This article was downloaded by: [University of Utah]

On: 18 April 2013, At: 17:07

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Fuel Science and Technology International

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lpet19

MODELING LIGNIN LIQUEFACTION 1. CATALYTIC

HYDROPROCESSING OF LIGNIN-RELATED
METHOXYPHENOLS AND INTERAROMATIC UNIT
LINKAGES
a a
Francis P. Petrocelli & Michael T. Klein
a
Department of Chemical Engineering, University of Delaware, Newark, DE, 19716
Version of record first published: 15 Mar 2007.

To cite this article: Francis P. Petrocelli & Michael T. Klein (1987): MODELING LIGNIN LIQUEFACTION 1. CATALYTIC
HYDROPROCESSING OF LIGNIN-RELATED METHOXYPHENOLS AND INTERAROMATIC UNIT LINKAGES, Fuel Science and Technology
International, 5:1, 25-62

To link to this article: http://dx.doi.org/10.1080/08843758708915845

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions

This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to
anyone is expressly forbidden.

The publisher does not give any warranty express or implied or make any representation that the contents
will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should
be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims,
proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in
connection with or arising out of the use of this material.
 FUEL SCIENCE L TECHNOLOGY INT'L., 5 ( 1 ) , 25-62 (1987)

MODELING LIGNIN LIQUEFACTION 1. CATALYTIC HYDROPROCESSING OF

LIGNIN-RELATED METHOXYPHENOLS AND INTERAROMATIC UNIT LINKAGES

F r a n c i s P. P e t r o c e l l i and Michael T. K l e i n

Department o f Chemical Engineering

Downloaded by [University of Utah] at 17:07 18 April 2013

U n i v e r s i t y o f Delaware
Newark, OE 19716

The r e a c t i o n s o f two s e t s o f l i g n i n model compounds over a

s u l f i d e d CoOMo03/y-A1203 c a t a l y s t were studied. The f i r s t s e t
mimicked l i g n i n methoxyphenol residues and comprised 4-methyl-
guaiacol, 4-methylcatechol, eugenol and v a n i l l i n . Oeorygenation
and hydrogenation were f a c i l e and l e d t o u l t i m a t e molar y i e l d s of
s i n g l e - r i n g products as h i g h as 0.70. The s e l e c t i v i t y t o s i n g l e -
r i n g products i n c r e a s e d w i t h increases i n temperature. o-hydroxy-
diohenvlmethane. ohenvl e t h e r and 0.0'-biohenol c o n s t i t u t e d t h e
s e i o n d s e t t h a t .m'imi&ed t h e r m a l l y i t a b l e ' l i g n i n bonds. Fragmen-
t a t i o n of o-hydroxydiphenylmethane and phenyl e t h e r occurred
r e a d i l y ; o,o';biphenol r e a c t e d t o d i benzofuran.

These r e s u l t s suggest t h a t t h e s i n g l e - r i n g products obtained

from c a t a l y t i c l i q u e f a c t i o n o f l i g n i n s should be more d e s i r a b l e
t h a n those o b t a i n e d from p y r o l y s i s because of b o t h h i g h e r y i e l d s
and reduced complexity.

INTRODUCTION

P y r o l y s i s i s a c o n v e n i e n t l y simple but nevertheless comner-

c i a l l y u n a t t r a c t i v e m t h o d for depolymerization o f l i g n i n t o higher

v a l u e phenolics. Both product y i e l d s and s e l e c t i v i t i e s are

Copyright O 1981 b y Marcel Dekker. Inc.

 26 PETROCELLI AND KLEIN

limiting. The most v a l u a b l e product f r a c t i o n of l i g n i n p y r o l y s i s

i s a t a r , o b t a i n e d i n approximately 30 w t % y i e l d , t h a t c o n t a i n s a

l a r g e number o f p h e n o l i c monomers, dimers and t r i m e r s ; no s i n g l e

molecule predominates. The p r o p e n s i t y of these p h e n o l i c s t o

p a r t i c i p a t e i n undesirable oligomerization reactions further

f r u s t r a t e s e f f i c i e n t p y r o l y t i c processing.
Downloaded by [University of Utah] at 17:07 18 April 2013

Pyrolyses of l i g n i n model compounds have p r o v i d e d i n s i g h t s

i n t o these issues. For example, t h e low-molecular-weight products

o f guaiacol p y r o l y s i s are gases, catechol. and phenol. The major

product i s an i l l - d e f i n e d , higher-molecular-weight char. Thus, t h e

u l t i m a t e molar y i e l d s o f t h e t o t a l o f t h e s i n g l e - r i n g products from

g u a i a c o l pyrolyses, b o t h neat and i n t h e presence of a hydrogen

donor (Hz, t e t r a l i n ) , are t y p i c a l l y l e s s than 0.30 (Bredenberg and

Ceylan. 1983; Ceylan and Bredenberg. 1982; K l e i n . 1981; Lawson and

K l e i n . 1985). T h i s e x p l a i n s why, d u r i n g l i g n i n p y r o l y s e s , t h e

r e a c t i o n o f s i n g l e - r i n g p h e n o l i c s i s l a r g e l y t o char and t h e

recovery of u s e f u l products i s low. Moreover, t h e n u l t i t u d e o f

guai acol r e a c t i o n paths e x p l a i n s t h e c o m p l e x i t y o f t h e s i n g l e - r i ng

p h e n o l i c product spectrum o b t a i n e d from l i g n i n p y r o l y s i s .

Model compound p y r o l y s e s a l s o suggest pathways o f char forma-

t i o n during l i g n i n pyrolysis. Methoxyphenols w i t h a t l e a s t two

oxygenated s u b s t i t u e n t s i n o r t h o p o s i t i o n s (e.g.. guaiacol ,

catechol, v e r a t r o l e ) form c h a r d u r i n g p y r o l y s i s w i t h nuch g r e a t e r

ease t h a n those c o n t a i n i n g o n l y one oxygenated s u b s t i t u e n t (e-g.,

phenol. a n i s o l e ) (Bredenberg and Ceylan. 1983; Connors e t al..

 UODELING LIGNIN LIQUEFACTION. 1 27

1980; K l e i n , 1981; Schlosberg e t al., 1983). This couples w i t h t h e

preceding i n f o r m a t i o n t o i n d i c a t e t h a t deoxygenation of t h e

guaiacols and catechols produced d u r i n g l i g n i n p y r o l y s i s would be

useful. Deoxygenation would e v i d e n t l y h i n d e r t h e i r secondary

thermal r e a c t i o n s t o char, and thus l e a d t o increased y i e l d s of

s i n g l e - r i n g phenolics, w h i l e simultaneously improving t h e p h e n o l i c

Downloaded by [University of Utah] at 17:07 18 April 2013

products ' s e l e c t i v i t y through c o n c e n t r a t i o n i n mono- and non-

oxygenated s i n g l e - r i n g aromatics.

Other model compound pyrolyses (Benjamin e t al.. 1978; Kamiya

e t al.. 1979; K l e i n , 1981; P e t r o c e l l i and Klein, 1984; Schlosberg

e t al.. 1981) c o l l e c t i v e l y suggest t h a t d u r i n g l i g n i n p y r o l y s i s , a t

t h e t y p i c a l temperatures of 300-500°C, o n l y bonds o f t h e a-ether,

8-ether and diphenylethane t y p e a r e appreciably r e a c t i v e , and, on

t h e contrary, biphenyl, o,o'-biphenol , diphenylmethane, o-hydroxy -

diphenylmethane and phenyl e t h e r l i n k a g e s are t h e r m a l l y stable.

The y i e l d s of p h e n o l i c dimers and t r i m e r s i n t h e t a r f r a c t i o n

o b t a i n e d from l i g n i n p y r o l y s i s are appreciable and thus l i k e l y

c o n p r i s e more valuable monomers l i n k e d by t h e t h e r m a l l y s t a b l e

d i a r y l , d i a r y l a l k a n e , and d i a r y l e t h e r linkages. C a t a l y s i s of t h e i r

fragmentation thus appears desirable.

The foregoing motivated t h e present experimental i n v e s t i g a t i o n

of t h e c a t a l y t i c hydrodeoxygenation o f l i g n i n phenolics. Standard

heterogeneous N i - o r Co-promoted t r a n s i t i o n metal c a t a l y s t s on

a c i d i c alumina supports, l o n g used f o r t h e removal of t h e nitrogen,

s u l f u r and metals found i n petroleum crudes (Furimsky, 1979; Gates

 28 PETROCELLI AND KLEIN

e t al.. 1979; Rollman, 1977; S a t t e r f i e l d and Yang, 1983; Weisser

and Landa. 1973) seemed a p p r o p r i a t e . The present r e p o r t i s t h e r e -

f o r e of t h e hydroprocessing r e a c t i o n pathways and k i n e t i c s of model

conpounds t h a t mimic two i m p o r t a n t s t r u c t u r a l aspects o f l i g n i n . A

f i r s t s e t of model compounds, 4 m e t h y l g u a i a c o 1 , 4-methylcatechol,

eugenol, and v a n i l l i n , were models o f l i g n i n s ' aromatic methoxy-

Downloaded by [University of Utah] at 17:07 18 April 2013

phenol s u b s t i t u e n t s and a second set, o-0'-biphenol, o-hydroxy-

diphenylmethane and phenyl e t h e r , were models of i t s t h e r m a l l y

stable interunit links. The c a t a l y s t was a p r e s u l f i d e d

CoOMo03/r-A1203, and t h e experimental r e s u l t s were i n c o r p o r a t e d

i n t o an a p r i o r i model ( w i t h respect t o l i g n i n ) o f b o t h milled-wood

and k r a f t l i g n i n l i q u e f a c t i o n t o be r e p o r t e d upon separately.

