Fuel Processing Technology 143 (2016) 151–161

Contents lists available at ScienceDirect

Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Fast pyrolysis of lignocellulosics in a twin screw mixer reactor

E. Henrich a, N. Dahmen a,⁎, F. Weirich a, R. Reimert b, C. Kornmayer c
a
Institute for Catalysis Research and Technology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
b
Engler-Bunte Institute, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany
c
WEHRLE-Werk AG, Emmendingen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: A process development unit (PDU) with 10 kg/h biomass capacity was designed, built and operated for fast
Received 8 July 2015 pyrolysis of biomass. A twin-screw type reactor, in earlier applications used for treatment of coal, oil shale, oil
Received in revised form 10 November 2015 sand and oil refinery residues, was used. Test campaigns with a variety of biomass types were performed. The
Accepted 12 November 2015
results with hard-wood, softwood, wheat straw and wheat bran are reported and discussed in this paper, verify-
Available online 3 December 2015
ing the suitability of the twin screw reactor along with a new product recovery procedure. Liquid pyrolysis
Keywords:
condensate, termed bio-oil, is the main product of FP and the yields are about 65 ± 10 wt.% for wood but only
Fast pyrolysis about 50 ± 10 wt.% for cereal straw, which is a typical result for all fast growing types of biomass with higher
Twin screw mixer reactor ash content. These product yields and properties are similar to those found for other FP reactor types and recov-
Bio-oil ery procedures.
Bio-slurry © 2015 Elsevier B.V. All rights reserved.
Lignocellulose
Biomass

1. Introduction a pressurized entrained flow (PEF) gasifier in a BTL (biomass to liquids)

The development of fast pyrolysis (FP) of biomass was initiated
more than 30 years ago in the wake of the oil price crisis in 1973 and
1980. The charming idea was the conversion of abundant woody bio-
mass in a cheap, single and simple conversion step by FP at 500 °C
into a liquid condensate termed bio-oil, with the aim to substitute a
substantial part of crude oil based fuel oils and motor fuels. The work
was pioneered by Scott and co-workers at the University of Waterloo
in Canada [1–4], a country exhibiting large forest biomass resources.
In the EU extensive research, development and demonstration work
was supported by the European Commission and co-ordinated by
Bridgwater since 1995 [5–7]. The actual technology status of FP is
reviewed by Bridgewater in [8] and the actual state-of-the-art in active
countries is reported by Meier [9]. Although some pilot plants in the
MW-range exist and first commercial plants are erected, no general
breakthrough of this technology can be observed. Crude bio-oil is a
mix of several hundred constituents and has a poor quality regarding
the direct use as a motor fuel. It is unstable and not miscible with diesel
or gasoline. Quality improvements by upgrading procedures or other
bio-oil applications are reviewed by Czernik and Bridgwater [10] and
Xiu [11]. A multistage hydrogenation process to upgrade bio-oil to a re-
finery feed is reported by Venderbosch [12].
Therefore, the aim of the FP process development work at KIT is not
bio-oil production for direct use as a fuel oil, but serves as a first step for
⁎ Corresponding author.
E-mail address: nicolaus.dahmen@kit.edu (N. Dahmen).
process for synthetic bio-fuel production by preparing a densified and
unified liquid feed from various types of biomass [13,14,15]. A large
PEF gasifier for syngas generation [16,17] is the central step of a thermo-
chemical biorefinery and is followed by syngas cleaning and the
catalysed production of organic platform chemicals or liquid transporta-
tion fuels, according to the concept of the bioliq process currently under
development at KIT [18].
A mixture of solid biochar particles suspended in liquid bio-oil is
termed bio-slurry or biosyncrude and produced by FP as an intermedi-
ate fuel with high energy density allowing for a more convenient
handling, storage, and transportation compared to the original biomass.
Simultaneously, a slurry is a suitable gasifier feed which can easily be
pumped and atomized into a pressurized entrained flow gasification
reactor [13,19]. Bio-oil contains ca. 60 ± 10% of the initial biomass
energy, but combined with the pyrolysis char, the energy content in a
bio-slurry can be raised to almost 90%.
Compared to the application of bio-oil in internal combustion
engines, a much lower quality is sufficient for gasification. Contamina-
tion with solids and especially ash containing char particles is a main
obstacle for more challenging applications. In a slagging entrained
flow gasifier [25] ash is even needed to generate a molten slag layer at
the inner gasifier wall to protect it from corrosion and erosion. The
lower quality requirements for the gasifier feed also allow some simpli-
fications of the FP process itself: No perfect separation of char from the
condensate is needed. In this paper even a simultaneous recovery of
pyrolysis char together with the pyrolysis condensate has been investi-
gated, and the results are reported.

