3.

6 Pyrolysis | Page 1 Manure Processing Technologies

What Is Pyrolysis?
Pyrolysis is the direct thermochemical conversion
(TCC) of organic material in an oxygen deficient
environment. It results in gaseous and liquid
products as well as a solid. The gaseous product
stream can contain both condensable gases
(those which become liquids at room
temperature), such as water, lighter hydrocarbons
(oil), and tars, and non-condensable gases
including carbon monoxide (CO), methane (CH
4
),
carbon dioxide (CO
2
) and hydrogen (H
2
). Pyrolysis
is described as occurring in three stages:
Stage I: the drying process (32-250
o
F);
Stage II: the main pyrolysis process (250-
850
o
F)
Stage III: the carbonization stage (> 850
o
F).

Figure 1. Overview of thermal conversion processes
(Corson-Lassiter, 2013)


Pyrolysis differs from combustion of biomass in two key areas: First, complete combustion of biomass
occurs at temperatures greater than 1250
o
F, which are higher than those typically used in pyrolysis, and
second, combustion requires oxygen to be present, while pyrolysis takes place under very low or no
oxygen conditions. Thermochemical decomposition, which leaves mostly carbon as the residue, is called
carbonization (Jenkins, 1999; Wikipedia-Pyrolysis, 2012). An example of carbonization is the conversion
of wood to make charcoal. Thermochemical conversion used to produce primarily a fuel gas is called
gasification. Figure 1 depicts the pyrolysis process. Typical process conditions for pyrolysis are
temperatures ranging from 750 to 1100
o
F and pressures ranging from 14.5 psi (atmospheric pressure) -
72.5 psi. In addition, pyrolysis requires the organic material to be dry (usually <10% moisture) before it
enters the reaction chamber.

Products of pyrolysis: The products generated from pyrolysis include gas, liquid (water and bio-oil), and
solids (bio-char). The synthesized gas (syngas) is typically a mixture of mostly CO, CO
2
, H
2
and CH
4
and
can be burned directly or processed to create higher energy fuels or chemical products. The bio-oil can
be further processed to produce higher-quality fuels such as biodiesel, combusted to produce heat or
electricity, or refined to produce chemical feedstocks such as resins and coatings. The biochar (char &
ash) can be used as a soil amendment, for a filtration or absorption media for water purification or gas
cleaning, or as charcoal for home cooking.

Feedstock Characteristics
Many sources of organic matter can be used as feedstocks for pyrolysis

(Klass, 1998; Cantrell et. al.,
2007). Plant sources can include sawdust, nut shells, straw, cotton trash, rice hulls, and switchgrass.
Manure Processing Technologies
3.6 Pyrolysis
Shannon Hollis, Harold Keener, and Meghan Smith


3.6 Pyrolysis | Page 2 Manure Processing Technologies
Animal sources can include waste streams, such as chicken manure, poultry litter, swine manure, beef
feedlot manure and dairy manure. In the pyrolysis process, moisture content, ash levels, and chemical
components of the feedstock will have a direct impact on the conversion of biomass to gas, liquid or
char.

Proximate analysis: The moisture, volatile matter, fixed carbon, and ash content of three animal
manures determined by prescribed methods (proximate analysis) are presented in Table 1. Because of
high moisture levels in fresh swine (>88%), cattle (>85%) and chicken manure (>70%), they need to be
dried ahead of the pyrolysis reactor.

Table 1. Proximate analysis results for swine, cattle and chicken manure
Manure Type Reference
Proximate analysis
1
(wt%)
Water Content
(ar)
Volatile Matter
d
Fixed Carbon
d
Ash
d
Swine Tu et.al. 2008 68.01 70.21 12.1 17.7
Swine ECN, Phyllis-#1366 92.1 51.3 13.3 35.4
Cattle Tu et.al. 2008 81.4 71.24 15.38 13.38
Cattle feedlot) ECN, Phyllis-#1882 13.88
2
70.27 13.86 15.87
Chicken Tu et.al. 2008 73.59 61.42 10.49 28.09
Chicken (layers) ECN, Phyllis-#3501 19.25
2
65.56 12.80 21.65
1
ar: as received basis, d: dry basis,
2
moisture content suggest air drying prior to collection/analysis