Previous experimental l i t e r a t u r e i n d i c a t e d t h a t hydrodeoxy-

g e n a t i o n would occur r e a d i l y a t temperatures lower than those

required for rapid pyrolysis. The major products of a n i s o l e

hydrodeoxygenation a t 250-350°C i n c l u d e d phenol, o - c r e s o l , benzene

and cyclohexane. whereas a t t h e same temperatures t h e major

g u a i a c o l hydrodeoxygenation products i n c l u d e d catechol, phenol,

benzene, and cyclohexane ( H u r f f and K l e i n . 1983). Note t h a t t h e

u l t i m a t e t o t a l molar y i e l d o f s i n g l e - r i n g products of 0.60 observed

by these i n v e s t i g a t o r s d u r i n g guaiacol hydrodeoxygenation a t 300°C

i s t w i c e t h e y i e l d t y p i c a l l y o b t a i n e d from i t s p y r o l y s i s . Vuori

and Bredenberg (1984) observed 4-propylcatechol and 3- and

4-propylphenol as predominant o f t h e s i n g l e - r i n g products t h a t were

a t t a i n e d i n an u l t i m a t e t o t a l molar y i e l d of 0 . B from t h e
 MODELING LIGNlN LIQUEFACTION. 1 29

hydradeoxygenation o f 4-propylguaiacol over Co-MolpA120~. The

c a t a l y t i c d e h y d r o x y l a t i o n of phenol, c r e s o l , o-ethyl phenol,

4-propylphenol, 1-naphthol and 4-hydroxydiphenylmethane (Frederick

and B e l l , 1984; Odebunmi and O l l i s , 1983; Rollman, 1977; Vogelzang

e t al., 1983; Weigold, 1982). as w e l l as oxygen removal from

molecules c o n t a i n i n g h e t e r o c y c l i c oxygen (Krisnamurthy e t a1 .,

Downloaded by [University of Utah] at 17:07 18 April 2013

1981; Lee and O l l i s , 1984; Rollman, 1977). has a l s o been reported.

EXPERIMENTAL METHODS

Table I l i s t s t h e s u b s t r a t e s , t h e c a t a l y s t composition, and

t h e experimental c o n d i t i o n s o f i n i t i a l s u b s t r a t e and c a t a l y s t con-

c e n t r a t i o n s , hydrogen pressure, heat-up time, r e a c t i o n temperature

and maximum h o l d i n g t i m e ( i n c l u d i n g heat-up). The substrates,

t h e n-hexadecane c a r r i e r o i l and t h e chemicals used i n GC a n a l y s i s

were a l l c o m n e r c i a l l y a v a i l a b l e and used as received. The

CoOMo03/y-A1203 c a t a l y s t was o b t a i n e d from h e r i c a n Cyanamid

( c a t a l y s t HDS-16A). P r i o r t o i t s use, t h e c a t a l y s t was crushed and

s i e v e d t o 8 0 t o 100 mesh p a r t i c l e s and was subsequently s u l f i d e d

and reduced by a 30 ml/min flow o f a 10% H2S/90% Hp m i x t u r e f o r 3

h r a t 400°C.

A r e p r e s e n t a t i v e experimental procedure c o n s i s t e d of p l a c i n g

180 m l hexadecane, 0.5 g s u l f i d e d c a t a l y s t , 2 g s u b s t r a t e and 0.3

ml CS2 ( t o m a i n t a i n t h e c a t a l y s t i n i t s s u l f i d i c form) i n t o t h e

r e a c t o r and s e a l i n g i t . Hexadecane was chosen as t h e c a r r i e r o i l

because i t s low vapor p r e s s u r e a t e l e v a t e d temperatures ensured

t h a t , a t reaction conditions, i t would remain i n t h e l i q u i d phase.

 Downloaded by [University of Utah] at 17:07 18 April 2013

W
TABLE I 0

Experimental Conditions f o r L i g n i n Model Compound Hydrodeoxygenation Experiments

Maximum Heat-Up Reactant Catalyst Hydrogen'

Reactant Temperature H o l d i n g Time Time Concent r a t i o n Concentration Pressure
("C) (5) (5) (mol/l) (ill]) (psig)

eugenol 300 21600 1800 .06 54 2.88 1000

vani 11i n 300 22020 1860 .0731 2.89 1000

0.0'-bi phenol 300 26640 1680 .0614 2.84 1000

330 29700 1980 .06 26 2.88 1000

o-hydroxydiphenyl- 300 21720 1800 .0611 2.84 1000 -u

methane 330 17880 2100 .0616 2.96 1000 2
?2
X
m
phenyl e t h e r 280 17760 1800 .06% 2.79 1000 r
300 22740 1680 .0675 2.89 1000
320 18000 0 .0450 3.08 1000
z..
Catalyst: CoO-MoO3/y-A1203, HDS-16A from American Cyanamid.
I n weight percent, 5.6:11.2:0.03:0.04 = CoO:Mo03:Na20:Fe 176 m2/g and 0.50 cm3/g.
*At r e a c t i o n c o n d i t i o n s .
 MODELINC L I G N I N LIQUEFACTION. 1 31

Bubble and dew p o i n t c a l c u l a t i o n s i n d i c a t e d t h a t , a t t y p i c a l

r e a c t i o n c o n d i t i o n s , o n l y 1% of t h e s u b s t r a t e and 0.5% of t h e

hexadecane loaded would be i n t h e vapor phase. The r e a c t o r was then

purged and p r e s s u r i z e d t o about 500 p s i g w i t h Hz and brought t o

r e a c t i o n temperature i n 30-35 min. Substrate conversion was always

low ( t y p i c a l l y l e s s than 0.10) a t t h e end of t h e heat-up period.

Downloaded by [University of Utah] at 17:07 18 April 2013

Approximately 1 0 l i q u i d samples, each 1-2 ml i n size, were w i t h -

drawn a t p e r i o d i c i n t e r v a l s d u r i n g each run. I n one case, namely,

t h e r e a c t i o n o f phenyl e t h e r a t 320DC, an e x t e r n a l loader apparatus

was used t o i n j e c t 30 mi of a phenyl ether/hexadecane m i x t u r e i n t o

t h e r e a c t o r a f t e r i t had a t t a i n e d t h e d e s i r e d temperature.

Product i d e n t i f i c a t i o n was by GCIMS ( p r o v i d e d by Dr. John

Obst, USDA F o r e s t Products L a b o r a t o r y ) on a F i n n i g a n 4510 i n s t r u -

ment w i t h e l e c t r o n impact mass s p e c t r a o b t a i n e d a t 70 e l e c t r o n

v o l t s and by c o i n j e c t i o n on an HP 5880 gas chromatograph equipped

w i t h a flame i o n i z a t i o n d e t e c t o r . A c e t y l a t i o n of t h e p h e n o l i c s by

t h e a d d i t i o n of 1 m l a c e t i c anhydride and 0.1 ml p y r i d i n e t o each

sample obtained from t h e autoclave experiments f a c i l i t a t e d t h e GC

s e p a r a t i o n over a 50 m SE-54 f u s e d - s i l i c a capi 1 l a r y column.

Approximately 10 mg of ethylbenzene and 10 mg o f e i t h e r guaiacol o r

eugenol were added t o each sample as e x t e r n a l standards. In all,

t h e s e analyses allowed f o r s e p a r a t i o n o f a l l products except

benzene and cyclohexane, which e l u t e d w i t h i d e n t i c a l r e t e n t i o n

t i m e s and w i l l t h e r e f o r e be grouped as a s i n g l e lump i n t h e r e s u l t s

t h a t follow. Use o f s e p a r a t e l y determined response f a c t o r s enabled

 32 PETROCELLI AND KLElN

c a l c u l a t i o n o f p r o d u c t y i e l d s and q u a n t i t a t i o n of an observable

products index (OPI), here defined as t h e percentage of i n i t i a l

s u b s t r a t e mass accounted f o r by t h e t o t a l mass o f e l u t e d peaks.

The experimental r e s u l t s a r e organized a c c o r d i n g t o s u b s t r a t e .

Downloaded by [University of Utah] at 17:07 18 April 2013

Several s p e c i e s ' lumps a r e used i n t h e p r e s e n t a t i o n of r e s u l t s t h a t

follow. F i r s t , t h e a n a l y t i c a l chemistry l i m i t a t i o n s r e q u i r e d a

benzene p l u s cyclohexane (benzene + cyclohexane) lump. Second, t h e

t e r m " c r e s o l " w i l l r e f e r t o t h e sum o f t h e meta and para isomers,

which t y p i c a l l y o c c u r r e d i n n e a r l y equal p r o p o r t i o n s , unless

s p e c i f i c a l l y s t a t e d otherwise. F i n a l l y , t h e t e r m "phenol" w i l l

represent a s i n g l e - r i n g aromatic species w i t h a s i n g l e a r y l hy-

d r o x y l s u b s t i t u e n t and no o t h e r o ~ y g e n - c o n t a i n i n g s u b s t i t u e n t s on

t h e aromatic r i n g . These w i l l be d i s t i n c t from "phenolics," which

i s g e n e r i c and w i l l apply t o guaiacols, catechols, and phenols.