http://dx.doi.org/10.1016/j.fuproc.2015.11.003
0378-3820/© 2015 Elsevier B.V. All rights reserved.
152 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161
Another characteristic of the FP process at KIT is the use of a special
pyrolysis reactor type. The so called twin screw mixer reactor has
originally been developed in Germany by Lurgi half a century ago for
the FP of materials like coal, oil shale or vacuum residues of an oil refin-
ery [20,21,22,23] and was already applied commercially. Twin screw
mixer reactors operated at 600 °C with up to 1.1 m outer screw diameter
and 600 m3/h circulating heat carrier were already built [25]. The essen-
tial design characteristic is the circulation of a hot grainy heat carrier in a
closed loop via the twin screw mixer reactor and a heat exchanger. The
heat exchanger and the reactor are the source and the sink of heat in the
closed loop. Heat carrier circulation is maintained either by a pneumatic
or a mechanical heat carrier lift followed by gravity flow.
This paper describes design and operation of a FP process develop-
ment unit (PDU) with a twin screw mixer reactor with 10 kg/h biomass
capacity. Product yields and compositions of pyrolysis char, condensate,
and gas from hardwood and softwood as well as from wheat straw and
wheat bran pyrolysis are reported and discussed. Conclusions are drawn
in view of a reasonable further development direction for biomass FP, as
it will be conducted utilizing the 2 MWth FP pilot plant also available at
KIT.
2. Description of the FP process development unit
Fig. 1 shows a flow scheme of the PDU designed for 10 kg/h biomass
feed capacity. The facility consists of a feeding section, a heat carrier loop
for FP operated at 500 °C, a cooling section for product recovery and a
final section for production and handling of bio-slurry products. These
sections are described in the following in more detail.
Fig. 1. Simplified flowsheet of the fast pyrolysis process development unit (PDU).
2.1. Feeding section
A batch of up to 100 kg crushed, dry lignocellulosic biomass is kept in
a closed feed storage vessel. A small characteristic biomass particle
length L of less than 0.5 mm and a water and ash content both below
ca.10 wt.% are desirable feed properties. Wood was fed as sawdust,
whereas chopped straw was further grained in a hammer or knife
mill, especially to smash the thick ca. 5 wt.% stem nodes, which present
a bottleneck to rapid heating-up as required for FP. Drying is achieved
by passing a stream of warm air through the well mixed feed bag
prior to operation
An expensive feed flow control system with a continuous balance
turned out to be rather sensitive to minor process disturbances and
caused frequent process disruptions. It was finally abandoned and re-
placed by a calibrated simple and robust screw feeder with volumetric
flow control, which supplies the FP reactor with a sufficiently constant
volume flow of feed material in a range of 6–16 kg/h.
2.2. Heat carrier loop
The purpose of the heat carrier is to supply the heat for pyrolysis by
quickly mixing a cold or preheated feed with a surplus of hot carrier ma-
terial of ca. 550 °C. The hot heat carrier loop consisting of the FP reactor,
a bucket elevator and an electric heater constitutes the technically most
complex and expensive section of the facility. Other design options e.g. a
pneumatic lift of 1 mm quartz or SiC sand with the hot flue gas of
pyrolysis gas combustion are discussed elsewhere [24,25,26].
 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161
2.2.1. Heat carriers
Heat carriers which have been tested in the PDU are temperature
and corrosion resistant grainy solids like 1 mm quartz or SiC sand or
1.5 mm diameter stainless steel (SS) balls. The most reliable operation
and the highest availability and throughput of the PDU were obtained
with the SS balls and further investigations were confined to this heat
carrier.
Up to 1.6 t/h SS spheres can be lifted with the bucket elevator and
circulated by gravity flow in a closed loop. The spheres showed negligi-
ble attrition; after 1.000 h of operation time the weight change of 1000
of SS spheres was found to be below 1%. In the pyrolysis reactor the cold
feed material (bulk density between 100 and 300 kg/m3) is rapidly
mixed with a surplus of hot SS balls (bulk density 4800 kg/m3). A
volume ratio of about one ensures efficient mutual contact surface for
heat transfer and results in a heat carrier-to-biomass bulk mass ratio
in between 30 to 100 (with sand only ca. 5–20) and a temperature
drop of 10–100 °C of the heat carrier between inlet and outlet of the
pyrolysis reactor.
2.2.2. Bucket elevator and heater
The heat carrier leaves the horizontal pyrolysis reactor with a
temperature of about 500 °C, is vertically lifted by 3 m with a bucket
elevator, and discharged into a small buffer vessel. The vessel is
arranged at the top of a 0.12 m diameter, 1.5 m long vertical cylinder
gap heat exchanger with 1.1 m2 surface area. About half of the ca.10 L
SS ball heat carrier inventory in the loop (ca. 50 kg or 10+ L) is in the
1 cm wide annular gap volume of the heater and passes the exchanger
by gravity in about one minute; it is heated electrically from
both, inner and outer, sides. A calibrated and controlled screw feeder
at the heater exit, transfers a constant heat carrier stream to the FP
reactor.
Fig. 2. Design of the twin screw mixer reactor process development unit with 10–20 kg/h capacity.
153
2.2.3. Twin screw mixer reactor
The design of the twin screw mixer reactor and its working principle
is shown in Fig. 2. The intertwining screws rotate in the same direction
and permanently clean each other as well as the inner reactor walls.
Radial mixing with a rotation speed is in the range of Froude number
one: Fr = (2 n)2 r/g = 1 with n = 3.53 s−1 (n rotational frequency,
r = 0.02 m outer screw radius, g = 9.81 m/s2 gravitational acceleration)
where centrifugal forces at the outer screw radius and gravitational
forces of the heat carrier just compensate each other, proved to be a
suitable design criterion for scale-up [35]. A dimensional analysis of
screw mixers shows, that the Froude number is part of the set of dimen-
sionless numbers needed for scaling [36,37]. This eases free flowing
similar to a fluid bed. A suitable balance between sufficient radial
mixing and axial transport is achieved by a pitch-to-diameter ratio of
the screws in the order of ca. 5 [21,26].
The residence time distribution of heat carrier and biomass in the
twin screw reactor shows a non-linear dependency on the rotation
frequency, see Fig. 3. Suitable operating conditions at about 3.5 Hz
with a Fr-number near 1 are indicated and lead to a Bodenstein number
above 50, indicating that plug flow conditions are a reasonable approx-
imation for reactor modelling. At these conditions up to 1.5 t/h heat
carrier circulation, the filling level in the reactor is about half of its
total volume or less as shown in Fig. 4. At higher levels there is a risk
of reactor plugging in case of feed flow fluctuations. Mixing of feed
and carrier at such low levels may not be very efficient, but sufficient
to serve its purpose [27].
2.3. Product recovery section
Much development work has been devoted to various types of FP
reactors [5], but dedicated reports on FP product recovery variations
154 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161

Fig. 3. Residence time distribution in the twin screw mixer reactor.

or design details are scarce. In most cases the standard recovery mode is tube condenser as an aqueous condensate at the final cooling tempera-
used without much explanation ture near ambient.

2.3.1. Standard FP product recovery mode
The first step in FP product recovery from the hot product gas is usu-
ally the separation of char dust particles by use of a cyclone at pyrolysis
temperature of 500 °C. Efficient char removal avoids the contamination
of bio-oil with ash containing char, which otherwise could prevent the
use as a motor fuel. In a second step, at temperatures somewhat
above ambient, a liquid condensate is recovered in a quench condenser
by injection of recycled, cooled condensate. The viscosity of the con-
densate obtained must be low enough for common circular pumps
(ca. ≤0.5 Pas) to avoid pumping problems and guaranties a sufficiently
high overall heat transfer coefficient for efficient cooling.
In the PDU, one or two-step condensation can be performed. A main-
ly organic condensate is first removed at a higher temperature between
60 and 90 °C. The higher condensation temperature allows for a water
content ≥15% in a homogeneous liquor without later phase separation
to maintain a sufficiently low viscosity for pumping. The organic and
water vapours remaining in the pyrolysis gas are then recovered down-
stream in a second condensation step with a conventional shell-and-
2.3.2. Alternative FP product recovery mode
In the standard mode the char and condensate(s) are recovered
separately. For gasification, they are mixed later on to produce the
desired bio-slurry feed. Separate handling of warm, highly porous FP
char powder in air involves a high risk of self-ignition and dust explo-
sion. This risk can be reduced with the following product recovery
mode:
For gasification, char particles and condensate are mixed anyway
later on to form a bio-slurry. Combining char and condensate recovery
in a single step already in the product recovery train can reduce the
technical effort and simultaneously eliminate the ignition and dust ex-
plosion risks of the pyrophoric pyrolysis char. This has been achieved
by contact cooling of the hot product stream immediately down-
stream from the FP reactor in a scratch cooler. At condensation temper-
atures above 100 °C, a tar with low water content condenses. The hot
liquid tar is soaked into the pore system of the char and solidifies
there after cooling. Some sticky tar film is left outside the particles and
agglomerates them to form larger char crumbs during cooling.

