Chapter 24

Fluidized-Bed Upgrading of Wood Pyrolysis

Liquids and Related Compounds

Ν. Y. Chen, D. E. Walsh, and L . R. Koenig

Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024

Mobil Research and Development Corporation, Central Research

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Laboratory, P.O. Box 1025, Princeton, N J 08540

The effective hydrogen index (EHI) is a

calculated indicator of the "net" hydrogen/
carbon ratio of a pure or mixed heteroatom­
-containing feed, after debiting the feed's
hydrogen content for complete conversion of
heteroatoms to NH , H S, and H O. Compounds
3 2 2

with EHI's less than about 1 are difficult to

upgrade to premium products over ZSM-5 catalyst
due to rapid catalyst aging in continuous fixed
bed processing.
However, high conversions of such feeds (acetic
acid, methyl acetate, and wood pyrolysis
liquids) can be maintained in a fluidized bed
system operating under methanol-to-gasoline
conditions and employing frequent catalyst
regenerations. Also, synergistic effects were
observed for blends of low and high EHI model
compounds, as well as for wood pyrolysis liquids
coprocessed with methanol. Based on these
results, a processing scheme is described in
which the char from the wood pyrolysis step is
gasified to make methanol which is cofed with
the pyrolysis liquids over ZSM-5.

Z e o l i t e ZSM-5 i s p a r t i c u l a r l y e f f e c t i v e f o r the
conversion of methanol t o g a s o l i n e range hydrocarbons
(1). I n a d d i t i o n t o methanol, other oxygenates,
i n c l u d i n g t h e i r complex mixtures, can be converted as
w e l l (see, f o r example, r e f e r e n c e s 2-8).

0097-6156/88/0376-0277$06.00/0
©1988 American Chemical Society

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ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 278 PYROLYSIS OILS FROM BIOMASS

The e f f e c t i v e hydrogen index i s d e f i n e d as:

H-20-3N-2S
(H/C) ££ective or EHI =
e
C

where H, C, 0, N, and S are atoms per u n i t weight of

sample of hydrogen, carbon, oxygen, n i t r o g e n and
sulfur, respectively.
Model oxygen c o n t a i n i n g compounds, or "oxygen-
11
a t e s , having EHI's <1 produce excessive amounts of
11
"coke , which leads t o r a p i d c a t a l y s t d e a c t i v a t i o n
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024

(5)(9) u s i n g ZSM-5. Thus, as shown i n Table I,

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i n i t i a l l y complete a c e t i c a c i d conversion d e c l i n e s to
about 60% a f t e r only 3 hours on stream. At t h a t p o i n t ,
the t o t a l hydrocarbon y i e l d i s l e s s than 10 wt.%, and
the g a s o l i n e y i e l d (C +) i s l e s s than 7% (8).
g

L i g n o - c e l l u l o s i c biomass i s a resource from which

l i q u i d hydrocarbon f u e l s p o t e n t i a l l y may be d e r i v e d .
P y r o l y z i n g the wood y i e l d s gas and l i q u i d products, but
a r e l a t i v e l y l a r g e percentage of the o r i g i n a l wood
carbon can be l o s t t o a low value char by-product.
Furthermore, l i k e the model oxygenates d e s c r i b e d above,
the EHI of the p y r o l y s i s l i q u i d products i s
s u b s t a n t i a l l y l e s s than 1.
The present study was undertaken t o examine the
p o t e n t i a l of s h o r t contact time r e g e n e r a t i v e f l u i d bed
p r o c e s s i n g t o obviate the problems a s s o c i a t e d with
r a p i d d e a c t i v a t i o n i n f i x e d bed c a t a l y t i c upgrading of
such low EHI feeds.
In f i x e d bed o p e r a t i o n , reduced c a t a l y s t aging
r a t e and s y n e r g i s t i c y i e l d s b e n e f i t s have been reported
f o r co-processing a low EHI (<1) model compound
( e . g . a c e t i c acid) with a s u f f i c i e n t amount of a high
EHI (>1) compound (e.g. methanol) (8-9). In another
f i x e d bed study, Chantai e t a l (10) coprocessed up to
10% methanol with an o i l d e r i v e d from s u p e r c r i t i c a l
e x t r a c t i o n of wood c h i p s . Although some b e n e f i t s i n
y i e l d s from the a d d i t i o n of methanol were evident,
based on the e a r l i e r work (8-9) the amounts of methanol
used by Chantai were too small to reduce c a t a l y s t
d e a c t i v a t i o n . I t was of i n t e r e s t t h e r e f o r e , to f u r t h e r
examine the p o t e n t i a l b e n e f i t s of methanol co-
p r o c e s s i n g f o r both model compound feeds and wood
p y r o l y s i s l i q u i d s i n s h o r t contact time r e g e n e r a t i v e
f l u i d bed p r o c e s s i n g .