4-Methylguaiacol

The major products o f t h e hydrodeoxygenation of methylguaiacol

a r e summarized i n Table I 1 f o r r e a c t i o n a t 300°C. The products

i n c l u d e d 4-methylcatechol. c r e s o l , an isomer o f methylguaiacol,

toluene, methylcyclohexane and f i v e a l k y l phenols, t h r e e of which

had a m o l e c u l a r weight of 122 and two of which had a m o l e c u l a r

weight o f 150. Minor products i n c l u d e d d i m e t h o ~ y t o l u e n e , an a l k y l

c a t e c h o l w i t h a m o l e c u l a r weight of 152 and, a t 325'C o n l y , phenol.

guaiacol, two a d d i t i o n a l a l k y l phenols (one o f m o l e c u l a r weight of

 Downloaded by [University of Utah] at 17:07 18 April 2013

TABLE 11
H
Representative Product Yields From Hydrodeoxygenation o f L i g n i n Model Compounds: Methoxyphenols P
*
0
2
E
Substrate 4-methylguaiacol 4-methylcatechol eugenol vanillin 5
Temperature, C
' 300 300 300 300 300 300 300 300 .g
Time, s 3144 15240 2850 20670 2646 21600 2640 18684 ;
Converslon .52 .99 .31 .99 .90 1.0 .57 1.0 P
El
6
Products Molar Yields

toluene
methylcyclohexene
methylcyclohexane
m-cresol + p-cresol
HC w i t h MW = 120
4-methylcatechol
HC w i t h MW- 126
propylphenols
4-methy lguai acol
methylguaiacol isomer
phenols w i t h MW = 150
propylcatechols
p r o p y l g u a i acols
phenol w i t h MI = 178
 34 PETROCELLI AND KLElN

136 and t h e o t h e r o f m o l e c u l a r weight of 150) and an a l k y l c a t e c h o l

w i t h a m o l e c u l a r weight o f 138. The observable products i n d e x

(OPI) m o n o t o n i c a l l y decreased w i t h i n c r e a s i n g h o l d i n g t i m e a t a l l

t h r e e r e a c t i o n temperatures b u t increased w i t h r e a c t i o n temperature

a t constant conversion. Reaction a t 250°C r e s u l t e d i n t h e produc-

t i o n of methylcatechol, t h e methylguaiacol isomer, c r e s o l and

Downloaded by [University of Utah] at 17:07 18 April 2013

dimethoxytoluene. Molar y i e l d s o f each increased m o n o t o n i c a l l y and

reached values of 0.085. 0.15. 0.075 and 0.021, respectively. at

t h e longest h o l d i n g t i m e (19320 s), where t h e conversion o f

methylguaiacol was 0.71.

Reaction a t 300'C i s sumnarized i n F i g u r e 1, which i l l u s t r a t e s

v a r i a t i o n s of t h e y i e l d s o f t h e major products w i t h conversion.

The molar y i e l d s of t h e p r i m a r y product methylcatechol proceeded

t h r o u g h a maximum of 0.25 a t a conversion of 0.52 a t a h o l d i n g t i m e

o f 3144 s. Before undergoing secondary decomposition, c r e s o l

appeared t o form from methylcatechol and i t s maximum y i e l d was 0.34

a t a conversion o f 0.98 (9882 s h o l d i n g t i m e ) . The i n i t i a l r a t e of

appearance of methylcatechol was n o t i c e a b l y l e s s t h a n t h e r a t e of

disappearance of methylguaiacol. i n d i c a t i n g t h a t p r i m a r y oligomer-

i z a t i o n r e a c t i o n s of methylguaiacol a l s o occurred. Hydrocarbons

were d e t e c t e d o n l y a f t e r a conversion of 0.76 had been achieved.

i n d i c a t i n g t h a t toluene. methylcyclohexane and methylcyclohexene

were secondary products t h a t formed through r e a c t i o n of c r e s o l .

Cresol a l s o r e a c t e d t o o t h e r u n i d e n t i f i e d minor products.

A d d i t i o n a l minor products of methylguaiacol r e a c t i o n a t 3009C

 NODELING L I G N I N L I Q U E F A C T I O N . 1

0.35

0.3

0.25
E
0
.% 0.2
L
o
5 0.15
E
Downloaded by [University of Utah] at 17:07 18 April 2013

0.1

0.05

0
0 0.2 0.4 0.6 0.8 1
conversion

FIG. 1. Major products of 4 m e t h y l guaiacol hydrodeoxygenation

300°C.

included a l k y l phenols whose molecular weights, but not exact

s t r u c t u r e s , could be discerned.

The phenols w i t h molecular weight o f 122 were secondary pro-

ducts t h a t l i k e l y evolved through deoxygenation of dimethyl- o r

e t h y l catechol species. (However, n e i t h e r of these l a t t e r two

species was observed a t 250°C o r 300°C, whereas one was observed a t

325'C.) The two a l k y l phenols w i t h a molecular weight of 150 were

a l s o secondary products, detected a f t e r a h o l d i n g time of 4422 s

(conversion = 0.76) a t 300'C and i n maximum combined y i e l d of 0.14.

The formation o f these a l k y l phenols was a t t r i b u t e d t o t h e combi-

n a t i o n o f l i g h t e r phenols (such as c r e s o l ) w i t h m t h y l groups made

a v a i l a b l e through e i t h e r demethylation of aromatic m t h o x y l s o r

p a r i n g from t h e aromatic rings. Since these a l k y l phenols were

 36 PETROCELLI AND KLEIN

a l s o observed from t h e r e a c t i o n o f methylcatechol (see next sec-

t i o n ) , p a r i n g appeared more l i k e l y . It i s noteworthy t h a t separate

c o n t r o l experiments, wherein neat r e a c t i o n o f methylguaiacol a l s o

l e d t o t h e formation o f b o t h of t h e a l k y l phenols w i t h a m o l e c u l a r

weight o f 150, e l i m i n a t e s t h e hexadecane c a r r i e r o i l as t h e source

o f t h e added methyl groups.

Downloaded by [University of Utah] at 17:07 18 April 2013

The r a p i d r e a c t i o n o f methylguaiacol a t 325'C l e d t o a con-

v e r s i o n o f 0.95 a f t e r 3780 s. As was t h e case a t 30OoC, methyl-

c a t e c h o l and c r e s o l . w e r e t h e dominant products, w i t h maximum

y i e l d s of 0.20 and 0.34. respectively. The formation o f phenol and

g u a i a c o l a t t h i s temperature r e p r e s e n t s p a r i n g of t h e a r y l methyl

group. The y i e l d s of phenols w i t h a molecular weight o f 150 were

lower t h a n a t 300°C, whereas those o f phenols w i t h a m o l e c u l a r

weight of 122 were h i g h e r . Three phenols w i t h molecular weights of

122 were i d e n t i f i e d a t 325'C. i n c l u d i n g t h e one i d e n t i f i e d a t

3OO0C.

The s e l e c t i v i t y of methy,lguaiacol reaction t o single-ring

phenols and hydrocarbons i n c r e a s e d w i t h i,ncreases i n r e a c t i o n

temperature. T h i s suggests t h a t deoxygenation of methylguaiacol

, .
occurred w i t h a h i g h e r a c t i v a t i o n energy t h a n c h a r formation.

The f o r e g o i n g i n d i c a t e s t h a t t h e methylguaiacol r e a c t i o n n e t -

work c o n s i s t s of i s o m e r i z a t i o n of methylguaiacol and major pathways

f o r r e a c t i o n of b o t h ' i s o m e r s t o methylcatechol. c r e s o l , a d i m e t h y l

o r e t h y l c a t e c h o l lump and coke. Secondary r e a c t i o n pathways i n c l u d e

decomposition of m e t h y l c a t e c h o l t o c r e s o l and t o coke, and.

 MODELING LIGNIN LIQUEFACTION. 1 37

f u r t h e r , r e a c t i o n o f c r e s o l t o hydrocarbons and phenols w i t h a

m o l e c u l a r weight of 150. Major primary pathways are i l l u s t r a t e d i n

F i g u r e 2, which a l s o l i s t s a s s o c i a t e d r a t e constants and Arrhenius

parameters deduced u s i n g a s e q u e n t i a l simplex search.

4-Methylcatechol
Downloaded by [University of Utah] at 17:07 18 April 2013

Methylcatechol r e a c t i o n products a r e summarized i n Table I 1

and i n c l u d e d c r e s o l , toluene, methylcyclohexane, methylcyclohexene.

an a l k y l - s u b s t i t u t e d catechol w i t h a m o l e c u l a r weight o f 166, and

t h e t h r e e a l k y l phenols w i t h a molecular weight of 150 t h a t were

a l s o observed from t h e r e a c t i o n s o f methylguaiacol. The OPI

decreased w i t h r e a c t i o n t i m e a t each temperature studied, a l t h o u g h

f o r a given conversion O P I i n c r e a s e d w i t h increases i n temperature.

Reaction a t 250°C y i e l d e d o n l y c r e s o l , toluene, m e t h y l c y c l o -

hexane and methylcyclohexene as products. Cresol, d e t e c t e d a t a

conversion o f l e s s than 0.10 and e a r l i e r t h a n any o t h e r species,

was a primary product. The hydrocarbons arose from secondary

deoxygenation and hydrogenation of c r e s o l . Coke formation was t h e

p r e f e r r e d pathway, s i n c e t h e molar s e l e c t i v i t y t o t o t a l low-

molecular-weight products was o n l y -35% a f t e r a conversion o f 0.5.