Fig. 4. Level in the FP reactor at increasing rotation frequency for three different heat carrier circulation rates.
 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161
To obtain a soft and less sticky product, lower condensation temper-
atures between 90 and 60 °C or even below can be applied, where most
of the water vapour condenses and the char particles are collected in a
sludgy product, which covers the heat exchanger surface in a thick but
soft layer. The layer has been removed in periods of several seconds
by a scraper to maintain sufficient heat transfer. To recover a small
remainder of aqueous and organic vapours in form of a clear, aqueous
condensate, a second conventional condenser was operated down-
stream at about ambient temperature. This small condensate volume
can be mixed with the quench product to produce a single gasifier
feed, at least during warming-up prior to gasification. If the exit temper-
ature of the scratch cooler is low enough to recover the majority of
water vapour, there might be no need for a second condensation step,
since the small remaining organic vapour fraction can contribute to
the calorific value of the pyrolysis gas which is used to heat the circulat-
ing heat carrier. Solid char crumbs or pasty bio-sludge products with a
viscosity ≥ca. 1 Pa⋅s are not suited for injection cooling and circulation
for quench condensation.
This one-step bio-sludge recovery process was tested in the PDU.
The scratch cooler is not a simple piece of equipment. The design of
the first scratch condenser was a vertical 1.5 m long SS pipe of 0.06 m
diameter, equipped with a cooling jacket and a half-cylinder scraper
for the inner pipe surface, operated periodically every several seconds
to discharge the condensate/char sludge layer into a vessel below.
3. Experimental procedure
The heat carrier loop is preheated by first circulating the heat carrier
with the bucket elevator at a constant rate of about 1 t SS balls per hour.
The 8 kW electrical heater in the heat carrier loop needs a few hours to
achieve a stable operation temperature of 500 °C in the facility. Some
more hours are required, until the thick thermal insulation of the PDU
heat carrier loop is approximately in thermal equilibrium. After this pe-
riod with manual heater control the facility can be kept at steady-state
conditions with automatic control and is ready for start-up.
3.1. Description of a test run
An air-dry, well mixed amount of 20–100 kg biomass feed allows for
several hours of operation and was found to be sufficient to determine
reliable mass and energy balances within the limits of reproducibility
(see chap. 5.1). After a change of the operating conditions, new steady
state conditions can be attained within several minutes, because of the
short char and heat carrier residence time of ca. 10–15 s in the pyrolysis
reactor. The heat carrier inventory of ca. 50 kg needs 2–3 min for one
pass
At a constant heat carrier circulation rate of 1.15 t/h, a constant bio-
mass feed rate of normally about 10 kg/h was fed into the pyrolysis
reactor by the volume calibrated screw feeder. At constant heat carrier
circulation, the reactor exit temperature of 490–500 °C and the temper-
ature drop of 20–50 K within the reactor could be kept at reasonably
constant values with occasional manual control of the heater and the
biomass feed rate. A constant stream of pyrolysis gases and vapours
carries out almost all the fine and highly porous char particles. The
moving SS balls of the heat carrier act like a ball mill, and the small
char remainder in the heat carrier is further crushed and then carried
out in a second or third pass. Heat carrier samples taken downstream
from the reactor during operation showed a low carbon content,
accounting for 10–20% of the biomass feed, a value which depends
strongly on reactor design and operating conditions, especially the gas
phase velocities in the reactor outlet section.
3.2. Feed and product analysis
For the experiments, four different types of biomass have been
selected, differing in chemical composition and fuel properties: Soft
155
and hard wood (Fir/spruce and beech wood, respectively), wheat
straw and wheat bran.
Biomass feed analysis: The water content was measured by drying
the material at 110 °C according to DIN 51718. The ash content was de-
termined using the DIN 51719 procedure at an oven temperature of 815
°C. The superior calorific HS value was measured in a bomb calorimeter
according to DIN 51900-1. The elemental composition (CHONS) was de-
termined with a Microelementar Vario EL instrument of Elementar; N, S
detection limits are 0.5%. Averages of four measurements and moisture
corrections have been applied. The total biomass feed for a run was de-
termined by weight.
FP product analysis: For char yield determination the char crumbs or
bio-sludge from the scratch cooler are extracted several times with dry
methanol by accelerated solvent extraction (ASE) in a Dionex apparatus
at 10 MPa and 40 °C. The char weight is determined after drying. Ion
chromatography shows, that also some solid ash components are eluted
during solvent extraction. The extract has therefore been analysed after
extraction for “residue” ash.
Complete deagglomeration and extraction of char crumbs requires
very efficient mixing. Measurements were repeated 3 times with a
relative standard deviation of ± 2% for liquid condensates and ± 5%
for char crumbs. CHONS elemental analysis was determined in the
Microelementar instrument mentioned above.
The water content of both condensates and char crumbs has been
determined with the Karl Fischer standard titration method (Metrohm)
after dilution with a 3/1 methanol–chloroform solution. The water
content is the sum of reaction water and moisture. The reaction water
fraction is calculated from the total water from Karl Fischer titration
minus the known moisture fraction of the dried feed material.
Pyrolysis gas samples are taken periodically during steady state con-
ditions, and an adequate number of samples resulted in a reasonably
accurate average value. Analysis was performed in a gas chromatograph
for determination of CO2, CO, CH4, H2 and C2–C5 alkanes and alkenes
after drying of the gas. The determination of the absolute volume flow
rate is achieved by adding a known, constant flow of Ne to the pyrolysis
reactor as an internal standard. The water vapour loss with the pyrolysis
gas was not determined and is part of the reported mass deficit.
3.3. Representative analytical samples
Taking representative samples, and their correct preparation for
analytical purposes is an important activity and decisive for the correct
evaluation of a test run. Samples of only few mg are needed for the
elemental CHONS-determination (ultimate analysis), and only ca. 1 g
for measuring the superior calorific value HS in a bomb calorimeter.
These two measurements are decisive for a correct energy balance.
Moisture in the bio-feed is measured by weight loss of larger samples.
If the liquid product separates into two phases, two samples have to
be analysed, and the composition of the total condensate and its calorific
value must then be calculated from the mass ratio of the separated
phases.
In the course of a run, bio-sludge samples are collected in several
10 L plastic buckets with a lid to avoid evaporation losses. Total yield de-
termination by weight difference between full and empty buckets is
simple and accurate, but taking small samples after homogenisation in
the range of a gram or less without evaporation losses is difficult and
requires much care. These difficulties are even greater for bio-sludge
samples from straw, which are prone to immediate phase separation.
The corresponding scatter in the elemental composition or in the
bomb calorimeter measurements increases the potential error in the
energy balance compared to the mass balance.
4. Experimental results
The yields of char (including the ash content), condensates and gas
produced are the essential basis for the selection of suitable FP process
156 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161

conditions and equipment design characteristics for an envisaged Table 2

application. Average yields of FP products in wt.% with standard deviation, referring to moist feedstock
as fed into the plant.
For comparison of the product mass and energy yields reported in
the literature, the char fraction in the bio-sludge obtained by the work FP feedstock Hardwood Softwood Wheat Wheat
described here was determined by extraction with methanol followed straw bran