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 24. CHEN ET AL. Fluidized-Bed Upgrading of Wood Pyrolysis Liquids 279

Table I A c e t i c A c i d Conversion over ZSM-5

F i x e d Bed Data
370°C, 1 atmosphere t o t a l pressure, 1 LHSV

Time on Stream, hr 0.3 1.3 3.0

Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024
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Conversion, % 100 71 61

Product S e l e c t i v i t y , %

CO 1 1

C0 2 16 23

H 0
2 56 24

Oxygenates* 7 37

Hydrocarbons 20 15

Hydrocarbons, %

C C
l + 2 2 2

C 3 5 4

Q A 8 26
4

C+ 5 85 68

+
Mainly Acetone

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 280 PYROLYSIS OILS FROM BIOMASS

Experimental

Catalyst. The c a t a l y s t used was a s i l i c a alumina bound

HZSM-5.

Production of Wood P y r o l v s i s L i q u i d s . Sawdust

( p r i m a r i l y pine and f i r ) p y r o l y s i s was c a r r i e d out i n a
f i x e d bed r e a c t o r , which h e l d about 200 ml of sample.
The sawdust charge had the f o l l o w i n g elemental a n a l y s i s
(dry b a s i s ) : C - 49.20», H - 6.80%, 0 - 43.40%, ash -
0.60%. The r e a c t i o n was conducted a t atmospheric
pressure by h e a t i n g the sample a t approximately
20°C/min. t o 520*0 i n helium f l o w i n g a t about 800
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024
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ml/min. The sample was then h e l d a t the f i n a l

temperature f o r three hours with helium gas f l o w i n g .

Reactor D e s c r i p t i o n and Run Procedures. A l l catalytic

runs were performed i n a computer c o n t r o l l e d f l u i d i z e d
bed apparatus (11) (Figure 1) o p e r a t i n g c y c l i c a l l y t o
e f f e c t s u c c e s s i v e and repeated r e a c t i o n / r e g e n e r a t i o n
i n t e r v a l s . Approximately 35 ml of the s i l i c a alumina
bound ZSM-5, having a mesh s i z e t y p i c a l of f l u i d
c a t a l y s t , was charged t o the Vycor r e a c t o r along with
15 ml of 120 - 200 mesh Vycor. Helium f l u i d i z i n g gas
entered through a f r i t a t the base of the tapered
s e c t i o n of the r e a c t o r bottom. A small flow of helium
a l s o swept through the feed o i l sidearm i n l e t l i n e .
The t o t a l helium flow (850 cc/min.) p l u s the vapor
phase r e a c t a n t and products maintained the bed i n
vigorous motion which, i n t u r n , i n s u r e d good
temperature c o n t r o l . Runs were c a r r i e d out a t 1 WHSV
based on the low EHI feed component, 410°C and
atmospheric pressure. The c a t a l y s t was a u t o m a t i c a l l y
o x i d a t i v e l y regenerated a f t e r each 10-20 minutes
reaction interval.
When p r o c e s s i n g wood p y r o l y s i s l i q u i d s , the two
p y r o l y s i s product l i q u i d l a y e r s were homogenized (EHI
of the blend was 0.32) by high speed mixing and f e d
immediately t o the f l u i d bed c a t a l y t i c r e a c t o r . When
co-processed with methanol, the two p y r o l y s i s l i q u i d
l a y e r s were d i s s o l v e d i n the methanol t o provide a
mixture having an apparent EHI of 1.2-1.3.
The aqueous phase product from the c a t a l y t i c f l u i d
bed was separated and analyzed by gas chromatography
f o r oxygenates from which conversion could be