Cresol, toluene, methylcyclohexane, methylcyclohexene, and two

o f t h e a l k y l phenols w i t h a m o l e c u l a r weight o f 150 were t h e major

p r o d u c t s r e s u l t i n g from r e a c t i o n a t 300°C and 340°C. The phenols

w i t h a molecular weight o f 150 were secondary products t h a t

appeared t o form through r e a c t i o n o f c r e s o l . Cresol was t h e domi-

nant product a t low and i n t e r m e d i a t e h o l d i n g times b u t underwent

 PETROCELLI AND KLEIN

4.35.1 5.9
1
Downloaded by [University of Utah] at 17:07 18 April 2013

COKE

&-" + #, ' ;4

OH OH OH

4.30.1 0.6

COKE
1 4.71.6.7

FIG. 2. Lignin model compound hydrodeoxygenation primary reaction

pathways and k i n e t i c s , as ( l o g 1 0 k 3 0 0 0 ~ . E*Ckcal/mol]) o r
(~oglok300~c).
a. 4-methyl guaiacol
b. 4-methylcatechol
c. eugenol
d. v a n i l l i n
e. 0.0'-biphenol
f . 0-hydroxydiphenylmethane
g. phenylether
 MODELING LIGNIN LIQUEFACTION. 1
Downloaded by [University of Utah] at 17:07 18 April 2013

COKE
C) sugsnol

=+,
GOMS
OH OH
OMS

1 '.-
COKE

FIG. 2 CONTINUED
Downloaded by [University of Utah] at 17:07 18 April 2013

1) o-hydroxydiphenylmsthons

g) phenyl ether

FIG. 2 CONTINUED
 MODELING LIGNIN LIQUEFACTION. 1

deoxygenation t o hydrocarbons. The r a t e of c r e s o l disappearance

c l o s e l y matched t h e r a t e o f hydrocarhon appearance a t h i g h

conversion.

F i g u r e 3 i l l u s t r a t e s t h e e f f e c t of r e a c t i o n temperature on

t h e y i e l d s o f phenols and hydrocarbons from r e a c t i o n of methyl-

catechol. T h i s p l o t of t h e combined y i e l d s o f a l l phenols and a l l

Downloaded by [University of Utah] at 17:07 18 April 2013

hydrocarbons vs s u b s t r a t e conversion demonstrates t h a t t h e s e l e c -

t i v i t y t o t h e l o w m o l e c u l a r - w e i g h t products increased w i t h

i n c r e a s i n g r e a c t i o n temperature; t h i s was a t t h e expense of char

formation.

The deduced methylcatechol r e a c t i o n network t h u s i n c l u d e d

p r i m a r y pathways t o c r e s o l and coke, w i t h secondary decomposition

of t h e former t o hydrocarbons and phenols w i t h a m o l e c u l a r weight

of 150. This i s i l l u s t r a t e d i n Figure E along w i t h a s s o c i a t e d

pseudo-first-order r a t e constants and Arrhenius parameters.

Eugenol

Reaction o f eugenol a t 300°C l e d t o 17 i d e n t i f i a b l e products.

T h i s s e t comprised a l l y l b e n r e n e , n-propylbenzene, allylcyclohexane,

4-propylcyclohexane, 4-n-propylphenol, another phenol w i t h a

m o l e c u l a r weight o f 136, t h r e e phenols w i t h a m o l e c u l a r weight of

150, two phenols w i t h a m o l e c u l a r weight of 178, 4-n-propyl-

g u a i a c o l , another guaiacol w i t h a m o l e c u l a r weight of 166, and four

a l k y l c a t e c h o l s w i t h molecular weights r a n g i n g from 152 t o 194.

i n c l u d i n g 4-n-propylcatechol. OPI decreased w i t h r e a c t i o n time.

T y p i c a l y i e l d s o f major p r o d u c t s a r e l i s t e d i n Table 11.
 PETROCELLI AND KLEIN

O" - w 250 C
"
0.8- 300 C
s
0)

0.7 - 0 340 C
5 0 D

b 0.6 -
'D a
f 2 0.5-
0

0 * a
a

6 -
0.4
' -m 0.3 -
D

.
I +

g 0.2 -
Downloaded by [University of Utah] at 17:07 18 April 2013

v
i
0

2 0.1-
0- t-: ,
0 0.2 0.4 0.6 0.8 1
conversion

FIG. 3. Influence of temperature on t h e s e l e c t i v i t y of C m e t h y l -

catechol hydrode0l;ygenation t o s i n g l e - r i n g products.

The propylguaiacols and propylcatechols were t h e major prod-

ucts, w i t h 4-propylguaiacol being predominant and primary. The

y i e l d s o f a l l phenolic products passed through maxima as r e a c t i o n

t i m e increased. and occurred i n t h e temporal order: guaiac'ols.

catechols and, f i n a l l y , phenols. I n t e r e s t i n g l y , t h e y i e l d s of

phenols w i t h a molecular weight of 150 and phenols w i t h a molecular

weight o f 178 were e&al a t a l l h o l d i n g times, as was a l s o t h e case

f o r catechols w i t h a molecular weight of 166 and catechols w i t h a

molecular weight o f 194. F i n a l l y , t h e r e l a t i v e abundance of pro-

p y l a t e d products demonstrated t h a t the propyl group was r e l a t i v e l y

s t a b l e under t h e r e a c t i o n c o n d i t i o n s studied.

The foregoing suggested a eugenol r e a c t i o n network comprising

primary pathways t o propylguaiacol and coke, and subsequent reac-

 HODELING LIGNIN LIQUEFACTION. 1

t i o n s of the propyl guaiacol t o propylcatechol , propylphenols and

coke. The phenols subsequently react t o y i e l d hydrocarbon prod-

ucts. The network also includes minor pathways f o r t h e r e a c t i o n

o f 4-n-propylphenol and i t s isomer t o form higher molecular weight

phenols and f o r the r e a c t i o n of 4-n-propylcatechol and i t s isomer

t o form higher molecular weight catechols; these are analogous t o

t h e production o f phenols w i t h a molecular weight of 150

Downloaded by [University of Utah] at 17:07 18 April 2013

from cresol t h a t was observed during t h e r e a c t i o n of rnethyl-

catechol. These pathways are i l l u s t r a t e d i n Figure 2 along w i t h

deduced r a t e parameters.

Vanillin

A l l of t h e i d e n t i f i e d products from t h e r e a c t i o n of v a n i l l i n

a t 300°C were also observed from the r e a c t i o n of methylguaiacol a t

t h e same temperature. The major products were thus methylguaiacol,

methylcatechol, cresol, phenol w i t h a molecular weight o f 150, and

toluene, methylcyclohexane and methylcyclohexene. No carbonylated

products were observed, and t h e OPI decreased w i t h increases i n

r e a c t i o n time. Typical y i e l d s of major products are l i s t e d i n

Table 11.

Methylguaiacol was t h e only primary r e a c t i o n product, and i t s

maximum molar y i e l d of 0.42 occurred a t a v a n i l l i n conversion of

0.57 and a h o l d i n g time o f 2640 s. The subsequent maximum i n t h e

y i e l d of methylcatechol o f 0.18 occurred a t a h o l d i n g time o f 7152

s (conversion = 0.92), and t h e maximum cresol y i e l d o f 0.22

occurred a t a h o l d i n g time o f 15294 s (conversion = 0.98).

 44 PETROCELLI AND KLEIN

The v a n i l l i n r e a c t i o n network t h u s had primary pathways t o

m e t h y l g u a i a c o l and coke, and t h e s e p a r a t e l y deduced secondary

r e a c t i o n s o f t h e methylguaiacol accounted f o r t h e f o r m a t i o n o f t h e

remainder of t h e observed products. The network and a s s o c i a t e d

r a t e parameters a r e shown i n F i g u r e 2.

o-~ydroxydiphenylmethane
Downloaded by [University of Utah] at 17:07 18 April 2013

The major products from t h e r e a c t i o n o f o-hydroxydiphenyl-

methane were t o l u e n e , phenol, benzene + cyclohexane and t h e two-

r i n g hydrocarbons diphenylmethane and cyclohexylphenylmethane. The

m i n o r p r o d u c t s c o n s i s t e d of o-cresol, two isomers o f o-hydroxy-

diphenylmethane, t h r e e a l k y l phenols w i t h a m o l e c u l a r weight of

136, two p h e n o l i c s w i t h a m o l e c u l a r weight o f 198 and a hydrocarbon

w i t h a m o l e c u l a r weight of 126. The OP1 was c o n s i s t e n t l y between

90 and 110%. o-Hydroxydiphenylmethane conversion was complete a t a

h o l d i n g t i m e of 21714 s a t 300°C and 8544 s a t 330°C. Typical

y i e l d s o f major products a t 330°C a r e summarized i n Table 111. The

v a r i a t i o n s of p r o d u c t s ' y i e l d s w i t h conversion a t 330°C a r e

p r e s e n t e d i n F i g u r e 4.

The r e s u l t s d i d not a l l o w d e c i s i v e discernment between primary

and secondary products. F i g u r e 4 i n d i c a t e s t h a t t h e major prod-

u c t s , t o l u e n e and phenol, were l i k e l y primary p r o d u c t s as w e l l .

The l e s s abundant o-hydroxydiphenylmethane isomers and

diphenylmethane p r o d u c t s a l s o appeared t o be primary. I n addition

t o these, t h e two p h e n o l i c s w i t h a m o l e c u l a r weight of 198 were

a l s o p r i m a r y products, as was i n d i c a t e d by t h e i r combined y i e l d of

0.11 a t an o-hydroxydiphenylmethane conversion o f 0.13 (300°C. 2682

 Downloaded by [University of Utah] at 17:07 18 April 2013

Z
TABLE 111 0

Representative Product Y i e l d s From Hydrodeoxygenation o f L i g n i n Model Compounds: lnteruni t Links g2

Z

Substrate 0.0'-biphenol o-hydroxydiphenylmethane phenyl e t h e r

Temperature, "C 330 330 330 330 320 320
Time, s 3358 13824 2970 15462 1842 18018
Conversion .40 .85 .54 1.0 .070 .98

Products Molar Y i e l d s

benzene + cyclohexane
toluene
phenol
o-cresol
phenols w i t h MW = 136
biphenyl
cvclobenzene

d i benzofuran
2-phenylphenol
benzylcyclohexane
 PETROCELLI AND KLEIN

0.9
0.8
0.7 Benzene + Cyclohex
0.6
9
f 0.5
-b 0.4
2 0.3
0.2
Downloaded by [University of Utah] at 17:07 18 April 2013

0.1
0
0 0.2 0.4 0.6 0.8
conversion

FIG. 4. Major products o f o-hydroxydiphenylmethane hydrodeoxygen-

a t i o n a t 330°C.

s holding time). These phenolics underwent rapid secondary

decomposition a t both 300 and 330°C. Yields o f benzene + cyclo-

hexane and toluene increased monotonically a t both t q e r a t u r e s .