by drying. To get the total condensate mass fraction, the amount of Number of runs 7 5 4 3
aqueous condensate from the second condenser with some volatile or- Water content 9.5 13.5 9.7 12.0
Ash 1.1 0.5 6.0 5.5
ganics was added to the bio-sludge minus char value.
Product wt.% wt.% wt.% wt.%
Char + ash 18.5 ±1.6 14.9 ±0.7 24.5 ±1.6 18.2 ±0.9
4.1. Feed properties Total condensate 66.5 ±1.3 69.1 ±1.4 51.4 ±3.9 60.0 ±3.5
Tar condensate 39.2 ±10.6 43.2 ±5.5 44.9 ±4.2 47.6 ±4.8
The composition and other properties of the feed materials are sum- thereof H2O 8.3 ±4.0 9.3 ±2.6 19.7 ±4.7 16.4 ±2.5
Aqueous condensate 27.3 ±10.8 25.9 ±5.9 6.5 ±1.9 12.5 ±3.3
marized in Table 1 together with the total feed mass, the average feed thereof H2O 13.2 ±4.9 15.1 ±3.8 4.7 ±1.5 7.8 ±2.1
rate and the number of runs in a campaign. The FP reactor throughput Pyrolysis gas (difference) 15.0 ±1.9 16.0 ±2.1 24.1 ±5.3 21.8 ±4.4
determines the volume of released gases and vapours of ca. 0.5 Nm3/ Measured gas 15.6 ±2.3 11.5 ±0.9 21.5 ±3.5 13.3 ±0.5
kg or ca. 13 m3/h at 500 °C for 10 kg/h feed rate. The known volume Deficit −0.7 ±3.6 4.5 ±1.4 2.6 ±7.6 8.5 ±3.9
of the facility from feed entrance until condensation amounts to 4 L
put together by the reactor, the condenser and, to a small extent, the cy-
clone and piping. This results in a residence time of little more than one the total dry gas volume, followed by 30–40 vol.% CO and 4–8 vol.%
second. CH4, the rest consists mainly of hydrogen and lower hydrocarbon
vapours (see Table 4). The large CO2 fraction reduces the superior calo-
4.2. FP product yields rific value of pyrolysis gases to less than half of that of biomass. For
wood with typically low ash content, the non-condensable gas fraction
In Tables 2 and 3 the measured yields of the solid, liquid and gaseous amounts to 15–20 wt.%; for biomass with more ash the amount can rise
products are presented as the average of all runs with one type of bio- up to 25 wt.% or more, since the inorganic ash constituents in the char
mass together with their standard deviations. In Table 2 the 100% can promote the catalytic vapour decomposition to smaller gas mole-
mass reference is the material as processed; Table 3 is obtained from cules. Correspondingly, lower condensate and also higher char yields
Table 2 by subtracting the moisture content of the different feedstocks can be observed. At convenient final condensation temperatures slightly
and refers to the dry material with ash. Water data in Table 3 refers to above ambient, water vapour still makes a significant contribution to
reaction water originating from the pyrolysis reaction. the gas volume, at 45 °C ca. 10 vol.%.
In Table 2 the experimental values for the condensate from the
scratch cooler and the condensate from the second stage are given to-
gether with their water content. The ratio of the two condensate yields 5. Discussion of the results
depends on the temperature after the first stage which usually varies
between 60 and 70 °C without control. Thus only the total condensate 5.1. Reproducibility of product yields
amounts are suited for comparison between the different types of
biomass! Before conclusions from the FP yield data are drawn, the limits set by
The solid, liquid and gaseous FP product yields are in the same range their experimental repeatability should be known to avoid over-
as known from other FP reactor types: for wood with ca. 1% ash, the interpretation. The scatter of experimental data is illustrated in four
mass yield for the total condensate is 65 ± 10 wt.% and 15–20 wt.% campaigns with runs at the same feed and operating conditions: seven
for both char and gas. For wheat straw with ca. 6 wt.% ash, yields for con- runs with hardwood and five runs with softwood in Table 5; four FP
densate are only 50 ± 10 wt.% and both char and gas are increased to ca. runs with wheat straw and three successive runs with wheat bran are
25 wt.%. summarised in Table 6, all using a well-mixed feedstock.
It is known by comparison of literature reports, that the yield data
4.3. Pyrolysis gas composition for many minor individual FP product constituents in the 1% range
and below, can differ up to half an order of magnitude or even more
After water vapour condensation the most abundant component of [6,28]. This fact is not well understood and probably partly caused by
dry pyrolysis gases is CO2 with about 2/3 of the mass and about half of analytical difficulties with the complex multi-component mixture.
Fortunately, for bio-slurry applications via gasification or combustion
Table 1
such composition details are not needed. Therefore we confine our
Fuel properties, elemental composition, and test run data of feed materials. repeatability check in Tables 6 and 7 to the main lumped products:
char plus ash, total condensate including reaction and moisture water
Parameter Hardwood Softwood Wheat straw Wheat bran
and the main non-condensable gas constituents CO2 and CO.
HS MJ/kg 19.5 20.4 18.0 19.2 The repeatability of the experimental yields is not excellent and it is
HI MJ/kg 18.1 18.7 16.3 17.9
not advisable to rely on a single run. Even the mean values of the
Ash wt.% 1.0 0.5 6.0 5.5
Moisture wt.% 9.5 13.5 9.7 12.0 lumped solid, liquid and gaseous products from several runs still show
Bulk density1) kg/m3 ≈280 ≈140 ≈100 ≈280

Elemental composition (moisture free): Table 3

C wt.% 48.3 49.5 43.8 46.0 Average yields of FP products in wt.% referring to moisture free feedstock (mf) with ash as
H wt.% 6.1 6.2 5.9 6.3 calculated from Table 2.
O wt.% 44.5 43.8 44.3 39.1
S, N wt.% S b 1, N b 0.5 S = 0.2, N = 2.9 Char + ash 20.5 ±2.0 17.3 ±1.1 27.1 ±2.0 20.7 ±1.0
Total condensate 63.0 ±1.5 64.3 ±1.6 46.1 ±4.8 54.5 ±4.8
Campaign data: Reaction water 13.2 ±1.0 12.7 ±2.0 16.3 ±4.1 13.9 ±0.3
Total biomass feed kg 400 280 100 160 Pyrolysis gas as difference 16.5 ±2.2 18.4 ±2.6 26.8 ±6.5 24.8 ±5.8
Feed rate range ca. kg/h 10–16 10–15 ~6+ 10–12 Gas, measured 17.2 ±2.8 13.2 ±1.1 23.8 ±4.3 15.1 ±0.7
Number of runs 7 5 4 3 Deficit −0.7 ±4.3 5.2 ±1.8 2.9 ±9.4 9.7 ±5.1
 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161 157