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 24. CHEN ET AL. Fïuidized-Bed Upgrading of Wood Pyrolysis Liquids 281

Clock

Hewlett-
Packard
9825A IR CO,
Vent
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024

C 0 Analyzer
2
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1 To Light Gas
Sample Bombs
and Vent

Liquid N 2

Trap

•Charge Oil

Pump

He Sweep
Gas

Flow Controller

0 En-
2

Iriched Air
Flow Controller Flow Controller

Figure 1. Cyclic Fixed Fluid Bed Apparatus

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 282 PYROLYSIS OILS FROM BIOMASS

c a l c u l a t e d . The hydrocarbon product l a y e r contained

only a very small amount of oxygenates (<1%).
The l i q u i d hydrocarbon product was a l s o analyzed
by gas chromatography as were gaseous products, the
l a t t e r being analyzed f o r both t h e i r hydrocarbon and
0 0 contents. Coke was c a l c u l a t e d by the computer from
χ

the data c o l l e c t e d v i a the o n - l i n e CO and COg i n f r a r e d

analyzer d u r i n g each c a t a l y s t r e g e n e r a t i o n . Elemental
and t o t a l m a t e r i a l balances were g e n e r a l l y >95%.
R e s u l t s presented were normalized t o a no-loss b a s i s .

R e s u l t s and D i s c u s s i o n
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024
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Conversion of Model Compounds. Experimental data are

presented i n Table I I . Two conversions are shown f o r
f,
each run. T o t a l conversion" represents the conversion
t o a l l products, while "conversion t o non-oxygenates"
represents conversion t o a l l hydrocarbon, 0 0 and HgO χ

products.

Methanol• The o v e r a l l y i e l d s from the methanol

experiment (EHI = 2.0) are i n good agreement with the
data obtained i n the f l u i d bed MTG process (12). The
hydrocarbon gas products, however, are higher i n
propene and lower i n isobutane, probably due t o the
lower r e a c t i o n pressure used i n t h i s study.

A c e t i c A c i d and Methvlacetate. The data obtained f o r

a c e t i c a c i d i l l u s t r a t e s e v e r a l i n t e r e s t i n g p o i n t s which
can be c o n t r a s t e d with the f i x e d bed o p e r a t i o n c i t e d
above. F i r s t , t o t a l conversions g r e a t e r than 90% may
be maintained i n d e f i n i t e l y provided p e r i o d i c c a t a l y s t
r e g e n e r a t i o n i s employed. In s p i t e of i t s having an
EHI of 0, which assumes t h a t oxygen i s r e j e c t e d as
water, our experimental data show t h a t d e c a r b o x y l a t i o n
takes p l a c e t o a l a r g e extent. As a r e s u l t , by
r e j e c t i n g oxygen as CO , s u b s t a n t i a l production of
hydrocarbons i s p o s s i b l e . Hydrocarbon l i q u i d product
y i e l d i s about 60% higher than t h a t obtained a t 2 hours
p r o c e s s i n g time i n the non-regenerative f i x e d bed
o p e r a t i o n and about 65% of the hydrocarbon product i s
C..+ g a s o l i n e with a predominantly aromatic c h a r a c t e r .
T h i s high s e l e c t i v i t y toward aromatics formation i s
c o n s i s t e n t with the low e f f e c t i v e hydrogen content of
the "hydrocarbon" f r a c t i o n of a c e t i c a c i d .