In proximate analysis volatile matter is a measure of the gases, oils and tars given off when biomass is
heated above 300
o
C and is determined by American Society for Testing Materials procedure (Klass,
1998). As can be seen in Table 1, volatile matter is 50-70% of the dry matter in manures. Ash is the
mineral matter left after complete combustion of the biomass has occurred. Table 1 indicates ash
content for swine, cattle, and chicken manure can be up to 35%, which is very high compared to other
biomass used in pyrolysis. For example, wood has typical ash contents between to 2%. These high ash
levels in animal manures results in less oil and gas per unit (volume or mass) of dry solids being
processed. In addition, animal waste may also contain soil, which increases the ash content of the
feedstock. Because ash generally contains alkali salts, in particular potassium, thermochemical
conversion of these materials may lead to surface fouling and corrosion of metals in pyrolysis reactor
systems. This will shorten the useful life of equipment, decrease system performance, and increase
maintenance requirements. On a positive note, certain elements in ash are catalytic to the thermal
decomposition process and at low levels may improve overall efficiency for producing a specific product
(Cantrell et. al., 2007). Fixed carbon is created in the pyrolysis process. It is calculated by subtracting out
the percent of water, volatile solids, and ash from the starting mass. Fixed carbon in animal manures
(Table 1) ranges from 10-15%. In standard lab analysis of manures fixed carbon is included in the
volatile solids measurement.

Chemical Components: Chemical components of biomass include cellulose, hemicellulose, lignin, lipids,
proteins, simple sugars, starches, hydrocarbons, and other compounds. The chemical composition of
swine, cattle and chicken manure are given in Table 2. Note in this table, neutral detergent soluble
includes lipids, proteins, and sugars. Variability in animal manures is expected due to feeding rations as
well as the animals metabolism.




3.6 Pyrolysis | Page 3 Manure Processing Technologies

Table 2. Chemical composition analysis for animal manures (Tu et. al., 2008)
Type
Neutral detergent soluble
(a.d. wt%)
Hemicellulose
(a.d.wt%)
Cellulose
(a.d. wt%)
Lignin
(a.d. wt/%)
Swine 43.001.00 27.333.21 14.671.15 6.330.58
Cattle 26.002.83 18.330.58 23.502.12 19.001.43
Chicken 54.331.53 24.000.58 4.337.51 16.001.40

Pyrolysis Process:
The pyrolysis process is described as slow, fast, and flash pyrolysis, as well as gasification. Ranges for
process parameters, including heat input rate, time, temperature, pressure, and moisture levels are
outlined in Table 3 along with ratios of expected distribution of products. Both pyrolysis time and
temperature are key operating parameters that influence product yields and distributions. Klass (1998)
stated moderate but optimized temperatures are needed at short resident times to maximize liquid
yields, whereas long resident times and low temperatures are needed to maximize char yields.

Table 3. Thermochemical Conversion Technologies Summary
Name Residence Time Temp (F) Heating Rate Major Products
Carbonization Hours-Days 572-932 Very Low Charcoal
Pyrolysis Hours 752-1112 Low Solids, Liquids, Gases
Fast Pyrolysis 5-30 Min 1292-1652 Medium Solids, Gases
Flash Pyrolysis <1 Sec 1202-1832 High Liquids, Gases
Gasification 10-20 Sec >930 High Gases
Hydrothermal
Liquefaction
15-120 Min <932 + High
Pressure
Medium Liquids
Adapted from Huber, Iborra & Corma, 2006; Klass,1998.

Pyrolysis Systems:
Klass (1998) stated:

Pyrolysis systems are as varied as combustion systems. The ancient process of making
charcoal by slow pyrolysis of a pile of wood --- to biomass pyrolysis reactors in industrialized
countries consisting of various types of ovens, and horizontal and vertical retorts, ---to
modern --- configurations of fixed beds, moving beds, suspended beds, fluidized beds,
entrained-feed solids reactors, stationary vertical-shaft reactors, inclined rotating kilns,
horizontal shaft kilns, high-temperature (1000 to 3000
o
C) electrically heated reactors with
gas-blanketed walls, single and multi-hearth reactors, and a host of other designs

Table 4 lists several reactor designs found in use today.