A t 330°C, t h e maximum molar y i e l d s o f both phenol and two-ring

hydrocarbons of 0.57 and 0.17, respectively. were lower than those

a t 300'C o f 0.72 and 0.23, respectively. This suggests thermal

a c t i v a t i o n of t h e secondary reactions.

The r e l a t i o n s h i p between toluene and phenol y i e l d s i s explored

i n t h e p a r i t y p l o t of Figure 5. The y i e l d s of toluene and phenol

were nearly equal f o r low conversions, whereas a t higher conver-

sions the toluene y i e l d s were generally higher than phenol y i e l d s . .

This was t r u e a t both temperatures. These data suggest t h a t t h e
 MODELING LIGNIN LIQUEFACTION. 1

0.8 -

-.a0 0.5 -
Downloaded by [University of Utah] at 17:07 18 April 2013

Molar Yield of Toluene

FIG. 5. Primary p r o d u c t s ' r e l a t i o n s h i p f o r o-hydroxydiphenyl-

methane hydrodeoxygenation a t 300 and 330°C.

f o r m a t i o n o f t o l u e n e and phenol was synchronous and t h a t t h e l a t t e r

underwent deoxygenation.

The o-hydroxydiphenylmethane r e a c t i o n network i s shown i n

F i g u r e 2 and comprises two major p r i m a r y pathways: i )

deoxygenation t o diphenylmethane, and i i ) fragmentation of

o-hydrowdiphenylmethane t o t o l u e n e + phenol and, t o a minor

extent, (benzene + cyclohexane) + o-cresol. Major secondary

pathways i n v o l v e d hydrodeoxygenation of phenol t o benzene +

cyclohexane and 0-cresol t o t o l u e n e and a l s o hydrocracking o f two

r i n g hydrocarbons t o (benzene + cyclohexane) + toluene. The r a t e

parameters are summarized i n F i g u r e 2.

 PETROCELLI AND KLEIN

0.0'-Biphenol

The major products from r e a c t i o n o f 0.0-biphenol a t b o t h 300

and 330°C i n c l u d e d dibenzofuran, 2-phenylphenol (PPOH), biphenyl,

cyclohexylbenzene, d i c y c l o h e x y l , and benzene + cyclohexane. Minor

p r o d u c t s c o n s i s t e d of phenol, an isomer of biphenol and two

u n i d e n t i f i e d p h e n o l i c products w i t h a m o l e c u l a r weight o f 228.

T y p i c a l y i e l d s of major p r o d u c t s a t 330°C a r e l i s t e d i n Table 111.

Downloaded by [University of Utah] at 17:07 18 April 2013

The average OPI was 117% a t 300°C and 107% a t 330-12. The major

p r i m a r y products were dibenzofuran and PPOH, which a t t a i n e d molar

y i e l d s o f 0.58 and 0.18, r e s p e c t i v e l y . a t a 0.0'-biphenol

c o n v e r s i o n o f 0.92 a t 300'C. Both phenol and t h e species w i t h a

m o l e c u l a r weight o f 228 were a l s o p r i m a r y products. The y i e l d s of

dibenzofuran, PPOH and phenol each passed through a maximum d u r i n g

r e a c t i o n a t 330bC. T h i s was accompanied by i n c r e a s e s i n t h e

u l t i m a t e y i e l d s of a l l t h e hydrocarbon products.

The 0.0'-biphenol r e a i t i on network t h u s i n c l u d e s p r i m a r y

pathways f o r i s o m e r i z a t i o n and r e a c t i o n t o dibenzofuran, PPOH.

phenol, and p h e n o l i c s w i t h a m o l e c u l a r weight o f 228; o n l y t h e

d i benzofuran and PPOH pathways were k i n e t i c a l l y i m p o r t a n t . The

'--
secondary r e a c t i o n of PPOH was t o e i t h e r phenol + (benzene +
cyclohexane) o r t o t w o - r i n g hydrocarbons, and dibenzofuran r e a c t s

t o t w o - r i n g hydrocarbons as w e l l ; phenol deoxygenates t a benzene +

cyclohexane. The t w o - r i n g hydrocarbons a r e s t a b l e end-products.

s i n c e t h e i r r e a c t i o n t o benzene + cyclohexane was not observed a t

t h e present c o n d i t i o n s . The network and p s e u d o - f i r s t - o r d e r r a t e

parameters a r e l i s t e d i n F i g u r e 2.
 MODELING L l G N I N LIQUEFACTION. 1

Phenyl E t h e r

The r e a c t i o n s o f phenyl e t h e r were s t u d i e d a t 280, 300 and

320°C; i n t h e l a t t e r case an e x t e r n a l l o a d e r apparatus was used t o

i n j e c t t h e r e a c t a n t a f t e r r e a c t i o n temperature had been achieved.

The o n l y products o f phenyl e t h e r r e a c t i o n were (benzene +

cyclohexane) and phenol. T y p i c a l y i e l d s of these products a t 320°C
Downloaded by [University of Utah] at 17:07 18 April 2013

a r e presented i n Table 111. The f i n a l phenyl e t h e r conversions

were 0.19, 0.95 and 0.98 a t 280, 300 and 320°C, respectively.

The y i e l d s of benzene + cyclohexane and phenol were a p p r o x i -

m a t e l y equal f o r a l l h o l d i n g t i m e s a t 280°C and s h o r t h o l d i n g t i m e s

a t 300 and 320°C. At t h e h i g h e r temperatures t h e y i e l d of phenol

passed through a maximum and subsequently decreased w i t h a c o r r e s -

ponding i n c r e a s e i n benzene + cyclohexane y i e l d s .

Reaction t o benzene + cyclohexane and phenol i s t h e o n l y

p r i m a r y pathway i n t h e phenyl e t h e r hydrodeoxygenation r e a c t i o n

network, which a l s o i n c l u d e s secondary deoxygenation of phenol t o

benzene + cyclohexane. These pathways and deduced p s e u d o - f i r s t -

o r d e r r a t e parameters a r e l i s t e d i n F i g u r e 2.

DISCUSSION

C a t a l y t i c l i g n i n l i q u e f a c t i o n and hydrodeoxygenation was

devised as a means o f i n c r e a s i n g t h e y i e l d and decreasing t h e

c o m p l e x i t y o f t h e s i n g l e - r i n g p h e n o l i c s ' product f r a c t i o n r e l a t i v e

t o t h a t r e a l i z e d through p y r o l y s i s . Product y i e l d s would i n c r e a s e

because: (1) t h e c a t a l y t i c hydrodeoxygenation of g u a i a c o l s and

 50 PETROCELLI AND KLEIN

catechols t o noncoking phenols (Jegers and Klein, 1985) should

reduce char formation, and (2) t h e c a t a l y t i c hydrocracking of many

t h e r m a l l y stable l i g n i n i n t e r u n i t l i n k s should be f a c i l e . Removal

of oxygen s u b s t i t u e n t s and, i n p a r t i c u l a r , mobile methyl groups

from aromatic m t h o x y l s , would also decrease t h e number o f d i f f e r -

e n t phenolics obtained. This o v e r a l l strategy was i n v e s t i g a t e d

h e r e i n through t h e reactions of model compounds which mimic t h e

Downloaded by [University of Utah] at 17:07 18 April 2013

coke-forming methoxyphenol s u b s t i t u e n t s and t h e t h e r m a l l y s t a b l e

i n t e r u n i t l i n k s found i n l i g n i n .

The discussion of t h e model compound experiments t h a t follows

i s d i v i d e d i n t o t h r e e sections. The f i r s t two p e r t a i n t o t h e

r e s u l t s o f t h e methoxyphenol and i n t e r u n i t l i n k model experiments.

respectively, and t h e t h i r d section considers t h e i m p l i c a t i o n s o f

these r e s u l t s t o l i q u e f a c t i o n of actual l i g n i n s .

Methoxylphenols

The c a t a l y t i c demethylation, dehydroxylation and hydrogenation

of methylguaiacol, m t h y l c a t e c h o l , eugenol and v a n i l l i n were f a c i l e

a t temperatures w e l l below those r e q u i r e d f o r any appreciable

thermal r e a c t i v i t y . A d d i t i o n a l l y . t h e more thermally a c t i v a t e d

p y r o l y s i s of guaiacol i s mostly t o char and lesser amounts of

catechol, phenol. cresol and other lowmolecular-weight products

(Bredenberg and Ceylan. 1983; Ceylan and Bredenberg. 1982; K l e i n and

V i rk, 1971; Lawson and Klein. 1985). For example, Ceylan and

Bredenberg (1982) observed a 0.57 conversion of guaiacol from neat

p y r o l y s i s a t 3 4 5 Y f o r a batch h o l d i n g time o f 2 h r ; molar y l e l d s o f

 MODELING LIGNIN LIQUEFACTION. 1

catechol, phenol and t o t a l i d e n t i f i e d products were only 0.098,

0.031 and 0.16. respectively. I n a separate study (Bredenberg e t

al.. 1983). these i n v e s t i g a t o r s pyrolyzed guaiacol f o r 2 h r i n

t e t r a l i n a t 345'C and found molar y i e l d s of 0.118 catechol and 0.033

phenol a t a conversion of 0.40. I n both instances, t h e l i g h t prod-

ucts, such as catechol, accounted f o r l e s s than 50% of t h e reacted

guaiacol . Further, once formed during guaiacol p y r o l y s i s i n i t s

Downloaded by [University of Utah] at 17:07 18 April 2013

maximum y i e l d o f t y p i c a l l y 0.2 (Lawson and Klein. 1985). catechol

appears t o react t o higher molecular weight m a t e r i a l ; thermal

d e h y r o v l a t i o n t o phenol i s not appreciable. F i n a l l y , pyrolyses o f

4-propylguaiacol a t 345'C corroborate (Vuori and Bredenberg. 1984).