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 24. CHEN ET AL. Fluidized-Bed Upgrading ofWood Pyrolysis Liquids 283

Table I I Model compound conversion data*

410*0, 1 atm., 1.0-1.1 WHSV, 20 min. reaction intervals
HZSM-5 in S i 0 / A l 0 2 2 3

Acetic Methyl 1.9/1 molar 3.8/1 molar

Methanol Acid Acetate MeOH/ MeOH/
CH 0H
3 CHgCOOH CH C0 CH3 2 3 Acetic Acid Acetic Acid

EHI of Charge 2.0 0.0 0.67 1.0 ( i.o) 1.3

Total Conversion 98.6 91.2 89.4 >91.0 (94.9) 95
Conversion to 98.6 79.8 86.1 90.4 (89.2)
Non-Oxygénâtes
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024

Products (Wt.%
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of Charge)
CO 0.0 3.7 6.2 2.1 (1.8) 1.1 (1.2).
C0 o 0.2 31.4 17.6 9.4 (15.8) 5.2 (10.6)
2
55.8 28.4 21.5 45.3 (42.1) 48.8 (46.7)
H 20
X o
1.4 20.2 13.9 9.6 (10.8) 5.2 ( 7.7)
Oxygenates 19.0 3.8 6.0 7.9 (11.4) 9.9 (13.9)
C - Hydro-
4

carbon gas 23.3 10.6 32.1 24.9 (17.0) 28.7 (19.1)

Cg+ Liquid
Hydrocarbon 42.3 14.4 38.1 32.8 (28.4) 38.6 (33.0)
Total Hydro-
carbons 0.3 1.9 2.7 0.8 ( i . i ) 1.1 ( 0.8)
Coke
Wt.Vs of
Hydrocarbon 5.4 1.5 5.6 7.2 7.6
CÏ • c 1.6
2
0.1 0.7 0.4 0.6
25.9 5.2 6.7 13.8 14.2
%- 5.5 0.5 0.3 0.4 0.5
ic ' 4
0.4 0.3 0.0 0.1 0.1
nC.' 5.8 15.7 1.4 1.6 1.9
Total C - 4
44.6 23.3 14.7 23.5 (34.0) 24.9 "(37.5)
Cg+ (gasoline) 54.7 65.0 78.7 74.1 (59.8) 72.3 (58.1)
Coke 0.7 11.7 6.6 2.4 ( 6.2) 2.8 ( 4.4)
H/C (effective)* * 1.7 1.3 1.3 1.4***
of C + 5

* Numbers shown i n parentheses are the calculated values which would be

expected i f the mixture's behavior was the arithmetic average of i t s
two components.
** Small amounts of oxygen were observed i n the Cg+ l i q u i d . The use
of the effective hydrogen index corrects for this.
*** Approximate numbers.

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ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 284 PYROLYSIS OILS FROM BIOMASS

On a weight b a s i s , a c e t i c a c i d y i e l d s only 40% as

much hydrocarbon as methanol. The lower y i e l d i n ZSM-5
p r o c e s s i n g r e s u l t s p r i m a r i l y from a c e t i c a c i d ' s carbon
l o s s due t o oxygen r e j e c t i o n through d e c a r b o x y l a t i o n t o
co .
2

Methylacetate has an EHI of 0.67 and thus,

o r d i n a r i l y , would a l s o be considered d i f f i c u l t to
process. I t s net hydrogen content, however, i s
s u b s t a n t i a l l y higher than t h a t of a c e t i c a c i d . Because
of i t s higher carbon content (48.6% C), and d e s p i t e
d e c a r b o x y l a t i o n and coking r e a c t i o n s , the observed
hydrocarbon y i e l d remains comparable t o t h a t of
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024

methanol. Moreover, hydrocarbon s e l e c t i v i t y f o r d i r e c t

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conversion t o C-+ g a s o l i n e i s higher than a c e t i c a c i d

or methanol. Thus, the d i r e c t y i e l d of Cg+ g a s o l i n e i s
32.1% on charge vs 23.3% f o r methanol.
From a hydrogen balance standpoint, both a c e t i c
a c i d and methyl acetate r e j e c t l e s s HgO and more 0 0 χ

than methanol, with r e s u l t a n t Cg+ l i q u i d s having

e f f e c t i v e H/C's of approximately 1.3 vs 1.7 - 2 f o r
methanol p r o c e s s i n g .