Table 4. Types of Pyrolysis Reactors
Reactor Design
Evaluated
Feedstocks
Capacity (Dry Biomass) Manufacturer Products
Fluidized Bed
1
400 kg/hr (10.6 tons/day)
Dynamotive,
Canada
Fuel
Wood
Waterloo Fast
Pyrolysis Process
2
Oil (80%), Water


3.6 Pyrolysis | Page 4 Manure Processing Technologies
250 kg/hr (6.6 tons/day) Wellman, UK Fuel
20 kg/hr (0.5 tons/day) RTI, Canada Research, Fuel
Circulating
Fluidized Bed
1
1500 kg/hr (40 tons/day)
Red Arrow, WI
(Ensyn Design)
Food Flavorings
/Chemicals
1700 kg/hr (45 tons/day)
Red Arrow, WI
(Ensyn Design)
Food Flavorings
/Chemicals
20 kg/hr (0.5 tons/day)
VTT, Finland (Ensyn
Design)
Research/Fuels
Rotating Cone
1
200 kg/hr (5.3 tons/day) BTG, Netherlands Research/Fuels
Vacuum
1
3500 kh/hr (93 tons/day) Pyrovac, Canada
Pilot Scale
Demonstration,
Fuels
Fluidized Bed
2
Wood 100 tons/day Ensyn Bio-Oil, Syn Gas
Fixed Bed, Up
Draft
2
Wood Nexterra Syn Gas
Rice hulls, turkey
litter, cotton gin
trash, wood
PRM Energy Syn Gas
Fixed Bed, Down
Draft
2

Dried biosolids,
paper, chicken litter,
cow manure, wood

Max West, Coaltec,
Inc.
Syn Gas (up to 30
mmBTU/hr)
Source:
1
Ringer et al., 2006;
2
Pytlar et al., 2010;
3
Yi et al., 2005

What are the System Components for Pyrolysis?
Many components are required for operation of a pyrolysis system, from the pre-process of drying and
size reduction to the separation and cleaning systems capturing the various products. An exception is
the simple ovens solely used for charcoal/char production (IBI, 2012). Flow diagrams for two pyrolysis
systems, a pilot scale and a commercial system, are shown in Figures 2 and 3, respectively. Table 5 lists
the key components for the two systems. The components of a pyrolysis unit will vary depending on
type of system used and characteristics of the feedstock.




Figure 2. USIG skid-mounted pilot-scale pyrolysis
system flow diagram. (Ro et. al., 2010)


Figure 3. KUG pyrolysis/gasification system. (Pyrolyzer,
LLC, 2011)





3.6 Pyrolysis | Page 5 Manure Processing Technologies
Table 5. Typical components for pilot and commercial scale pyrolysis units
Process Step Component Considerations
M
a
n
u
r
e

H
a
n
d
l
i
n
g

Manure collection at farm Storage pit, barn
Manure transport to pyrolysis reactor Auger, conveyor, pump, other
Feedstock preparation (mix, grind) Holding/mixing tank, grinder
Feedstock dewatering/drying Dryer
P
y
r
o
l
y
s
i
s

S
y
s
t
e
m

Pyrolysis reactor Feed element, heating element, high temperature reactor
Control system Required for system monitoring & operations
Energy reclamation system Heat capture and recycle to reduce energy requirements
Product movement Pump
Product separation
Separator (gas-oil-char), char processor, venture/gas scrubber
(gas clean-up)
Support equipment for gas scrubber
Recirculating water tank, water chiller, gas discharge pump,
bladder tank, compressor, gas storage tank,
Energy recovery equipment Heat exchanger
P
r
o
d
u
c
t

U
t
i
l
i
z
a
t
i
o
n

Syn gas to heat/electricity Boiler, gas engine, turbine
Bio oil Extraction system to dewater, storage system
Bio char Dryer, storage equipment
Waste water Storage, land application, treatment
Waste heat Steam turbine
References: Ro et al., 2010 and Pyrolyzer, LLC., 2011.