Reactions both i n benzene and a hydrogen atmosphere r e s u l t e d i n a

4-propylguaiacol conversion of 0.59. of which only 0.18 was t o

i d e n t i f i e d l i g h t products. Thus, t h e thermal r e a c t i v i t y of s u b s t i -

t u t e d guaiacols was s i m i l a r t o t h a t o f guaiacol i t s e l f , i n d i c a t i n g

t h a t t h e reactions of t h e guaiacyl moiety are l a r g e l y unaffected by

t h e presence of other r i n g substituents.

I n comparison t o these pyrolyses, t h e present c a t a l y t i c reac-

t i o n s o f s u b s t i t u t e d guaiacols and catechols a t 250 t o 340°C were

t o higher y i e l d s o f thermally s t a b l e phenols. For example, t h e

maximum t o t a l s i n g l e - r i n g phenols' y i e l d obtained from methyl-

guaiacol a t 325'C was 0.54 and t h e maximum obtained from r e a c t i o n

of methylcatechol a t 340°C was 0.64. At these conditions, cresol

was by f a r t h e predominant s i n g l e - r i n g phenol i n both instances.

w i t h y i e l d s of 0.34 and 0.60, respectively. Corresponding y i e l d s

 52 PETROCELLI A N D K L E I N

of t o t a l s i n g l e - r i n g hydrocarbons were 0.098 and 0.16. respec-

tively.

The p r e s e n t work accords w i t h prevtous hydrodeoxygenation

experiments w i t h t h e r e l a t e d compounds guaiacol and 4-propyl-

guaiacol. H u r f f and K l e i n (1983) r e p o r t e d u l t i m a t e molar y i e l d s of

0.35 phenol, 0.10 cyclohexane and 0.03 benzene from t h e hydrode-

Downloaded by [University of Utah] at 17:07 18 April 2013

oxygenation o f guaiacol a t 250°C o v e r a CoMoIy-A1203 c a t a l y s t . The

r e a c t i o n o f guaiacol o v e r s u l f i d e d Ni -Mo/Si02-A1203 catalyst i n a

f l o w r e a c t o r a t 30OoC by Bredenberg e t a l . (1982) l e d t o a guaiacol

c o n v e r s i o n o f 0.48 and molar y i e l d s o f 0.221 phenol. 0.129 c a t e c h o l

and 0.118 c r e s o l s . I n t e r e s t i n g l y , hydrocarbon y i e l d s were q u i t e

low. Reaction o f 4-n-propylguaiacol over s u l f i d e d CoMoIy-Alp03

( V u o r i and Bredenberg, 1984) a t 295-C l e d t o a 4-n-propylguaiacol

c o n v e r s i o n o f 0.824 and molar y i e l d s of 0.126 4-n-propylcatechol,

0.232 3- and 4-propylphenols and approximately 0.30 t o t a l phenols.

I n s h o r t , t h e present and p r e v i o u s r e a c t i o n s of l i g n i n - r e l a t e d

methoxyphenols suggest t h a t hydroprocessing l i g n i n would u s e f u l l y

a l t e r r e a c t i o n pathways o f g u a i a c o l s and c a t e c h o l s toward h i g h e r

p r o d u c t i o n of phenols and hydrocarbons than t h a t o b t a i n e d from

pyrolysis.

Several a d d i t i o n a l o b s e r v a t i o n s m e r i t note. The n a t u r e o f t h e

p a r a P o s i t i o n S u b s t i t u e n t on s u b s t i t u t e d g u a i a c o l s and c a t e c h o l s

affected t h e r e a c t i v i t y o f t h e guaiacyl substituent imperceptibly.

Also, t h e a l k y l s u b s t i t u e n t s o f b o t h ' t h e ' r e a i t a n t s and t h e products

were l a r g e l y u n r e a c t i v e , as was found by Odebunmi and O l l i s (1983)

 MODELING LIGNIN LIQUEFACTION. I

f o r r e a c t i o n of c r e s o l s and Vuori and Bredenberg (1984) f o r reac-

t i o n o f 4-n-propylguaiacol and 4-n-propylcatechol. The non-alkyl

hydroxypropenyl and carbonyl s u b s t i t u e n t s on eugenol and v a n i l l i n

were converted r a p i d l y i n t h e formation of 4-propylguaiacol and

methyl guaiacol, r e s p e c t i v e l y . The l a t t e r r e a c t i o n i s s i m i l a r t o

t h e f a c i l e conversion of ketones such as cyclohexanone and benzo-

phenone t o t h e i r hydrocarbon analogues observed by Durand e t a l .

Downloaded by [University of Utah] at 17:07 18 April 2013

(1984) o v e r a NiOMo03/r-A1203 c a t a l y s t a t 250°C. Therefore, t h e

r e l e v a n t r e a c t i v i t y o f methylguaiacol, methylcatechol, eugenol and

v a n i l l i n was t h a t o f t h e i r guaiacyl (0-methoxy- and o-hydroxy-

phenol) m o i e t i e s . It i s a l s o i n t e r e s t i n g t h a t t h e y i e l d s o f m- and

p - c r e s o l were n e a r l y equal a t a l l t i m e s d u r i n g t h e r e a c t i o n o f

methylguaiacol, methylcatechol and v a n i l l i n . This indicates t h a t

deoxygenation o f e i t h e r t h e 1- o r 2 - p o s i t i o n o f t h e aromatic r i n g

was e q u a l l y f a c i l e and t h a t e l e c t r o n i c a c t i v a t i o n o f t h e 1 - p o s i t i o n

was not i m p o r t a n t .

P a r t i a l l y and f u l l y hydrogenated aromatic hydrocarbons were

present i n t h e hydrodeoxygenation product s p e c t r a o f a l l four

methoxyphenol models and accounted f o r more than 20% of t h e i n i t i a l

s u b s t r a t e mass i n several instances. However, no p a r t i a l l y o r

f u l l y hydrogenated phenolics were ever detected. These observa-

t i o n s a r e c o n s i s t e n t w i t h those from p r e v i o u s hydrodeoxygenation

s t u d i e s ( H u r f f and K l e i n . 1983; Webunmi and O l l i s . 1983). and

support t h e consensus (Krisnamurthy e t a l . , 1981) t h a t hydrogenated

p h e n o l i c s a r e u n s t a b l e i n t e r m e d i a t e s a t t y p i c a l hydrodeoxygen-

a t i o n experimental c o n d i t i o n s . Note, however, t h a t t h e primary

 54 PETROCELLI AND KLEIN

f o r m a t i o n of c r e s o l from methylcatechol demonstrates t h a t hydro-

deoxygenation does n o t r e q u i r e p r i o r aromatic r i n g hydrogenation.

The m i g r a t i o n of a l k y l s u b s t i t u e n t s was minor b u t observed

d u r i n g t h e r e a c t i o n of each methoxyphenol. This migration often

l e d t o products o f s l i g h t l y h i g h e r m o l e c u l a r weight t h a n t h a t o f

t h e substrate. I s o m e r i z a t i o n o f methylguaiacol d u r i n g t h e reac-

t i o n s o f methylguaiacol and v a n i l l i n , and o f 4-n-propylguaiacol

Downloaded by [University of Utah] at 17:07 18 April 2013

d u r i n g t h e r e a c t i o n of eugenol, was a l s o observed. Vuori and

Bredenberg (1984) s i m i l a r l y i d e n t i f i e d b p r o p y l g u a i a c o l as a

p r o d u c t of t h e r e a c t i o n o f 4-propylguaiacol. It i s i n t e r e s t i n g

t h a t b o t h o f these guaiacol isomers were products o f t h e r e a c t i o n

o f 4-propylcatechol .
The decreases i n OPI observed d u r i n g t h e r e a c t i o n of each of

methylguaiacol, methylcatechol, eugenol and v a n i l l i n a r e c o n s i s t e n t

w i t h t h e p a r t i c i p a t i o n of b o t h g u a i a c y l and o - d i h y d r o x y l m o i e t i e s

i n r e a c t i o n t o h i g h e r m o l e c u l a r weight compounds, even i n t h e

presence of a c a t a l y s t . However. t h e s e l e c t i v i t y t o l i g h t products

r e l a t i v e t o char formation i n c r e a s e d w i t h increases i n tempera-

tures. For example, t h e apparent a c t i v a t i o n energies f o r r e a c t i o n

o f methylcatechol t o c r e s o l and t o char were 29.3 k c a l l m o l and

10.6 k c a l l m o l , r e s p e c t i v e l y .

I n t e r u n i t Linkages

The r e s u l t s of t h e experiments i n v o l v i n g t h e i n t e r u n i t l i n k s

were nuch more h i g h l y substrate-dependent t h a n t h e experiments w i t h

methoxyphenols. The r e a c t i o n o f 0.0'-biphenol was predominantly t o

 UODELINC LIGNIN LIQUEFACTION. 1 55

two-aromatic r i n g compounds, and o n l y l i m i t e d h y d r o c r a c k i n g of t h e

b i p h e n y l l i n k occurred. However, b o t h o-hydroxydiphenylmethane and

phenyl e t h e r cracked r e a d i l y t o s i n g l e - r i n g products. Thus, c a t a -

l y t i c r e a c t i o n of t h e i n t e r u n i t l i n k s i s c l e a r l y d i f f e r e n t from

t h e n n o l y s i s , as phenyl e t h e r and biphenol a r e t h e r m a l l y s t a b l e t o

temperatures g r e a t e r t h a n 500°C. and p y r o l y s i s o f o-hydroxy-

d i pheny lmethane i s a p p r e c i a b l e o n l y above 400°C ( K l e i n , 1981).

