10 11 12 13 14 15
4000 3000
700
H-4
WAVELENGTH MICRONS
to 11 12 13 u
-H
4000 3000
- |20
1500
120C 1000 900
CM
800
70C
H-6-b-l
100
WAVELENGTH MICRONS
14 15
4000 3000
2000
H-6-B-2
90
-------
100
4000 3000
WAVELEN
ENGTH (MICRONS)
8 9 10 11 12 13 14 15
2000
1500
1200
CM1
1000 900
800
700
WAVELENGTH
7 8
(MICRONS)
9 10 11
4000 3000
2000
700
M-S-I
WAVELENGTH [MICRONS]
6 7 8 9 10 11
12 13
U
4000 3000
700
G-2
-------
APPENDIX D
WASTE PRODUCTION AS RELATED
TO ANIMAL FEED*
General - This section deals primarily with feeds for beef cattle
and the quantity and quality of the resultant waste. The basic approach
used to estimate the waste characteristics can be extended to other animals
using the concepts outlined and applicable data for specific animal species.
The type of feed consumed by an animal affects the quantity and
characteristics of the waste that is produced. Fresh beef cattle manure
will contain 80 to 85% moisture and will contain undigested feed from the
digestive tract, unabsorbed digestive juices, residue of the digestive tract,
and waste minerals. Lignin and hemicellulose are relatively stable mate-
rials that are not easily digestible by cattle and will exist in the waste.
These materials are a large fraction of high roughage feeds and are in all
rations to some extent.
It can be expected that the waste matter in beef cattle feedlots
will be different from that of cattle on general farms or on pasture. Since
the early 1960's, more efficient rations and feeding programs have helped
maintain the economic position of the cattle feedlot operation. Increas-
ingly large numbers of feeder cattle are fed high concentrate rations in
the feedlots. High concentrate rations lend themselves to mechanical proc-
essing and handling. A concentrate:roughage ratio of 4:1 has been sug-
gested as ideal with respect to rate of gain, feed efficiency, and carcass
merit for commercial feeders. The large feedlot operator will prefer to feed
a completely mixed feed.
A large quantity of cattle are still fed on farms and ranches that
produce large quantities of harvested roughage or pasture. Because of the
higher quantity of nondigestible matter in roughage, cattle on pasture or
roughages will be expected to produce a higher quantity of waste per day
than_cattlefed a large quantity of concentrates.
Fattening cattle will consume daily an amount of dry feed equal to
about 2.5 - 3.0$ of their body weight. The type of roughage utilized in a
feed ration will be a function of the operator's choice and relative feed
costs.
Nutrition studies have established that the protein level in the
feed ration will have a marked effect on the total digestibility of the
* Based on a report to the project by Dr. Raymond C. Loehr, Cornell Univer-
sity.
-------
dry matter in ruminant rations. The addition of protein compounds to a
ration having a low protein content will increase the breakdown of the
carbohydrates and makes other nutrients more digestible. The feeding of
1 - 2 Ib. of protein supplement apparently has no significant effect on
the amount of grain and roughage consumed by an animal but can account for
better digestibility of roughage.
Feed Rations - The ration fed beef cattle will vary from region to
region, due to the costs of specific feed components, and will vary with the
age of the animal. "Typical" feed rations rarely exist; however, examples
can be noted to illustrate general composition:
AVERAGE RATIONS
A B
Ground corn Corn silage
Corn silage Soybean meal
Protein supplement
COMMERCIAL FEEDLOT HIGH ENERGY RATION
Ground alfalfa hay
Cottonseed hulls
Steam processed milo
Cottonseed pellets
Most of the large feedlot operations have installed their own feed
processing operations, frequently automated and controlled by a skilled an-
imal nutritionist. In addition to feed chopping and grinding, many feeds
are pelleted or flaked prior to feeding.
Estimated Waste - The best approach to determine the waste pro-
duced by a given feed is to conduct nutritional trials and measure the quan-
tity and quality of excreted wastes. While quite accurate, the process is
time consuming and costly.
It is possible to estimate the quantity and quality of the waste
if the nature and digestion coefficients for a feed are known. Such data
have been obtained from nutritional studies over the years and have been
compiled by Morrison^/ and others. The data are available on the quantity
of protein, fat (ethyl ether extract), fiber, nonfiber extract (MFE), and
mineral matter in the feed. Other nutritional data of interest, such as
94
-------
major mineral components, are also frequently available. The digestion co-
efficients for protein, fat, fiber, and NFE are listed by Morrison for cer-
tain feeds.