Mixtures of A c e t i c A c i d and Methanol. P r o c e s s i n g a

1.9/1 or a 3.8/1 molar mixture of CH^OH and a c e t i c a c i d
provided o b s e r v a t i o n s s i m i l a r t o those already
d i s c l o s e d by Chang e t a l (8), v i z , an enhancement i n
Cg+ l i q u i d y i e l d a t the expense of C^- vs what might be
expected i f the mixture behaved as the average of i t s
two components, the c a l c u l a t e d values f o r which are
shown i n parentheses i n Table I I . The s e l e c t i v i t i e s of
the hydrocarbon products amplify the observed synergism
with r e s p e c t t o Cg+ l i q u i d s . Furthermore, there i s an
enhancement i n t o t a l hydrocarbon y i e l d vs l i n e a r
combination expectations.
As shown i n Table I I , the e f f e c t of i n c r e a s i n g
mole percent methanol i n the MeOH/acetic a c i d charge i s
an attendant decrease i n oxygen r e j e c t i o n as COg and an
i n c r e a s e i n oxygen removal as HgO. Thus, more carbon
remains a v a i l a b l e t o form hydrocarbon products, much of
i t becoming Cg+ l i q u i d s .
The above f i n d i n g s demonstrate t h a t a short
contact time f l u i d bed r e a c t o r o p e r a t i n g i n a c y c l i c
mode can be used t o process low EHI compounds to y i e l d
s u b s t a n t i a l amounts of C + l i q u i d hydrocarbon products.
K

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 CHENET AL. Fluidized-Bed Upgrading of Wood Pyrolysis Liquids 285

By co-processing a low EHI m a t e r i a l with a high

EHI compound such as methanol, a s h i f t i n oxygen
r e j e c t i o n from d e c a r b o x y l a t i o n t o dehydration takes
p l a c e . The s h i f t r e s u l t s i n an i n c r e a s e d y i e l d of
hydrocarbons.
The r e a c t i o n of a c e t i c a c i d may have p o t e n t i a l
a p p l i c a t i o n i n c o n v e r t i n g fermentation products t o
hydrocarbons. A c e t i c a c i d i s a major by-product i n
b a c t e r i a l fermentation of biomass t o ethanol (13).
Mixtures of a c e t i c a c i d and ethanol may a l s o be
processed t o hydrocarbons (14).

Upgrading of Wood P y r o l y s i s L i q u i d s . The products from

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sawdust p y r o l y s i s a t 520°C i n f l o w i n g helium a t

atmospheric pressure produced the y i e l d s shown i n Table
III.

e
Table I I I . Wood P y r o l y s i s a t 520 C and 1 atm.

Product Wt.%
CH4 1.4
CO 7.1
C02 8.5
L i q u i d Oxygenates 55.0
Char 28.0

Because the o b j e c t of these experiments was t o t r a c k

the amount of wood carbon which could be converted t o
hydrocarbons by pyrolysis/ZSM-5 upgrading schemes, the
amount of water produced by p y r o l y s i s was not measured,
and water i n the p y r o l y s i s l i q u i d s was f e d along with
the oxygenated products i n subsequent ZSM-5 p r o c e s s i n g .
Elemental analyses and the apparent EHI's ( i n c l u d i n g
any water) are presented i n Table IV. I n s p e c t i o n of
these data i n d i c a t e t h a t the l i q u i d products c o n t a i n
about 31% o f the o r i g i n a l wood carbon. The char
product accounts f o r another 49 wt% of the o r i g i n a l
wood carbon, and i s a v a i l a b l e f o r i n d i r e c t l i q u e f a c t i o n
v i a g a s i f i c a t i o n and methanol s y n t h e s i s . The remaining
20% of the wood carbon becomes CO, COg and methane,
about h a l f of which (as C H and CO) i s a l s o p o t e n t i a l l y
4

a v a i l a b l e f o r conversion t o methanol.
When processed i n the presence of methanol, wood
p y r o l y s i s l i q u i d s e x h i b i t e d synergisms and s e l e c t i v i t y
s h i f t s s i m i l a r t o those d i s c u s s e d above f o r the model

