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M.Seitz | Catalytic Cracking of Lignites
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Methods for predicting the
hydrocarbon yield in the catalytic
cracking of lignite
8th International Freiberg Conference on IGCC & XtL
Technologies
Innovative Coal Value Chains
12-16 June 2016, Cologne, Germany
Mathias Seitz*, Armin Engelhardt*, Jens Zimmermann*, Timo
Stam-Creutz*, Thomas Hahn**
* University of Applied Science, Merseburg, Germany, **MLU
Halle-Wittenberg, Halle, Germany
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M.Seitz | Catalytic Cracking of Lignites
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BGR 2008
reserves
In Gt
assumed
accumulated
production
since 1950
resources reserves production
Introduction (1) Lignite: reserves, resources and production
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M.Seitz | Catalytic Cracking of Lignites
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Introduction (2): different types of lignites
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M.Seitz | Catalytic Cracking of Lignites
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oil
lignite
H rich
yellow lignite:
- high content of liptinite
high content of aliphatic molecules
Introduction (3): different types of lignites
1872 Riebeck‘schen Montanwerke am Standort Oberröblingen;
Quelle: LMBV
Historical oil and paraffin production
by low-temperature carbonisation
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M.Seitz | Catalytic Cracking of Lignites
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Batch Concept of Catalytic Cracking
cracking in situ
at 400 – 600°C no use of hydrogen
no heavy tar formation
catalyst regeneration
catalyst coated beads
inert gas
solids
(char/catalyst separation)
vapor
(gas/liquid separation)
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M.Seitz | Catalytic Cracking of Lignites
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meth
an
e
eth
an
e
eth
en
e
pro
pan
e
pro
pen
e
bu
tan
e
bu
ten
e
pen
tan
e
pen
ten
e
hexan
e
hexen
e
C7
C8
ben
zen
e
tolu
en
e
eth
ylb
en
zen
e
xyle
ne
meb
0,0
0,5
1,0
1,5
2,0
yie
ld [
%m
af]
without catalyst
catalyst powder
beads
excess powder
Typical products
Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst
ratio = 20 : 1; MFI
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M.Seitz | Catalytic Cracking of Lignites
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mining
NIR-
analysis
prediction
H/C ratio
prediction
HC yield
batch
prediction
HC yield
continuous
Three steps of modeling - from mining to hydrocarbons -
H/C ratio as a light
measurable factor
to predict the
hydrocarbon yield.
Easy statements
about the
achievable
products.
Prompt information
about the potential of
the lignite.
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M.Seitz | Catalytic Cracking of Lignites
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Characterization of molar H/C ratio
NIR spectrum of lignite to determine the molar H/C-ratio Cepus,
V., et. al. IR Spectroscopic Characterization of Lignite as a Tool
to Predict the Product Range of Catalytic Decomposition,
International Journal of Clean Coal and Energy (2016) 5, pp.
13-22
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M.Seitz | Catalytic Cracking of Lignites
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Characterization of molar H/C ratio
Cepus, V., et. al. Journal of Clean Coal and Energy (2016) 5,
pp. 13-22
Assumption:
- molar O/C ratio
has no influence
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M.Seitz | Catalytic Cracking of Lignites
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Influence of the molar H/C ratio
Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst
ratio = 20 : 1; MFI
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M.Seitz | Catalytic Cracking of Lignites
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0.00 0.02 0.04 0.06 0.08 0.100
5
10
15
20
different CTC; H/C 1.3
variation modulus H/C; 1.3
different CTC; H/C 1.02
variation modulus H/C; 1.02yie
ld p
er
lig
nit
e (
ma
f) i
n M
a-%
amount of acid sites (maf) in mmol/g
Influence of the amount of acid sites
Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst
ratio = 20 : 1; MFI
CTC: catalyst to
coal ratio (mass)
modulus: molar
Al2O3/SiO2 ratio
of the catalyst
modulus > 60 because of less
contact of catalyst and lignite
and coking
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M.Seitz | Catalytic Cracking of Lignites
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Influence of the amount of …
Conditions: Batch:, T = 400 °C, τ = 100 s , coal(maf) /catalyst
ratio = 20 : 1; MFI
- different catalysts
- different catalyst properties
- H/C ratio; O/C ratio
- temperature
- catalyst to coal ratio
- gas residence time
- solid residence time
- inert gas/solid ratio
- reactor operation mode; flash behaviour
- coal/catalyst contact
- water content of the lignite
Nearly all measurements
of the batch process
(except some catalyst
types) were used to find a
an as easy as possible
model !