The digestion coefficients represent the percent of the feed com-
ponent that is not in the waste matter. They represent the maximum utili-
zation of a feed component by an animal. Some digestion coefficients, such
as for protein, represent apparent digestibility because the waste contains
metabolic as well as digested nitrogen. The digested or used portion is not
determined directly in the case of any of the nutrients and the term coef-
ficient of apparent digestibility frequently is used since the coefficients
are determined by difference.
Digestion coefficients are not constants for a given feed or ani-
mal species and are influenced by factors such as the nature and relation-
ships of the nutrients fed. Crude fiber tends to exert a protective influ-
ence against the digestibility of all nutrients. It is recognized that the
digestibility of a mixture is not necessarily the average of the values for
its constituents determined separately or indirectly. Each feed component
may exert an influence on the digestibility of the other. In addition in-
dividual lots of a particular feed may differ from the average.
Even though these differences and variations are recognized, di-
gestion coefficients can be used to estimate the quantity and quality of
waste from a given feed. This has been done for selected feeds that may be
components of beef cattle feed rations. The data on the composition of the
wastes are presented in Table D-l. The data on the feed composition were
obtained from Morrison.—/ Examples showing how the data were obtained are
presented on page 93.
Assumptions implicit in the data noted in Table D-l require clari-
fication. It has been assumed that all of the mineral matter in the feed
exists in the feces, i.e., the waste. The soluble minerals such as sodium,
potassium, and urea are in the urine and may not be part of the feces de-
pending upon how the wastes are held before collection and treatment or
disposal. Depending upon the characteristics of the mineral content of the
feed, up to about 50% of these minerals will be excreted with the urine and
may not be part of the feces. Thus the data for mineral content of the
waste as noted in Table D-l may be on the high side . The actual mineral
content of the wastes also will be a function of the quantity of dirt and
inerts consumed by the animal in addition to that in the feed.
Urine from large beef cattle can be produced at a rate of 20 Ib.
per animal per day and contains about 6% dry matter. It is a major source
of fluid in accumulated cattle wastes. Urine contains by-products of metab-
olism and serves as the major carrier of mineral wastes from the animal.
95
-------
The data In Table D-l are expressed as waste dry matter. While
the -waste may be defecated with 80-85$ moisture content, the actual moisture
content as well as chemical composition will be affected by the environmental
conditions and the time the wastes lay in the feedlot prior to collection.
Decomposition of organic matter and loss of nitrogenous matter will occur,
especially during wet and warm weather.
The volatile content of the waste can be estimated by the sum of
the protein, fat, fiber, and NFE percentages of the dry waste. The mineral
content can be used as an estimate of the ash content. The composition of
the fiber and NFE can be estimated as combinations of lignin, cellulose, and
hemi-cellulose.
The estimated wastes for selected feeds (Table D-l) indicate that
for dry roughages, green roughages, and silage, the waste matter is from 50
to 46$ of the dry matter in the feed and that the mineral content of the
waste is from 12 to 55$ for these feeds as well as for concentrates. As ex-
pected the waste from the concentrates is a smaller portion of the dry mat-
ter in the feed, 11 to 35$.
This information may be useful in estimating the difference in the
composition of wastes from cattle fed different feed rations. If this point
is critical to a study, it is suggested that information be obtained regard-
ing typical rations of the region as well as actual characteristics of wastes
resulting from these feeds.
1. Morrison, F. B., Feeds and Feeding, 22nd Edition, Morrison
Publishing Company, 1961.
2. Maynard, L. A., and Loosli, J. K., Animal Nutrition, 6th
Edition, McGraw Hill, 1969.
3. Newmann, A. L. , and Snapp, R. R., Beef_Cattle, 6th Edition
Wiley, 1969.
4. Wagnon, K. A., Albaugh, R., and Hart, G. H., Beef Cattle
Production, Macmillan, 1960.