Table 4 Table 6
Composition of the dry pyrolysis gas in wt.% and vol.%. Feed properties and mass yield percentage data for individual FP runs at comparable
conditions.
Component Hardwood Softwood Wheat straw Wheat bran
Run no. 1 2 3 4 1 2 3
wt.% vol.% wt.% vol.% wt.% vol.% wt.% vol.%
Biomass Straw Straw Straw Straw Bran Bran Bran
CO2 10.81 52.16 10.84 44.19 17.51 52.82 17.22 57.33
CO 4.91 37.22 6.39 40.94 7.44 35.28 6.32 33.08 Moisture % 9.57 9.95 9.65 9.70 12.03 12.50 11.50
H2 0.03 2.67 0.05 4.57 0.03 2.29 0.03 2.22 Ash % 6.0 6.0 6.0 6.0 5.5 5.5 5.5
CH4 0.46 6.10 0.71 8.00 0.76 6.27 0.48 4.41 Feed batch kg 25.40 19.70 27.90 29.55 60.0 50.0 50.0
C2H6 0.07 0.52 0.11 0.65 0.24 1.08 0.21 1.03 FP products in mass %:
C2H4 0.12 0.88 0.16 1.04 0.14 0.65 0.19 0.97 Char + ash 23.78 23.65 26.95 23.55 17.72 17.70 19.24
C3H8 0.07 0.35 0.13 0.53 0.22 0.66 0.20 0.67 Total condensate 53.26 49.20 55.80 47.20 57.13 58.90 63.96
i-C4H10 0.00 0.00 0.00 0.01 0.11 0.25 0.01 0.03 Total gas 26.50 18.27 21.86 19.59 13.80 13.22 12.78
n-C4H10 0.02 0.09 0.02 0.07 0.31 0.70 0.10 0.25 Product sum 103.54 91.12 104.61 90.34 88.65 90.82 95.98
sum 16.49 18.41 26.76 24.75 Deficit (100%-sum) - 3.54 8.88 - 4.61 9.66 11.35 9.18 4.02
CO2 17.30 12.34 13.98 12.69 9.73 9.12 8.82
CO 7.44 .97 6.06 3.45 3.38 3.32

a relatively large standard deviation in the range of about 10% relative.

Corresponding percentage errors from Table 6 are:
and about 10 wt.% reaction water, the resulting water concentration in
For straw: char 24.5 ± ~ 7%, condensate 51.4 ± ~ 7%, gas 21.6 ± the smaller bio-oil volume would be around 40 wt.% and a phase sepa-
~16%, CO2 14.1 ± ~17%. ration is almost inevitable. This must be kept in mind for the FP of ash
For bran: char 18.2 ± ~10%, condensate 60.0 ± ~6%, gas 13.3 ± ~4%, rich low quality biomass types. The phenomenon of phase separation
CO2 9.2 ± ~4%. is not completely understood and deserves further investigation. In a
recent paper by Oasmaa the state of knowledge today is presented
5.2. Mass and energy balance and discussed [38].

The calorific value data from bomb calorimetry (Table 1) and the
superior calorific values HS calculated from the elemental composition
with the Channiwala equation [29] (see Table 7) are in good agreement.
The HS values of the averaged products have been calculated in the same
way; the corresponding data are compiled in Table 7. The diagrams in
Fig. 5 show the energy share of the different FP product fractions. The
chars contribute a significant part to the calorific values of the bio-
slurries, on the average about 1/3.
5.3. Stability of pyrolysis condensates
It is known that bio-oils with a higher water content of typically
≥25 wt.% are prone to almost immediate phase separation into a lighter
aqueous phase with dissolved organics and a heavier organic phase,
which contains the entrained char particles. Even at lower water con-
centrations a delayed phase separation is frequently observed and indi-
cated by different top and bottom compositions in storage vessels. The
same phenomenon is observed for our bio-sludge products from
wheat straw and is a nasty nuisance for correct sampling.
Preliminary data for the composition of light aqueous phase separat-
ed from bio-oils, sludge or slurry show a water content of about one half,
about a quarter of dissolved non-volatile sugar derivatives and about a
quarter volatile water soluble organics [30]. The heavy phase has usually
a larger volume of 75–80% and contains the char and a still significant
amount of water in the order of 10 wt.%.
Low quality biomass with much ash like straw shows lower bio-oil
yields in the range of only 50 wt.%, i.e. 10–20 wt.% lower compared to
wood (see Table 2). For an ash-rich lignocellulose with 10 wt.% moisture
5.4. Mass balance deficit
In the FP experiments it was observed, that a large fraction of volatile
organic vapours can escape with the pyrolysis gases, especially at higher
condensation temperatures.
A mix of volatile vapours being in equilibrium with the aqueous
condensate mixture (solubility in water) escapes in the last condensa-
tion step together with the pyrolysis gases. These oxygenate vapours
are usually not determined in the GC of the pyrolysis gas and thus usu-
ally are not considered in the mass and energy balance.
Constituent CH2O CH3CHO CH3OCH3 CHOCHO CH3OH C2H5OH
Boiling point/K 254 294 249 324 338 352
The mass balance deficit of several percent as frequently reported in
the literature [5–7] can be explained in this way at least to a certain
extent. A better and detailed explanation and quantification of the
deficit phenomenon still remains an issue to be done.
The high mass balance deficit of wheat bran is probably partly
caused by the high 2.9 wt.% nitrogen content and originates from the
ca. 18 wt.% protein content. Conversion of the organic nitrogen in the
feed to molecular N2 could not be analyzed. Most of the protein's nitro-
gen forms ammonia which increased the pH value of the bio-oil from
usually 3 to about 5 in this case. Acetic acid is one of the major FP
products and a pH of 5 indicates the presence of an ammonium
acetate/acetic acid buffer.

Table 5
Mass yield percentage data for individual FP runs at comparable conditions.

Run no. 1 2 3 4 5 6 7 1 2 3 4 5

Biomass H H H H H H H S S S S S
Char & ash 16.6 17.6 18.0 18.1 18.6 19.2 21.7 14.1 15.3 14.4 15.7 15.2
Total condensate 65.7 66.4 67.1 68.1 67.7 64.5 66.1 67.2 69.9 68.0 70.0 70.5
Total gas 17.7 16.0 14.9 13.8 13.7 16.3 12.2 18.7 14.8 17.6 14.3 14.3
sum 100 100 100 100 100 100 100 100 100 100 100 100
deficit 4.7 1.4 −1.1 −4.4 −3.8 2.6 −1.6 6.3 2.9 5.7 3.9 3.6
Total water 20.0 20.6 21.6 21.2 21.7 23.8 22.9 25.6 26.0 23.0 23.4 24.0
CO2 7.8 9.6 12.3 12.4 10.7 9.4 9.4 6.8 7.2 7.0 6.6 6.1
CO 4.5 4.3 5.3 5.0 5.7 3.7 3.9 4.7 3.9 4.2 3.2 3.9
158 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161

Table 7
Mean elemental composition and superior calorific values calculated with the Channiwala equation. Energy yields are calculated from the corresponding mass yields.