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 286 PYROLYSIS OILS FROM BIOMASS

Table IV. Elemental A n a l y s i s , wt%

Aqueous L i q u i d Organic L i q u i d
Sawdust Laver (51%} Laver (4%) Char

c 49.2 25.9 55.0 87.3

H 6.8 8.8 7.5 3.9
0 43.4 65.3 37.5 8.0
Ash 0.6 - - -
EHI 0.3 0.3 0.6
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compounds. The d e t a i l s of t h i s behavior are presented

below w i t h i n the context of two p o t e n t i a l p r o c e s s i n g
arrangements shown i n F i g u r e s 2 and 3. A major f e a t u r e
common t o both i s the use of the p y r o l y s i s char as a
cheap source of methanol.
F i g u r e 2 shows the products obtained i n a scheme
i n which d i r e c t upgrading of the wood p y r o l y s i s l i q u i d s
over ZSM-5 occurs i n p a r a l l e l with upgrading of
methanol obtained from s y n t h e s i s gas d e r i v e d from
g a s i f i c a t i o n of the p y r o l y s i s char. In F i g u r e 3, the
methanol i s mixed with the p y r o l y s i s l i q u i d s p r i o r to
co-processing over ZSM-5. Approximately 40 l b s . of
methanol per 100 l b s . of dry wood feed i s p o t e n t i a l l y
a v a i l a b l e from the char and p y r o l y s i s gas products.
T h i s amount would provide a weight r a t i o of
methanol/pyrolysis l i q u i d s of 0.73.
In the p a r a l l e l p r o c e s s i n g scheme, a t o t a l of 2 0 . 6
l b s . of hydrocarbon (approximately 85% Cg+ g a s o l i n e ,
i n c l u d i n g a l k y l a t e ) per 95 l b s . of t o t a l feed
( p y r o l y s i s l i q u i d and methanol) i s obtained. In the
co-processing mode, approximately 3 l b s . of a d d i t i o n a l
hydrocarbon r e s u l t concomitant with reduced oxygenates
and coke.
Stated d i f f e r e n t l y , without char g a s i f i c a t i o n ,
o n l y about 6% of the carbon i n the wood could be
upgraded t o hydrocarbon products even i f a l l the
oxygenates produced by p y r o l y s i s were r e c y c l e d to
e x t i n c t i o n . P a r a l l e l upgrading of methanol d e r i v e d
from char g a s i f i c a t i o n can i n c r e a s e t h i s value to
approximately 36%, i . e . , about 6% from the p y r o l y s i s
l i q u i d s and 30% from methanol. Methanol co-processing
boosts the percent of wood carbon transformed i n t o

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 24. CHEN ET AL. Fluidized-Bed Upgrading of Wood Pyrolysis Liquids 287

17 LBS. GAS ( C O . C 0 . C H )
2 4

28 L B S . CHAR GASIFICATION OXYGEN

100 LBS. PYROLYSIS AND
DRY WOOD WATER
SHIFT

SYNTHESIS
GAS

55 LBS.
PYROLYSIS I METHANOL
LIQUIDS CONVERSION

40 LBS.
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024

METHANOL
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ZSM-5 ZSM-5
PROCESSING PROCESSING