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M.Seitz | Catalytic Cracking of Lignites
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Batch model
4
6
8
10
12
14
16
18
20
22
24
ad
jus
ted
hy
dro
ca
rbo
n y
ield
C1
-C9
[%
ma
f]
0,8 0,9 1 1,1 1,2 1,3 1,4molar H/C-ratio [-]
0,2 0,4 0,6 0,8modificated acidic centre ratio [-]
450 500 550temperature [°C]
Adjusted Response Graph - Hydrocarbon yield C1-C9 (86
experiments)
a -1,13E+02 9,91%
b 4,14E-01 11,52%
c 3,13E+01 4,95%
d -5,37E-02 8,52%
e -3,16E-04 15,71%
R2 = 0,9827
𝒀𝑪𝟏−𝟗 = 𝒂 + 𝒃 ∙ 𝑻 °𝑪 + 𝒄 ∙𝒏𝑯𝒍𝒊𝒈𝒏𝑪𝒍𝒊𝒈
∙𝒏𝑨𝒄𝒎𝒐𝒅𝒎𝒍𝒊𝒈
+ 𝒅 ∙ 𝑻 ∙𝒏𝑨𝒄𝒎𝒐𝒅𝒎𝒍𝒊𝒈
+ 𝒆 ∙ 𝑻𝟐
HC yield
parity plot
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M.Seitz | Catalytic Cracking of Lignites
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Continuous concept of catalytic cracking
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M.Seitz | Catalytic Cracking of Lignites
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batch reactor conti reactor
From batch to a continuous reactor
carrier
gas
carrier
gas
Reaction parameters:
gas residence time: 1 sec
lignite residence time 40 sec
Reaction parameters:
gas residence time: 100 sec
lignite residence time 40 min
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M.Seitz | Catalytic Cracking of Lignites
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0
2
4
6
8
oil
ph
as
e
me
b
xy
len
e
C7
eth
ylb
en
ze
ne
he
xe
ne
tolu
en
e
be
nze
ne
C8
he
xa
ne
yie
ld [
% m
af]
batch H/C 1.1
batch H/C 1.3
continuous H/C 1.3
pe
nte
ne
pe
nta
ne
bu
ten
e
bu
tan
e
pro
pe
ne
pro
pa
ne
eth
en
e
eth
an
e
me
tha
ne
Batch and continuous reactor
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M.Seitz | Catalytic Cracking of Lignites
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Continuous model:
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Continuous model: parameter value error
3.207 ± 18 %
0.929 ± 18 %
2.284 ± 7,4 %
HC yield
parity plot
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M.Seitz | Catalytic Cracking of Lignites
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Continuous model vs batch
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M.Seitz | Catalytic Cracking of Lignites
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Continuous model vs batch
more
catalyst
activity has to be
adjusted to the
amount of volatile
matter and the gas
residence time
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M.Seitz | Catalytic Cracking of Lignites
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H/C 1.3 (with transfer of the linear batch relation to the
continuous model)
CTC 1:10; T 600°C
batch model: YHC = 27.7%
continuous model: YHC = 27.0%
continuous measured: YHC = 28.7%
Continuous model vs batch –
extrapolation/validation
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M.Seitz | Catalytic Cracking of Lignites
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Summary
lignite is an interesting feedstock
- cheap, - available, - can obtain paraffins
catalytic conversion in situ without hydrogen to
olefins (about 11 % maf) and aromatics is possible
model for
- rapid prediction of molar H/C ratio is possible
- prediction of HC yield of batch process is possible
- prediction of HC yield of continuous process is possible
but work is to be done.
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M.Seitz | Catalytic Cracking of Lignites
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- physico-chemical based models
- models to describe the single products
- extension to different lignites with higher O/C
- improvement of the continuous model in
consideration of the residence time
- catalyst and its properties
Outlook
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M.Seitz | Catalytic Cracking of Lignites
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Acknowledgement
for financial support
for cooperation
03WKBZ05