Production Units:
The literature on pyrolysis technologies for animal manures is almost solely based on results from
laboratory-scale, batch reactors, or micro-scale thermo-gravimetric analyzers (TGAs). These small scale
studies have provided a knowledge base for operating pilot scale and commercial pyrolysis units with
animal manures as feedstocks. While there are numerous commercial pyrolysis systems being used for
cellulosic feedstocks, few reports have been found on the performance of large scale pyrolysis units
using animal waste as feedstock. Below are results for one commercial system which has been used for
the conversion of livestock manure.

USIG Skid-Mounted Pyrolysis System. This system is manufactured by US Innovation Group, Inc. (USIG,
Indianapolis, IN. It is used to produce combustible gases from various carbon wastes (Ro et. al., 2010).
A picture of the system is shown in Figure 4. Figure 2 is the flow diagram for the system. Ro et al. used
this system to produce combustible gas and biochar at 1150
o
F from three sources, chicken litter, swine
solids, and a mixture of swine solids with rye grass. The bio-char produced from pyrolysis of these three
feedstocks showed that while 100% of the P and K present in the starting biomass remained in the
resulting bio-char, approximately 73% of the N and 77% of the S were lost to other product streams.
This result should be noted when considering pyrolyzed bio-char as a soil amendment.


3.6 Pyrolysis | Page 6 Manure Processing Technologies

What are the Benefits and Limitations of
Pyrolysis?
Pyrolysis technologies may provide advantages
including compact design, fast treatment times,
reduction of odors, reduction of BOD, and
elimination of sludge. The application of this
technology may reduce land disposal charges (i.e.
fuel, tipping, transportation) as the nutrients are
concentrated into a nutrient-dense, residual solid
(Cantrell, 2007) that can be more cost effectively
transported. The volume and weight of the waste
material is significantly reduced during the process
of pyrolysis, which is important in managing
livestock waste. However, investment and
operating costs are significant and management of
the system requires a high level of expertise. It may
be less costly to dry the manure, which would
achieve weight reduction, volume reduction, and
potentially minimize N losses, but would not require the same level of technical expertise to operate the
processing system. Currently, other manure processing technologies appear to offer similar benefits
with less risks. Table 6 gives a list of benefits and limitations for pyrolysis of livestock manures.

Table 6. Benefits and Limitations of Pyrolysis Systems
Benefits
Can produce valuable products (bio-gas, bio-oil, bio-char).
Can reduce manure odors and biological oxygen demand (BOD).
Allows for easier transport of nutrients and removal from the watershed.
Commercial systems are available.
Limitations
Practical only for dry biomass (moisture content <30%). Most animal manures will
require supplemental drying.
High maintenance costs, due to the high ash content in animal manures, cause
equipment fouling and corrosion.
Requires the management of three product streams after processing (liquid, solid, gas).
Currently, no economically viable commercial scale systems for processing of high
moisture content livestock manure exist.

What is the Income Potential of Pyrolysis?
Due to the lack of commercial systems that are designed to process livestock manure is difficult to
quantify the economics of a farm-scale system. Currently, operational data and products produced
when processing manure by pyrolysis is lacking. However, for manure at moisture levels > 10% one can
expect that supplemental energy will likely be necessary to dry the manure. Due to this additional
drying step, based on available data in the literature, pyrolysis would not be expected to generate any
income for high moisture manures (>30% moisture).

Table 7 shows the energy to dry material (i.e. manure) at various moisture contents to levels suitable for
pyrolysis. At $2.30 per gallon for propane, cost to dry 30% moisture manure (e.g. broiler litter) to 10%
moisture is projected to be $29.87/ton of dry matter whereas drying 50% moisture manure to 10%
Figure 4. USIG skid-mounted pilot scale pyrolysis
system. Ro et al., 2010


3.6 Pyrolysis | Page 7 Manure Processing Technologies
would cost $83.81/ton per ton of dry matter. Assuming a current value of urea, DAP and potash at
$385.00, $507.50 and $390.00 per ton, respectively, the fertilizer value of chicken litter, cattle manure
and swine manure at 10% moisture would be approximately $69, $18 and $44 per ton, respectively
(ECN, Phyllis- #3195; ECN, Phyllis- #2833; ECN, Phyllis- #3069).