7" J
3.2 LBS. HYDROCARBON 17.4 LBS. HYDROCARBON
17.6 LBS. OXYCENATES 22.6 LBS. WATER
26.4 LBS. WATER
4.2 L B S . C 0 2

3.6 LBS. C O K E

Figure 2 . P a r a l l e l Processing Scheme

17 LBS. GAS (CO, C 0 , C H )

2 4

GASIFICATION OXYGEN
100 LBS. 28 LBS. CHAR
PYROLYSIS AND
DRY WOOD" WATER
SHIFT

SYNTHESIS
GAS

55 LBS.
PYROLYSIS METHANOL
LIQUIDS CONVERSION

40 LBS.
METHANOL

ZSM-5
PROCESSING

23.6 LBS. HYDROCARBON

10.6 LBS. O X Y C E N A T E S
59.0 LBS. WATER
1.8 LBS. C O K E

Figure 3. C o p r o c e s s i n g Scheme

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 288 PYROLYSIS OILS FROM BIOMASS

hydrocarbon products t o approximately 42%, i . e . , about

12% from the p y r o l y s i s l i q u i d s and 30% from methanol.

Conclusions

Hydrocarbon y i e l d s can be increased s i g n i f i c a n t l y when

wood p y r o l y s i s l i q u i d s are coprocessed with methanol
over ZSM-5 c a t a l y s t vs separate p r o c e s s i n g of the two
streams over the same c a t a l y s t . Thus, coprocessing
p y r o l y s i s l i q u i d s with methanol produced from char
g a s i f i c a t i o n i s one means of producing hydrocarbon
f u e l s from wood. R e s u l t s obtained i n t h i s study
provide a b a s i s f o r comparison with other p r o c e s s i n g
Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024
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schemes such as wood g a s i f i c a t i o n followed by e i t h e r

F i s c h e r - T r o p s c h s y n t h e s i s o r methanol s y n t h e s i s plus
Mobil's MTG process.

Literature Cited

1. Chang, C. D. and Lang, W. H., U. S. Patent 3 894 103,

1975 .
2. Chang, C. D. and Silvestri, A. J., J. Catal. 1977,
47, 249.
3. Kuo, J. C., Prater, C. D. and Wise, J. J., U. S.
Patent 4 041 094, 1977.
4. Ireland, H. R., Peters, A. W. and Stein, T. R., U.S.
Patent 4 045 505, 1977.
5. Haag, W. O., Rodewald, P. G. and Weisz, P. B., U. S.
Patent 4 300 009, 1981.
6. Brennan, J. Α., Caesar, P. D., Ciric, J. and Garwood,
W. E., U. S. Patent 4 304 871, 1981.
7. Weisz, P. B., Haag, W. O. and Rodewald, P. G.,
Science, 1979, 206, 57.
8. Chang, C. D., Chen, Ν. Υ., Koenig, L. R. and Walsh, D.
E., "Synergism in Acetic Acid/Methanol Reactions Over
ZSM-5 Zeolites", Am. Chem. Soc. Div. Fuel Chem.
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9. Chang, C. D., Lang, W. H. and Silvestri, A. J., U.S.
Patent 3 998 898, 1976.
10. Chantal, P., Kaliaguine, S., Grandmaison, J. L. and
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11. Walsh, D. E., U. S. Patent 4 419 328, 1983.
12. Lee, W., Maziuk, J., Weekman, Jr., V. W. and Yurchak,
S., "Mobil Methanol-to-Gasoline Process," Large
Chemical Plants, Elsevier Scientific Publishing
Co., Amsterdam, The Netherlands, 1979.

Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.
 24. CHEN ET AL. Fluidized-Bed Upgrading of Wood Pyrolysis Liquids 289

13. Cooney, C. L., Wang, D. I. C., Wang, S. D., Gordon, J.

and Jiminez, Μ., Biotech. Bioeng. Symp., 1978, 8, 103.
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Chemtech, 1986, 16, 506.

RECEIVED March 31, 1988

Publication Date: September 30, 1988 | doi: 10.1021/bk-1988-0376.ch024
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Soltes and Milne; Pyrolysis Oils from Biomass

ACS Symposium Series; American Chemical Society: Washington, DC, 1988.