Hardwood (mf) C H O Ash HS Mass Energy Yield

g/kg g/kg g/kg g/kg MJ/kg kg/kg MJ/kg e%

Feed 482.6 61.0 445.4 11.0 19.41 1.000 19.41 100

Char + ash 137.3 8.0 48.9 11.0 25.36 0.205 5.20 26.8
Gas (corrected) 56.4 1.9 106.6 0.0 5.87 0.165 0.97 5.0
Reaction water − 14.7 117.5 − − 0.132 − 0.0
Condensate, total 288.8 36.5 172.4 0.0 25.32 0.498 12.60 64.9
Org. condensate 200.1 21.7 119.7 0.0 24.31 0.341 8.30 42.8
Aqu. condensate 88.8 14.8 52.7 0.0 27.50 0.156 4.30 22.1
Products-feed −0.64 −3.3

Softwood (mf) C H O Ash HS mass energy yield

g/kg g/kg g/kg g/kg MJ/kg kg/kg MJ/kg e%
Feed 495.3 61.8 437.9 5.0 20.04 1.000 20.04 100.0
Char + ash 120.0 7.0 40.6 5.0 26.58 0.173 4.59 22.9
Gas (corrected) 65.9 3.0 115.3 0.0 7.61 0.184 1.40 7.0
Reaction water − 14.1 112.5 − − 0.127 − −
Condensate 309.4 37.7 169.5 0.0 26.11 0.517 13.49 67.3
Org. condensate 218.7 19.6 153.5 0.0 21.34 0.392 8.36 41.7
Aqu. condensate 90.7 18.0 16.1 0.0 41.07 0.125 5.13 25.6
Products-feed −0.56 −2.8

Wheat straw (mf) C H O Ash HS mass energy yield

g/kg g/kg g/kg g/kg MJ/kg kg/kg MJ/kg e%
Feed 437.8 59.1 442.8 60.3 17.55 1.000 17.55 100.0
Char + ash 172.6 8.8 29.6 60.3 24.42 0.271 6.62 37.7
Gas (corrected) 93.5 4.0 170.1 0.0 6.65 0.268 1.78 10.1
Reaction water − 18.1 144.8 − − 0.163 − −
Condensate 171.7 28.3 98.3 0.0 27.87 0.298 8.31 47.4
Products-feed −0.83 −4.7

Wheat bran (mf) C H O N S Ash HS mass energy yield

g/kg g/kg g/kg g/kg g/kg g/kg MJ/kg kg/kg MJ/kg e%

Feed 460.0 63.1 390.8 29.1 2.0 55.0 19.32 1.000 19.32 100.0
Char + ash 106.1 5.4 33.3 7.2 0.0 55.0 18.69 0.207 3.87 20.0
Gas (corrected) 83.5 2.7 161.4 0.0 0.0 0.0 5.46 0.248 1.35 7.0
Reaction water − 15.5 123.7 − − − − 0.139 −
Condensate 270.4 39.5 72.5 21.8 2.0 0.0 32.83 0.406 13.33 69.0
Products-feed −0.76 −3.9

1 calculated with the Channiwala relation [Cha02]. Pyrolysis gas based on measured values.

5.5. Condensate-to-char ratio for bio-slurry production For wood sufficient condensate is available to suspend all pyrolysis
char. For wheat straw the condensate yield is still sufficient. Potential
In view of the bio-slurry preparation for the bioliq process it is desir- lack of condensate can be compensated for with a mixed feedstock,
able, that the recovered condensate volume is sufficient to suspend all using the surplus condensate of wood or any other waste liquids.
recovered char maintaining a slurry well to be pumped, if possible. As
an experienced rule of thumb a condensate-to-char mass ratio of two 6. Energy consumption for FP
or more results in a free flowing slurry, at least after warming and
mixing [19]. The condensate requirements are caused by the high pyrol- The heat needed for FP corresponds to the enthalpy of the pyrolysis
ysis char porosity, which first soaks up much bio-oil until sufficient free reaction ΔrH plus the energy to heat the pyrolysis products from
liquid remains outside the char particles. The following condensate/char ambient to the final pyrolysis temperature of 500 °C. The pyrolysis
mass ratios are obtained from the experimental yields in Tables 2 and 3: reaction enthalpy for lignocellulose is not constant but varies with the
product spectrum. ΔrH can be calculated by summation over the
known or estimated heats of combustion or formation of each educt
Hardwood Softwood Wheat straw Wheat bran
and product in an empirical stoichiometric pyrolysis equation. The
Moist 3.6 ± 0.3 Moist 4.6 ± 0.1 Moist 2.1 ± 0.1 Moist 3.3 ± 0.1 heat of combustion of complex organic compounds or moisture-free
Dry 3.3 ± 0.3 Dry 3.7 ± 0.1 Dry 1.7 ± 0.1 Dry 2.6 ± 0.1
liquid or solid organic mixtures whose elemental compositions are

Table 8
Experimental energy consumption during FP of dry lignocellulosics.

Feed HS (dry) MJ/kg FP reactor type Heat carrier Heat for FP MJ/kg(wf) Number of runs Ref.

Hardwood 19.5 Twin screw SS balls 1.32 ± 0.36 8 [27]