Downloaded by [University of Utah] at 17:07 18 April 2013

C a t a l y t i c removal of hydroxyl m o i e t i e s occurred both before .

and a f t e r cleavage o f t h e biphenol and o-hydroxydiphenylmethane

i n t e r u n i t links. On t h e one hand, t h e major r e a c t i o n s of o,ol-

biphenol were t o e i t h e r dibenzofuran o r 2-phenylphenol , with re-

j e c t i o n o f one oxygen s u b s t i t u e n t i n both cases. Direct cracking

o f t h e b i p h e n y l bond t o produce s i n g l e - r i n g products was minor, and

t h e phenol y i e l d never exceeded 0.07 d u r i n g t h e 0.0'-biphenol

experiments. On t h e o t h e r hand. d i r e c t fragmentation t o phenol and

t o l u e n e was t h e dominant o-hydroxydiphenylmethane r e a c t i o n pathway.

A t 330°C, t h e y i e l d s o f t o l u e n e and phenol ( o r i t s r e a c t i o n prod-

u c t s ) were each as h i g h as 0.60. However, t h e presence o f d i -

phenylmethane, cyclohexylbenzene and d i c y c l o h e x y l a l l i n d i c a t e t h a t

oxygen removal occurred p r i o r t o i n t e r u n i t bond cleavage also.

As i n t h e methoxyphenol experiments, hydrogenated hydro-

carbons w i t h a s a t u r a t e d r i n g formed d u r i n g t h e r e a c t i o n s o f

0.0'-biphenol, o-hydroxydiphenylmethane and phenyl e t h e r b u t

p h e n o l i c s w i t h a s a t u r a t e d r i n g ' d i d not. I n contrast t o the

methoxyphenol experiments. OPI was c o n s i s t e n t l y near 100% d u r i n g

 56 PETROCELLI AND KLEIN

t h e i n t e r u n i t l i n k experiments. which f u r t h e r i m p l i c a t e s g u a i a c y l

and o - d i h y d r o x y l m o i e t i e s as coke p r e c u r s o r s .

Comparison w i t h p r e v i o u s work i s a v a i l a b l e i n a few i n s t a n c e s .

Krishnamurthy e t a l . (1981) r e a c t e d dibenzofuran and 2-phenylphenol

o v e r a NiMo/y-Alp03 c a t a l y s t a t temperatures o f 325-375OC. Oxygen

removal occurred v i a d i r e c t e x t r u s i o n , w i t h o u t r i n g hydrogenation,

Downloaded by [University of Utah] at 17:07 18 April 2013

as w e l l as through t h e f o r m a t i o n o f hydrogenated i n t e r m e d i a t e s ; t h e

l a t t e r pathway was predominant. Formation o f s i n g l e - r i n g products

appeared t o occur o n l y through an o-cyclohexylphenol i n t e r m e d i a t e .

F r e d e r i c k and B e l l (1984) r e a c t e d 4-hydroxydiphenylmethane i n the

presence o f z i n c h a l i d e c a t a l y s t s a t 325'C. Major products i n -

c l u d e d phenol, t o l u e n e and diphenylmethane, w i t h molar y i e l d s o f

phenol approaching 0.4 a t a h o l d i n g t i m e o f about 4 hr. Oiphenyl-

methane was a t t r i b u t e d t o t h e r e a c t i o n o f t h e benzene s o l v e n t w i t h

t h e substrate. I n c o n t r a s t w i t h t h e p r e s e n t work, t h i s c a t a l y s t

system l e d t o about 40% s e l e c t i v i t y t o u n i d e n t i f i e d products and

t h e f o r m a t i o n o f a high-molecular-weight r e s i d u e . I n formal

p a r a l l e l w i t h t h e p r e s e n t methoxyphenol and o-hydroxydiphenyl-

methane r e s u l t s , i s o m e r i z a t i o n o f 4-hydroxydiphenylmthane t o

o-hydroxydiphenylmethane was s i g n i f i c a n t , w i t h y i e l d s of

o-hydroxydiphenylmethane r e a c h i n g 0.15. F i n a l l y , Cassidy e t a l .

(1982) r e p o r t e d phenyl e t h e r t o be s t a b l e i n t h e presence of

i r o n - o r t i n - b a s e d c a t a l y s t s a t temperatures r a n g i n g from 340 t o

460°C f o r a h o l d i n g t i m e o f 1 hr.
 MODELING LIGNIN LIQUEFACTION. 1

IMPLICATIONS TO LIGNIN LIQUEFACTION

As an o p t i m i s t i c l i m i t i n g case, t h e present model compound

r e a c t i o n pathways and s e l e c t i v i t i e s can be t r a n s f e r r e d t o t h e

a n a l y s i s of t h e h y p o t h e t i c a l l i q u e f a c t i o n o f l i g n i n by r e a c t i o n i n

t h e presence of t h e CoMoIv-Alp03 c a t a l y s t . This f i r s t - o r d e r

analysis c l e a r l y neglects deactivation, i n h i b i t i o n , c a t a l y s t

Downloaded by [University of Utah] at 17:07 18 April 2013

e f f e c t i v e n e s s and o t h e r phenomena t h a t a more r e a l i s t i c a n a l y s i s

need address.

From p y r o l y s i s alone, t h e " t a r " product f r a c t i o n c o n s i s t s o f

b o t h monomeric and polymeric phenolics. The t o t a l t a r f r a c t i o n can

account f o r up t o about 3a by weight of t h e l i g n i n , and a t

temperatures o f about 400°C, single-ring phenolic y i e l d s o f

approximately 10 wt% and p h e n o l i c dimer and t r i m e r y i e l d s of

approximately 10 wt% a r e t y p i c a l (Connors e t al., 1980; l a t r i d i s

and Gavalas, 1979; Jegers. 1982). However, t o t a l s i n g l e - r i n g

monohydroxyl phenol y i e l d s are l e s s than 2 w t X . The formation of

s i n g l e - r i n g hydrocarbons i s i n s i g n i f i c a n t .

The s i n g l e - r i n g product f r a c t i o n c o n s i s t s p r i m a r i l y o f sub-

s t i t u t e d g u a i a c o l s w i t h l e s s e r amounts o f s u b s t i t u t e d c a t e c h o l s and

phenols a l s o present. At l o n g e r batch h o l d i n g times, however, t h e

t o t a l y i e l d s o f s i n g l e - r i n g products decrease as s i n g l e - r i n g

g u a i a c o l s and c a t e c h o l s r e a c t mostly t o coke (Connors e t al., 1980;

Jegers and K l e i n , 1985). It i s l i k e l y t h a t o l i g o m e r i c p h e n o l i c s

w i t h g u a i a c y l and 0-dihydroxyl m o i e t i e s a l s o p a r t i c i p a t e i n c o k i n g
 58 PETROCELLI AND KLEIN

r e a c t i o n s since nearly h a l f of l i g n i n ' s i n t e r u n l t linkages are

t h e r m a l l y stable.

The present r e s u l t s suggest t h a t c a t a l y t i c hydroprocessing

should reduce t h e formation of char from t h e r m a l l y l i b e r a t e d

s i n g l e - r i n g phenolics; i t i s reasonable t o expect t h e same t o be

t r u e f o r m u l t i r i n g phenolics. This alone could increase t h e y i e l d s

of s l n g l e - r i n g products obtained from l i g n i n l i q u e f a c t i o n by

Downloaded by [University of Utah] at 17:07 18 April 2013

several times over those a t t a i n a b l e from p y r o l y s i s . The r e s u l t a n t

l a r g e s i n g l e - r i n g product f r a c t i o n would also be concentrated i n

phenols and hydrocarbons due t o t h e c a t a l y t i c oxygen removal.

Further, since t h e phenolic dimers and t r i m e r s . which consist o f

aromatic r i n g s j o i n e d p r i m a r i l y by t h e r m a l l y s t a b l e but c a t a l y t i -

c a l l y r e a c t i v e i n t e r u n i t l i n k s , are produced during l i g n i n

p y r o l y s i s i n mass y i e l d s t y p i c a l l y equal t o those of s i n g l e - r i n g

phenolics, c a t a l y t i c cleavage of biphenyl, diphenylmethane and

phenyl e t h e r bonds could f u r t h e r enhance t h e t o t a l y i e l d of

s i n g l e - r i n g products obtained from l i g n i n depolymerization.

S p e c i f i c a l l y , q u a n t i t a t i v e a p p l i c a t i o n of t h e model compound

hydrodeoxygenation r e s u l t s t o l i g n i n suggests t h a t t h e t o t a l y i e l d

of s i n g l e - r i n g p r o d u c t s o b t a i n e d from l i g n i n l i q u e f a c t i o n could
p o t e n t i a l l y be two t o t h r e e times greater than t h a t possible from

p y r o l y s i s alone. And t h e predominant s i n g l e - r i n g products would be

a l k y l - s u b s t i t u t e d d e r i v a t i v e s o f phenol, benzene and cyclohexane,

r e s u l t i n g from hydrodeoxygenation and hydrogenation of s u b s t i t u t e d

guaiacols and catechols.