96
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TABLE D-l
POTENTIAL QUALITY AND QUANTITY OF WASTE FROM SELECTED FSEDS
Total Dry Matter Waste
Feed in Feed (%) Parameter
Dry Roughages
Alfalfa Hay 90.5
Brcme Jrass Hay 88.8
Clover Hay, Red 88.3
C.^rii rodder, '.veil
Eared, Very Dry ?1.1
3ras3 Hay, Mixed,
Good Quality 39.0
Mile Fodder 88.5
Pasture Grass,
and Clovers,
Dry, Fertile
Pasture J0.0
Sorghum Fodder
Dry, Sweet 88.9
rim." thy Hay 89.0
3reen Roughages
Alfalfa Hay,
Jreer. 24.4
Clover, Red 24.5
Grasses, Mixed
Pasture 28.1
Pasture Grasses
and Legumes,
Mixed 22.0
Sorghum Fodder
Sweet 24.9
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Cf Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
* Of Total
Lb/100 Lb.
% Cf Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
73 Of Total
Lb/100 Lb.
Cf Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
Protein
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
4.
10.
5.
12.
4.
4
4
1
5
,8
12.6
4,
11.
3
9
5
12
5
20
2
6
3
8
T
11
1
14
1
12
1
15
0
.0
.7
.5
.1
.0
.5
.3
.4
.6
.6
.5
.5
.1
.0
.2
.0
.2
.8
.2
.8
.7
Fat
1.3
3.2
1.3
3.2
1.1
2.9
0.6
1.8
1.3
3.4
1.3
3.0
1.2
4.6
o.e
2.1
1.2
2.9
0.6
6.0
0.3
3.5
0.3
8.5
0.5
6.6
0.3
Fiber
15.7
36.9
11.6
28.4
12 . 6
33 . 3
8.4
24.6
12.0
31.0
8.5
21.2
4.1
15.8
9.6
25.7
13.0
30.6
3.5
35.0
2.8
32.0
1.6
17.0
1.3
17.1
2.7
GFB
11.
27.
14.
35.
12.
34.
14.
43.
16.
42.
18.
46.
7
29
17
46
ie
45
2
26
2
26
3
32
2
35
3
0
0
4
3
9
2
7
0
4
4
4
0
, 7
. 6
.3
7
.4
.7
.6
.0
.3
.5
.0
.0
"7
.6
. 5
Mineral Dry
Matter Total of
8,
19.
8.
20.
6.
17.
0 40.5
'
2 40.6
0
4 37.6
0
• W&ste .-. = Percer.t
Dry Matter in Feed
45
46
43
6.4 34.1 37
18.8
5,
14,
6
17
-?
29
"7
is
5
- o
2
22
2
24
2
29
1
25
I
,5 38.7
,2
.9 40.0
.2
.7 26.0
. 6
.1 3S.1
.6
. 0 41.1
•2
.2 10.0
.0
.1 8.7
.0
.8 9.4
•7
.9 7.6
.C
.4 8.6
43
45
"9
43
45
41
36
33
34
35
% Cf Total Waste 8.1 3.5 31.4 40.7 16.3
97
-------
TABU3 D-L (Concluded)
Total Dry Matter Waste
Feed in Feed (%) Parameter
Silages
Alfalfa, Not
Wilted 24.7
Atlas Sorghum 29.7
Clover, Red
Not Wilted 29.5
Corn, Well
Matured 2? . 6
Concentrates
Blood Meal 91.6
Clover Seed,
Red 87.5
Corn , Grade
No. 1 Si. 0
Corn Gluten
Meal ?1.6
Cottonseed Meal
rT Caka 459c
Protein Or More 94.3
Linseed Meal 91.1
Milo Grain 89.0
Lb/].00 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lc/100 Lb.
=£ Of Total
Lb/100 Lb.
* Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
% Of Total
Lb/100 Lb.
Protein
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
Waste
Feed
% Of Total Waste
Peanut Oil
Meal, 45 %
Protein Grade ?4.0
Lb/100 Lc.
Feed
* Of Total Waste
1.5
12.
1.
8.
1.
10.
1.
11.
23.
74.
5.
27.
6
1
5
3
2
1
0
8
0
2
,4
2.0
20,
6
42
6
31
4
22
2
19
3
23
.0
.5
.5
.4
.6
.6
.0
.4
.0
.9
.8
Fat
0.
3.
0.
3.
0.
5.
0.
2.
1.