Softwood 20.4 Twin screw SS balls 1.96 ± 0.42 10 [27]
Oak wood Fluid bed Quartz sand 1.46 ± 0.28 [34]
Pine wood Fluid bed Quartz sand 1.64 ± 0.33 [34]
Maize plants Fluid bed Quartz sand 1.35 ± 0.28 [34]
Oak chaff Fluid bed Quartz sand 0.78 ± 0.20 [34]
Wheat straw 18.0 Twin screw SS balls 1.25 ± 0.30 2 [27]
Wheat bran 19.2 Twin screw SS balls 1.28 ± 0.30 3 [27]
 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161
Fig. 5. Energy yield spectrum in percent of the initial biofeed.
known, can be estimated with ca. ± 1.5% error with the Channiwala
equation.
H S inðMJ=kgÞ ¼ 34:91 C þ 117:83 H–10:34 O þ 10:05 S–1:51 N–2:11 A
C; H; O; S; N and A ðashÞ in wt:%of the elements and ash A
ð1Þ
As the Channiwala relation for HS depends linearly on the elemental
composition, an application of this equation to all educts and products
of a stoichiometric chemical equation must result in zero reaction
enthalpy. However, it is reasonable to use for the simple pyrolysis gas
molecules like CO2, CO, H2O, etc., or for C in char their well-known
calorific data. Then, and when applying the Channiwala relation to the
remaining components a reliable value for the enthalpy of the pyrolysis
reaction ΔrH can be achieved. The higher the carbon (char) and water
yields during pyrolysis, the more heat of reaction is released. A rather
simplified equation for the decomposition of dry lignocellulose to
water and carbon is:
C6 H8 O4 →C6 ðH2 OÞ4 →6 C þ 4 H2 OΔr H ¼ −560 kJ=mol:
H S ≈ 2:880 kJ=mol H S ¼ 6  393:5 kJ=mol HS ¼ 0
This lets expect that lignocellulose decomposition to char and reaction
water would be a highly exothermal reaction, liberating almost 20% of
the heat of combustion. Slow pyrolysis of dry wood gives rise to high
char yields – especially at higher pressures [31] – and can sometimes
proceed spontaneously even without external heat supply, like the
self-sustained Stafford process [32]. During slow pyrolysis of wood
the charcoal plus water yields are high and amount to about 50 wt.%.
The corresponding yields during a FP are reduced down to almost
25 wt.% in favour of the desired organic condensate. The reaction heat
of FP is then expected to be no more sufficient for a self-sustained
heating of the products to 500 °C. A thermo-neutral lignocellulose
pyrolysis is expected in the range of about 17% char yield [31,33],
which is within the typical experimental range for FP of lignocellulose
with higher ash contents like cereal straw. The specific heat cp of either
lignocellulose or the pyrolysis products cannot be measured up to the
hypothetic 500 °C pyrolysis temperature due to decomposition. An
extrapolation of cp from ambient temperature to 500 °C predicts values
of about 2 kJ/kg⋅K, resulting in ca.1 MJ/kg heat consumption for heating
159
FP products from ambient to 500 °C. In addition, FP reaction enthalpy
contributes between 0 and 1 MJ/kg, resulting in a total of about 1–2
MJ/kg, or 5–10% of the HS of water and ash free lignocellulosic biomass.
These practical considerations have been confirmed experimentally
in literature [33,34] and in own experiments. Fig. 6 shows a typical
temperature recording at the reactor inlet and outlet during a run. The
energy flow Q_ (kJ/h) which is transferred from the constant heat carrier
_ HC (cp (SS balls) ≈ 0.7 kJ/kg⋅K at ca. 550 °C) to a constant
mass flow M
co-current hardwood flow F_ at steady state conditions, can be calculated
from the temperature difference ΔT between inlet and exit of the pyrol-
ysis reactor Q = M⋅cp ⋅ΔT.
In most of the test runs a temperature drop ΔT between 20 and 40 K
along the reactor was observed. Corrections considering some energy
input or loss from or to the reactor environment have been estimated
from the temperature drop at zero feed flow immediately after feed
stop. In addition there is also some heat consumption by the small
nitrogen flushing stream. Experimental values from [34] in Table 8 are
compared with our own data. Data corrections are explained in [27].
The broad variation of different educts and product yield spectra
is responsible for the relatively large range of FP process energy
demand.
The discussion above explains why a range rather than a definite
value for heat consumption for FP of lignocellulose exists. According
to Table 8, energy consumption for FP is in a range between 1 and
2 MJ/kg or 5 to 10% (some insulation loss included) of the lignocellulose
HS value depending on feed material, product composition, and operat-
ing conditions. The energy demand for straw pyrolysis (≈1.26 MJ/kg) is
lower than that for wood (≈ 1.64 MJ/kg) because of the higher char
yield. This amount of energy can be supplied by efficient combustion
of the pyrolysis gases, eventually together with some residual vapours
of volatile organics escaping at optimized, higher condensation temper-
atures. Higher final condensation temperatures have the additional
advantage to ease cooling for product recovery and supply also
sufficient energy for wood pyrolysis.
It can therefore be concluded, that an efficient use of the combustion
energy of the pyrolysis gases is sufficient for a self-sustained FP process
and obviates pyrolysis char combustion for this purpose. Thus the char
remains completely for the bio-slurry and contributes a very significant
part of the resulting ca. 90% (Table 7) of energy (related to the water
free feed material) maintained in the combined product. In this way, a
160 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161
Fig. 6. Typical temperature recording of the heat carrier at the reactor inlet and exit during a FP run.
gasification fuel with maximum energy content can be provided to
syngas production.
7. Summary and conclusions
Fast pyrolysis can convert more than half of a lignocellulosic biomass
into a liquid condensate, called bio-oil, for more convenient handling,
storage, transport and use. In the bioliq process the bio-oil is used as a
feed for a pressurized entrained flow gasifier. For gasification, the qual-
ity requirements for bio-oils are much lower and large char and ash con-
tents can be tolerated. Even all pyrolysis char can be suspended in the
bio-oil to prepare a pumpable bio-slurry or biosyncrude as a gasifier
feed with up to 85–90% of the initial bioenergy and a high volumetric
energy density, corresponding to about 60% of heating oil.
The low quality requirements for bio-oils or bio-slurries allow FP
process simplifications and modifications.
In order to investigate suitable versions, a process development unit
with 10–20 kg/h biomass capacity has been designed, built and operat-
ed. Different to the conventional design with a fluid sand bed for pyrol-
ysis and a separate char recovery with a hot cyclone and bio-oil recovery
with a quench condenser, the focus of our test facility was on a twin
screw mixer reactor for pyrolysis integrated into a heat carrier loop
with small SS spheres circulated with a bucket elevator. The usual
product recovery with a cyclone and a quench condenser was replaced
by a scratch cooler for simultaneous recovery of char and bio-oil as a
slurry or sludge.
Individual yields of char and bio-oil have been obtained after slurry
separation with methanol. From wood with ca. 1% ash, about 65% of
the initial bioenergy was recovered in the bio-oil, from straw and herba-
ceous biomass with usually ≥5% ash only around 50% energy in bio-oil
could be recovered; char and gas yields are in the 15–20% range. This
is in reasonable agreement with the usual process versions described
in the literature, despite the significant differences in our process de-
sign, as summarized in Table 8.
This indicates that the fast pyrolysis process for lignocellulosic
biomass seems to be sufficiently flexible and robust, to tolerate consid-