 MODELING LIGNIN LIQUEFACTION. 1 59

As w i l l be r e p o r t e d separately, these model compound r e s u l t s

can be used w i t h a p r o b a b i l i s t i c i n t e r p r e t a t i o n o f l i g n i n s t r u c t u r e

and r e a c t i o n s i n an a p r i o r i , q u a n t i t a t i v e p r e d i c t i o n o f t h e y i e l d s

of i n d i v i d u a l products evolved d u r i n g l i g n i n l i q u e f a c t i o n i n t h e

presence of a c a t a l y s t . The model compound r e s u l t s , then, a r e

vdewed as t h e i n t r i n s i c chemistry u n d e r l y i n g t h e r e a c t i o n o f a

complex macromolecule j u c h as l i g n i n .
Downloaded by [University of Utah] at 17:07 18 April 2013

CONCLUSIONS

The u l t i m a t e products o f t h e hydrodeoxygenation of methyl-

guaiacol,.methylcatechol, eugenol and v a n i l l i n a t temperatures of

250-325Y a r e a l k y l phenols and s i n g l e - r i n g hydrocarbons. Combined

m o l a r y i e l d s o f t h e two a r e as h i g h as 0.70. These increased

y i e l d s , r e l a t i v e t o p y r o l y s i s , a r e a t t h e expense of c h a r

formation.

The h y d r o c r a c k i n g of t h e r m a l l y s t a b l e o-hydroxydiphenylmethane

and phenyl ether, models o f key l i g n i n i n t e r u n i t linkages, i s

f a c i l e a t temperatures of 280-330°C. The c a t a l y t i c cleavage of t h e

b i p h e n y l l i n k a g e d u r i n g r e a c t i o n o f 0.0'-biphenol i s limited, with

t h e major primary r e a c t i o n products b e i n g dibenzofuran and

2-phenylphenol.

These model compound r e s u l t s i n d i c a t e t h a t t h e c a t a l y t i c

l i q u e f a c t i o n of l i g n i n should r e s u l t i n a g r e a t e r y i e l d of a l e s s

c o q l e x s i n g l e - r i n g product f r a c t i o n t h a n obtained through

p y r o l y s i s f o r two reasons. F i r s t . hydrodeoxygenatlon of guaiacyl

 60 PETROCELLI AND KLEIN

and o-dihydroxyl m o i e t i e s should reduce coke f o r m a t i o n and t h e

number o f d i f f e r e n t p h e n o l i c products and, second, t h e hydro-

c r a c k i n g o f t h e r m a l l y s t a b l e i n t e r u n i t l i n k a g e s should be t o

s i n g l e - r i n g products.

ACKNOWLEDGMENTS

We a r e g r a t e f u l f o r t h e support o f t h i s work by t h e N a t i o n a l
Downloaded by [University of Utah] at 17:07 18 April 2013

Science Foundation (RCPE-840 4452). and Exxon Education Foundation

( F e l l o w s h i p t o FPP).

REFERENCES

Benjamin, 0. M., V. F. Raaen, P. H. Maupin, L. L. Brown, and C. J.

Collins. 1978. Thermal cleavage of chemical bonds i n s e l e c t e d
c o a l - r e l a t e d s t r u c t u r e s . Fuel, 57:269-72.

Rredenberg, J. B-son, and R. Ceylan. 1983. Hydrogenolysis and

h y d r o c r a c k i n g o f t h e carbon-oxygen bond. 3. Thermolysis i n
t e t r a l i n of s u b s t i t u t e d anisoles. Fuel, 62:343-44.

Bredenberg, J. B-son, M. Huuska, J. Raty, and M. Korpio. 1982.

Hydrogenolysis and h y d r o c r a c k i n g of t h e carbon-oxygen bond. J.
Catal., 77:242-47.

Cassidy, P. J.; P. A. Hertan, W. R. Jackson, F. P. Larkins, and D.

Rash. 1982. Hvdroqenation o f brown coal. 3. Roles of hvdroqen
and hydrogen-donor i o l v e n t s i n systems c a t a l y s e d by i r o n i n d i i n
colrpounds. Fuel, 61:939-46.

Ceylan, R., and J . B-son Bredenberg. 1982. Hydrogenolysis and

h y d r o c r a c k i n g o f t h e carbon-oxygen bond. 2. Thermal cleavage
of t h e carbon-oxygen bond i n guaiacol .
Fuel, 61:377-82.

Connors, W. J., L. N. Johanson, K. V. Sarkanen, and P. Winslow.

1980. Thermal d e g r a d a t i o n o f k r a f t l i g n i n i n t e t r a l i n .
Holzforschung, 34:29-37.

Ourand, R., P. Geneste, C. Moreau, and J. L. P i r a t . 1984.

Heterogeneous hydrodeoxygenation o f ketones and a l c o h o l s on
s u l f i d e d NiO-M003/~-A1203 c a t a l y s t . J, Catal., 90:147-49.
 MODELING LIGNIN LIQUEFACTION. 1 61

F r e d e r i c k , T. J., and A. T. B e l l , 1984. Cleavage of diarylmethanes

i n t h e presence of z i n c h a l i d e s . J. Catal., 87:196-209.

Furimsky, E. 1979. C a t a l y t i c removal of s u l f u r , n i t r o g e n , and

oxygen from heavy gas o i l . AIChE J., 25(2):306-11.

Gates, 8. C.; J. R. Katzer, and G. C. A. Schuit. 1979. Chemistry

o f C a t a l y t i c Processes. McGraw-Hill, New York.

Hurff, S . J., and M. T. K l e i n . 1983. Reaction pathways a n a l y s i s

o f thermal and c a t a l y t i c l i g n i n fragmentation by use of model
compounds. Ind, Eng. Chem. Fundam., 22:426: 30.

I a t r i d i s , 8.. and G. R. Gavalas. 1979. F y r o l y s i s o f a p r e c i p i -

Downloaded by [University of Utah] at 17:07 18 April 2013

tated kraft lignin. Ind. Eng. Chem. Prod. Res. Dev., 18:127-30.

Jegers, H. E. 1982. "Thermolysis of l i g n i n . M.Ch.E. thesis,

U n i v e r s i t y o f Delaware.

Jegers. H. E., and M. T. K l e i n . 1985. Primary and secondary

l i g n i n p y r o l y s i s r e a c t i o n pathways. Ind. Eng. Chem. Proc. Des.
Dev., 24:173-83.

Kamiya, Y., T. Yao, and 5. Oikawa. 1979. Thermal treatment of

c o a l - r e l a t e d aromatic e t h e r s i n t e t r a l i n s o l u t i o n s . Prepr., Div.
Fuel Chem., Am. Chem. Soc., 24:116-24.

K l e i n , M. T. 1981. Model pathways i n l i g n i n t h e r m o l y s i s . Sc.D.

t h e s i s . Massachusetts I n s t i t u t e of Technology.

K l e i n , M. T., and V i r k , P. S. 1981. Model pathways i n l i g n i n

thermolysis. MIT Press Energy Lab Ser. 5.

- . 5 . .. S. Panvelker. and Y. T. Shah. 1981.

Krishnamurthv.
Hydrodeoxygenation o f dibenzofukan and r e l a t e d compounds. AlChE
J., 27(6):994-1001.

Lawson, J. R., and M. T. K l e i n . 1985. I n f l u e n c e of water on

guaiacol pyrolysis. Ind. Eng. Chem. Fundam., 24(2):203-08.

Lee, C.-L.. and D. F. O l l i s . 1984. C a t a l y t i c hydrodeoxygenation of

benzofuran and o-ethylphenol . J. Catal., 87:325-31.

Odebunmi, E. 0.. and D. F. O l l i s . 1983. C a t a l y t i c hydrodeoxygen-

a t i o n . J. Catal., 80:56-64.

P e t r o c e l l i , F. P.. and M. T. K l e i n . 1984. Model r e a c t i o n pathways

i n k r a f t l i g n i n p y r o l y s i s . Macromolecules, 17:161-69.

Rollman, L. D. 1977. C a t a l y t i c hydrodeoxygenation of model

n i t r o g e n , s u l f u r , and oxygen corpounds. J. Catal., 46:243-52.
 62 PETROCELLI AND KLEIN

S a t t e r f i e l d , C. N.. and S. H. Yang. 1983. Simultaneous

hydrodenitrogenation and hydrodeoxygenation of model compounds i n a
t r i c k l e bed reactor. J. Catal., 81:335:46.

Schlosberg, R. H., W. H. Davis, and T. R. Ashe. 1981. P y r o l y s i s

s t u d i e s o f o r g a n i c oxygenates. 2. Benzyl phenyl e t h e r p y r o l y s i s
under batch autoclave c o n d i t i o n s . Fuel, 60:201-09.

Schlosberg, R. H., P. F. Szajowski, G. D. Dupre, J . A. Danik, A.

Kurs, T. R. Ashe, and U. N. Olmstead. 1983. P y r o l y s i s s t u d i e s of
o r g a n i c oxygenates. 3. High temperature rearrangement o f a r y l
a l k y l ethers. Fuel. 62:690-94.

Vogelzang, M. W., C.-L. L i , G. C. A. Schuit, B. C. Gates, and L.

Downloaded by [University of Utah] at 17:07 18 April 2013

P e t r a k i s . 1983. Hydrodeoxygenation of l-naphthol: A c t i v i t i e s and

s t a b i l i t i e s o f molybdena and r e l a t e d c a t a l y s t s . J. Catal.,
84: 170-77.

Vuori, A., and J. 8-son Bredenberg. 1984. Hydrogenolysis and

hydrocracking o f t h e carbon-oxygen bond. HOlzforSChung, 3:133-47.

Weigold, H. 1982. Behaviour of Co-Mo-A1 03 c a t a l y s t s i n t h e

hydrogenation o f phenols. Fuel, 61:1021-$6.

Weisser, 0.. and S. Landa. S u l f i d e c a t a l y s t s , t h e i r p r o p e r t i e s and

a p p l i c a t i o n s . 1973. Pergamon, New York.

RECEIVED: May 1 9 , 1 9 8 6 ACCEPTED: J u l y 1 6 , 1986