Table 7. Energy to dry feedstock (Btu and gallons propane per ton of dry biomass and weight of water
lost per unit dry matter, %)
Feedstock
Moisture
Dry to 0%
(eff=60%)
Dry 0% (60% eff) Dry 10% (60% eff)
% wb BTU/ton
dm

1
gal/ton
dm

2
$/ton
dm

weight
loss, %
1
gal/ton
dm

2
$/ton
dm

weight loss,
%
10 410,370 4.6 10.49 11 0.0 0.00 0
30 1,582,857 17.6 40.45 43 13.0 29.87 29
50 3,693,333 41.0 94.39 100 36.4 83.81 80
70 8,617,778 95.8 220.23 233 91.2 209.65 200
90 33,240,000 369.3 849.47 900 364.7 838.89 800
1
Propane ~90,000 Btu/gallon;
2
Propane price = $2.30/gallon


Additional Resources
Bridgewater, IEA Bioenergy Biomass Pyrolysis Overview:
http://www.ieabioenergy.com/MediaItem.aspx?id=5416
Pytlar, Staus of Existing Biomass Gasfication and Pyrolysis Facilities in North America:
http://www.seas.columbia.edu/earth/wtert/sofos/nawtec/nawtec18/nawtec18-3521.pdf
USDA Biomass Pyrolysis Research: http://www.ars.usda.gov/Main/docs.htm?docid=19898
Washington State University, Economic Value of Biochar in Crop Production:
http://faculty.ses.wsu.edu/WorkingPapers/sgalinato/WP_2010-03.pdf

Acknowledgement
This project was funded by the USDA-NRCS Conservation Innovation Grant program with additional
financial support from the Ohio Soybean Council.

Disclaimer
Any specific company or process mentioned in these documents is for informational purposes only and
should not be considered an endorsement.

References:
Cantrell, K., K. Ro, D. Mahajan. 2007, Role of Thermochemical Conversion in Livestock Waste-to-Energy
Treatments: Obstacles and Opportunities. Industrial & Engineering Chemistry Research. Vol 46
26:8918-8927.
Corson-Lassiter, J. 2013. The Farm Manure to Energy Initiative: Chesapeake Bay Region. Presented at
the From Waste to Worth: Spreading Science & Solutions Conference, Denver, CO. April 1-5, 2013.
ECN. http://www.ecn.nl/phyllis2/ Accessed 2013. (ECN is Energy research Centre of the Netherlands)


3.6 Pyrolysis | Page 8 Manure Processing Technologies
IBI. Biochar Production Units. http://www.biochar-international.org/technology/production accessed
2012
Jenkins. B.M. 1999. Part 3.2.2 Pyrolysis Gas. Pp 222-248 in O. Kitani, T. Jungbluth, R.M. Peart, and D.
Ramdani, eds. CIGR Handbook of Agricultural Engineering. Volume V: Energy and Biomass Engineering.
Copyright ASAE. St. Joseph, Michigan. USA: American Society of Agricultural Engineers.
Keener, H.M. 2006. Chapter 1. Manure characteristics. In: The Ohio Livestock Manure Management
Guide, Bulletin 604. The Ohio State University Extension. Columbus, OH.
Klass, D.L. 1998. Biomass for Renewable Energy, Fuels, and Chemicals. Elselvier Press, San Diego, CA.
Ro, K.S., K.B. Cantrell, and P.G. Hunt. 2010. High Temperature Pyrolysis of Blended Animal Manures for
Producing Renewable Energy and Value-Added Biochar. Ind. Eng. Chem. Res. Vol.49: 10125-10131.
Tu D., H. Dong, and B. Shang. 2008. Pyrolysis behavior of selected manures using TG-FTIR Techniques. .
2008
Ringer, V. Putsche, J. Scahill. 2006. Large-Scale Pyrolysis Oil Production: A Technology Assessment and
Economic Analysis; Technical Report NREL/TP-510-37779. November 2006.
PryolyzerLLC. Pyrolyzer. Next Generation Waste-to-Energy Technology. 2011 (www.PryolyzerLLC.com)
Wikipedia-Pyrolysis. http://en.wikipedia.org/wiki/Pyrolysis#cite_note-inno-0. Accessed August 2013.
Wikipedia-Biochar. http://en.wikipedia.org/wiki/Biochar. Accessed August 2013.