erable process modifications, as long as the essential process character-
istics – fast heating up and pyrolysis at 500 °C in absence of oxygen and
rapid vapour condensation within a few seconds – are maintained. It is
obvious, that the design flexibility of the fast pyrolysis process is by no
means exhausted and especially the potential product recovery options
should be further investigated.
The bio-oils from lignocelluloses with much ash like straw have a
higher water content of usually N30 wt.% and are prone to phase sepa-
ration. The heavier, dark and viscous organic phase collects the char
particles, and a smaller (around a quarter) volume of a lighter ca. 50%
aqueous solution of volatile water-soluble oxygenates and non-
volatile sugar derivates separates at the top.
Measurements of the residence time distribution in the twin screw
mixer reactor show that plug flow behaviour is an adequate approxima-
tion for modelling. Optimization of process conditions could become of
special interest as soon as small bio-oil fractions are removed as
valuable raw materials for chemistry and the large remainder is still
converted to biosyngas.
The energy consumption of the FP process was measured at constant
biomass feed rate and heat carrier circulation, by the temperature drop
of the heat carrier stream between inlet and outlet of the pyrolysis
reactor. Measured values range from 5 to 10% of the initial biomass
superior calorific value (1–2 MJ per kg water and ash free biomass).
The large variation is caused by different biomass feed types and oper-
ating conditions resulting in different product yields. The combustion
energy of the pyrolysis gases should be sufficient to supply the heat
for the fast pyrolysis process without char, eventually supported by
some organic vapours remaining in the pyrolysis gas at somewhat
higher final condensation temperatures.
References
[1] D.S. Scott, J. Piscorz, The flash pyrolysis of aspen poplar wood, Can. J. Chem. Eng. 60
(1982) 666–674.
[2] D.S. Scott, J. Piskorz, The Continuous flash pyrolysis of wood for the production of
liquid fuels, 7. Symposium on Energy from biomass and wastes 1983,
pp. 1123–1146.
[3] D.S. Scott, J. Piskorz, The continuous flash pyrolysis of biomass, Can. J. Chem. Eng.
Res. 27 (1984) 8–15.
[4] D.S. Scott, P. Majerski, J. Piskorz, D. Radlein, A second look at fast pyrolysis of
biomass — the RTI process, J. Anal. Appl. Pyrolysis 51 (1999) 23–37.
[5] A.V. Bridgwater, G.V.C. Peacoke, Fast pyrolysis for biomass, Renew. Sust. Energ. Rev.
4 (2000) 1–73.
[6] A.V. Bridgwater, et al. (Eds), Fast Pyrolysis of Biomass — a Handbook, CPL Press,
Newbury, (Volume I, 1999, II, 2002, III, 2005).
[7] A.V. Bridgwater, Fast pyrolysis of biomass, in: A.V. Bridgwater, H. Hofbauer, S. van
Loo (Eds.), Fast Pyrolysis of Biomass, Newbury, CPL Press 2009, pp. 37–78.
[8] A.V. Bridgwater, Review of fast pyrolysis of biomass and product upgrading, Biomass
Bioenergy 38 (2012) 68–94.
[9] D. Meier, B. van de Beld, A.V. Bridgwater, D.C. Elliott, A. Oasmaa, F. Preto, Stat-of-the-
art of fast pyrolysis in IEA bioenergy member countries, Renew. Sust. Energ. Rev. 20
(2013) 619–641.
[10] S. Czernik, A.V. Bridgwater, Overview of application of biomass fast pyrolysis oil,
Energy Fuel 18 (2004) 590–598.
 E. Henrich et al. / Fuel Processing Technology 143 (2016) 151–161
[11] S. Xiu, A. Shahbazi, Bio-oil production and upgrading research: a review, Renew.
Sust. Energ. Rev. 16 (2012) 4406–4414.
[12] A. Ardiyanti, S. Khromova, R. Venderbosch, V. Yakovlev, I. Melian-Cabrera, Catalytic
hydrotreatment of fast pyrolysis oil using bimetallic Ni–Cu catalysts on various
supports, Appl. Catal. A Gen. 449 (2012) 121–130.
[13] E. Henrich, E. Dinjus, F. Weirich, A new concept for biomass gasification at high pres-
sure, Proc. of the 12th European Biomass Conference, Volume 1, Amsterdam 2002,
pp. 628–632.
[14] E. Henrich, K. Raffelt, R. Stahl, F. Weirich, Clean syngas from biooil/char-slurries, in:
A.V. Bridgwater, D.G.B. Boocock (Eds.), Science in Thermal and Chemical Biomass
Conversion, 2, CPL press 2006, pp. 1565–1579.
[15] N. Dahmen, E. Henrich, E. Dinjus, F. Weirich, The bioliq bio-slurry gasification
process for the production of biosynfuels, organic chemicals and energy, Energy
Sustain. Soc. Springer Online J. 2 (2012) 3 (http://www.energysustainsoc/content/
2/1/3).
[16] M. Schingnitz, Darstellung des Noell Konversionsverfahrens, in: J. Carl, P. Fritz (Eds.),
Noell Konversionsverfahren zur Verwertung und Entsorgung von Abfällen, Berlin,
EF-Verlag 1994, pp. 24–53.
[17] M. Schingnitz, Flugstromvergasung, Gaskombinat Schwarze Pumpe Verfahren
(GSP), in: J. Schmalfeld (Ed.), Die Veredelung und Umwandlung von Kohle,
DGMK, Hamburg 2008, pp. 537–552.
[18] N. Dahmen, E. Dinjus, T. Kolb, U. Arnold, H. Leibold, R. Stahl, State of the art of the
bioliq process for synthetic biofuels production, Environ. Prog. Sustainable Energy
31 (2012) 176–181.
[19] K. Raffelt, E. Henrich, J. Steinhardt, E. Dinjus, Preparation and characterization of
biomass slurries: a new feed for entrained flow gasification, in: A.V. Bridgwater,
D.G.B. Boocock (Eds.), Science in Thermal and Chemical Biomass Conversion,
Volume 2, Newbury, CPL press 2006, pp. 1547–1558.
[20] E. Henrich, F. Weirich, A twin screw mixer reactor for fast pyrolysis of biomass, Proc.
2nd World Biomass Conference, Volume 1, Rome 2004, pp. 982–985.
[21] W. Peters, Schnellentgasung von Steinkohlen, Habilitation thesis, RWTH Aachen,
1963.
[22] W.R. Rammler, et al., Gewinnnung von Öl durch Schwelen von Öl und Teersand als
Beitrag zur Energieversorgung, Chem. Ing. Tech. 53 (1981) 96–104.
161
[23] H. Weiss, J.F. Pagel, A Novel Process for Refinery Residue Conversion, 16th World
Petroleum Congress, Calgary, Canada, 2000.
[24] C. Kornmayer, E. Dinjus, E. Henrich, F. Weirich, R. Reimert, Entwicklung von
Verfahrensvarianten zur Schnellpyrolyse von Lignocellulosen im LR-Mischreactor,
DGMK-Fachtagung Energetische Nutzung von Biomassen, Velen, 2006.
[25] J. Schmalfeld, Pyrolyse, Lurgi-Ruhrgas-Verfahren (LR), in: J. Schmalfeld (Ed.), Die
Veredelung und Umwandlung von Kohle, DGMK, Hamburg 2008, pp. 157–173.
[26] C. Kornmayer, E. Dinjus, E. Henrich, F. Weirich, R. Reimert, Advanced Fast Pyrolysis
of Lignocellulose in a Twin Screw Mixer Reactor, 15th European Biomass Conference
and Exhibition, Berlin, Germany, 2007.
[27] C. Kornmayer, Verfahrenstechnische Untersuchungen zur Schnellpyrolyse von
Lignocellulose im Doppelschnecken-MischreaktorPhD-Thesis Karlruhe University
(TH), 2009.
[28] C. Branca, et al., Multistep mechanism for the devolatilisation of biomass fast
pyrolysis oils, Ind. Eng. Chem. Res. 44 (2006) 799–810.
[29] S.A. Channiwala, P.P. Parik, A unified correlation for estimating the HHV of solid,
liquid and gaseous fuels, Fuel 81 (2002) 1051–1063.
[30] R. Stahl, KIT; Private Communication, 2012.
[31] M.J. Antal, M. Gronli, The Art, Science and Technology of Charcoal Production, Ind.
Eng. Chem. Res. 42 (2003) 1619–1640.
[32] E.R. Riegel, Industrial Chemistry, 2nd ed. The Chemical Catalog Company, New York,
1933 p. 253.
[33] W.S.L. Mok, M.J. Antal, Effects of pressure on biomass pyrolysis, II Heats of reaction
of cellulose pyrolysis, Thermochim. Acta 68 (1983) 165–186.
[34] D.E. Daugaard, R.C. Brown, Enthalpy for pyrolysis of several types of biomass, Energy
Fuel 17 (2003) 934–939.
[35] W. Peters, Schnellentgasung von Steinkohle, Habilitationsschrift, RWTH Aachen,
1963.
[36] M. Zlokarnic, Dimensional Analysis und Scale-up in Chemical Engineering, Springer,
Heidelberg, 1991 79.
[37] J. Pawlowski, Einwellen-Schnecken; Förder-, Homogenisier- und
Wärmetauschverhalten, Sauerländer & Co, Aarau, 1990.
[38] A. Oasmaa, T. Sundqvist, E. Kuoppala, M. Garcia-Perez, Y. Solantausta, C. Lindfors, V.
Paasikallio, Energy Fuel 29 (2015) 4373–4381.