4
4
4
4
4
2
2
0
2
3.7
1.0
5.2
0.4
4
0
1
0
0
0
1
0
5
.0
.2
.3
.2
.8
.4
.9
.7
.6
0.5
3.0
Fiber
4.1
34.5
3.1
26.5
4.2
33.1
2.3
23.0
0.7
2.2
1.7
9.0
0.9
9.0
1.6
10.5
5.8
22.0
3.6
17.2
1.0
8.0
2.7
16.5
KFE
3.
30.
4.
41.
4.
33.
4.
49.
0.
2.
4.
6
3
8
0
3
9
9
0
7
2
4
23.1
5,
50
2
17
5
19
6
31
6
51
3
23
,0
.0
.7
.7
.2
.7
.6
.5
. 4
.7
.9
.6
Mineral Dry
Matter Total of
2.3 11.9
19.3
2.3 11.7
19.6
2.5 12.7
19.7
1.6 10.1
16.0
5.7 32 . 1
17.7
6.7 19.0
35.2
1.3 9.9
13.0
4.3 15.3
28.1
6.8 26.4
25. B
5.7 20.9
27.2
2.1 12.6
16.7
5.4 16.4
33.0
waste As Percei
Dry Matter in Fi
48
39
43
37
35
22
11
17
28
23
14
17
-------
EXAMPLES OF ESTIMATING WASTE CHARACTERISTICS
FROM SPECIFIC FEEDS
Waste = Feed (l-Digestion Coefficient)
Dry Roughage
Alfalfa hay, all analyses
Protein
Fat
Fiber
NFE
Mineral
Total
Average
Composition
W
15.3
1.9
28.6
36.7
8.0
Digestion
Coefficient
71
30
45
70
0
Waste
4.4
1.3
15.7
11.0
8.0
Component
in Waste
(%}
10.9
3.2
38.9
27.0
19.7
90.5
40.5 100.0
Therefore, 100 Ib. of this roughage as feed, would contain 90.5 Ib. of total
dry matter which would produce 40.5 Ib. of dry waste matter, i.e., 45$ of
the dry matter intake.
Concentrate
Mi lo Grain
Protein
Fat
Fiber
NFE
Mineral
Total
Average
Composition
(*)
10.9
3.0
2.3
70.7
2,1
Digestion
Coefficient
78
78
58
91
0
Waste
2.4
0.7
1.0
6.4
2.1
Component
in Waste
/ _/ \
(%}
19.0
5.6
8.0
50.7
16.7
89,0
12.6
100.0
Therefore, 100 Ib. of this concentrate as feed, would contain 89.0 Ib. of
total dry matter which would produce 12.6 Ib. of dry waste matter, i.e.,
of the dry matter intake.
99
-------
1
Accession Number
w
5
2
Subject Field & Group
05D
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Organization Midwest Research Institute
Kansas City, Missouri 64110
Title
THE DISPOSAL OF CATTLE FEEDLOT WASTES BY PYROLYSIS
10
Authors)
Dr. William Garner
Dr. Ivan C. Smith
16
Project Designation
Project No. 13040 EGH; Contract No. 14-12-850
21
Note
22
Citation
Environmental Protection Agency report
number, EPA-R2-73-096, January 1973.
23
Descriptors (Starred First)
*Pyrolysis, *Qualitative Organic Separation, *Gas Condensation
25
Identifiers (Starred First)
*Pyrolysis, *Feedlot Waste, *Economic Analysis
27
Abstract
Beef cattle (steer) manure was obtained from a source that was free of soil
contamination, and subsequently dried and pulverized. Replicate batch pyrolyses
were carried out in stainless steel, glass, and iron tubes utilizing axial flow,
at various levels of elevated temperature, and at atmospheric and lower pressures.
Exhausts were carried by inert gas to traps and condensers. Qualitative
separations and extractions were performed to determine the presence and quantity
of various gasas, ash, tar, and organics. Many constituents were extracted, but
in such small quantities that their value may not pay for the cost of pyrolizing.
Larger scale pyrolyzing units should be tested to either confirm or disprove
these findings.
Abstractor
n.
F,
Anderson
Institution
ntal Protc
icticm
Agpnry,
OR&M
WR:102 (REV- JULY 1969)
WRSIC
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 20240
1HJ.S. GOVERNMENT PRINTING OFFICE: 1973 514-152/164 1-3
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