Fuel Processing Technology, 19 (1988) 31-50 31

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

Ki net i c St udi es of Upgr adi ng Pi ne Pyrol yt i c Oil by
Hydrot reat ment
YU-HWA E. SHEU, RAYFORD G. ANTHONY
Kinetic, Catalysis and Reaction Engineering Laboratory, Department of Chemical Engineering,
and
ED J. SOLTES
Wood Chemistry Laboratory, Department of Forest Science, Texas A&M University, College
Station, Texas 77843 (U.S.A.)
ABSTRACT
Pyrolytic oil, produced by the Tech-Air Corporation from Southern Pine sawdust and bark, was
hydrotreated in a trickle bed reactor system. Changes in product composition as a function of
reaction temperature, hydrogen pressure, space velocity and catalyst type were determined quan-
titatively by size exclusion chromatography - gas chromatography (SEC-GC) analyses and ele-
mental analyses. The catalysts used in the reactions were Pt/Al203/Si02, and sulfided CoMo/;,-
A1203, Ni-W/7-A1203 and Ni-Mo/7-A1203. The reaction temperatures ranged from 623 K to 673
K, and the reaction pressures varied from 5,272 kPa (750 psig ) to 10,433 kPa ( 1,500 psig ). Weight-
hourly space velocity was changed from 0.5 to 3.0 h- ~.
Two models, one for overall oxygen removal and the other for the compositional changes in
hydrotreated oil, were developed. Oxygen removal was not a function of space velocity and was
modeled by an empirical function of temperature and pressure. A pseudo first order reaction net-
work was used to relate the kinetics of a five "lump" model.
INTRODUCTION
Biomass, whi ch includes forest and agricultural product s and residues, ani-
mal wastes, and muni ci pal solid waste, is a renewable resource t hat could play
a significant role in providing for future energy needs. A number of biomass
t her mal conversion processes are current l y being developed, including com-
bustion, gasification, and pyrolysis. Pyrolysis refers to incomplete t her mal
degradat i on whi ch yields t hr ee maj or products: char (mostly carbon), oil (us-
able as a liquid fuel), and fuel gas (usable in any combust or). Conditions for
biomass pyrolysis and product s are somewhat di ct at ed by react or type and
design. An excellent and det ai l ed summar y of biomass pyrolysis is given by
Chat t erj ee [ 1 ].
Al t hough report ed at t empt s at pyrolytic oil utilization are usually rel at ed to
0378-3820/88/$03.50 1988 Elsevier Science Publishers B.V.
32
di rect combust i on, pyrol yt i c oil is a poor boi l er fuel. It is viscous, not com-
pl et el y volatile, corrosive, exhi bi t s hi gh oxygen cont ent , and does not mi x wi t h
convent i onal fuels.
In order to i mprove pyrol yt i c oil as a liquid fuel, t he oil mus t be processed to
reduce viscosity, i mprove volatility, remove acidity, and lower oxygen cont ent .
A catalytic hydr ot r eat i ng react i on was pr oposed t o i mprove t he qual i t y of t he
oil. Reduct i on of oxygen cont ent resul t s in more hydrocarbon-l i ke mol ecul es
wi t h t he hi gher energy cont ent preferred in fuels. Hydr ot r eat i ng can effectively
lower t he oxygen cont ent , resul t i ng in bet t er fuels while usual l y pr omot i ng
some cracki ng to enhance volatility.
Onl y l i mi t ed i nf or mat i on is available on hydr ot r eat ment of bi omass-deri ved
oils. All hydr ot r eat i ng work on bi omass pyrol yt i c oil to dat e has been done in
bat ch reactors. Li n [2] r epor t ed t hat use of pl at i num and ot her noble met al
catalysts for hydr ot r eat i ng pyrolysis oils yields a gasoline-diesel mixture. Soltes
and L in [3, 4] r epor t ed t hat pyrol yt i c oils (t ars) from a vari et y of agri cul t ural
residues and t hei r hydroprocessed pr oduct s were si mi l ar in composi t i on re-
gardless of bi omass feedst ock used.
Pyrol yt i c oil obt ai ned from pi ne bark and wast es by t he Tech-Ai r pyrol ysi s
process was used in t hi s research. Anal yses of t he Tech-Ai r pyrol yt i c oil, re-
por t ed by El der [5 ] and El der and Soltes, [6-9 ] i ndi cat e t hat sol vent ext ract -
able phenol i cs compri se appr oxi mat el y 13 wt.% of t he oil. Pyrol yt i c oil also
cont ai ns volatile organic acids, as well as a vari et y of neut r al component s [9].
The maj or vol t at i l e component s (det ect abl e by t he gas chr omat ogr aphi c
anal ysi s) in t he oil are t he phenol i cs, e.g. phenol , cresol, some alkyl phenol s,
guaiacol, and eugenol [ 10 ]. A hi gh per cent age of t he component s of pi ne pyr-
olytic oil have hi gh mol ecul ar weights. Less t ha n 15 wt.% of t he pi ne pyrol yt i c
oil can be det ect ed by gas chr omat ogr aphy. The oil is very hygroscopic and has
about 10 wt.% moi st ure. Fur t her mor e, t he oil is heat -sensi t i ve and subject to
re-pol ymeri zat i on, so it cannot be f r act i onat ed by di st i l l at i on.
An anal yt i cal met hod combi ni ng size excl usi on chr omat ogr aphy (gel per-
meat i on chr omat ogr aphy) ( SEC) and hi gh resol ut i on gas chr omat ogr aphy
(GC) was devel oped by Sheu et al. [10] t o analyze pyrol yt i c oil and its hydro-
t r eat ed product . The separ at i on met hod utilizes t he concept t hat SEC sepa-
rates pyrol yt i c oil i nt o fract i ons whi ch are composed pri mari l y of t he following
t ypes of chemi cal compounds; nonvol at i l es, al kanes, phenol s, and aromat i cs.
Gas chr omat ogr aphy (GC) wi t h t he use of an i nt er nal st andar d (1-decene)
gives percent ages of volatiles. Changes in composi t i on dur i ng t he hydrot reat -
ing process were det er mi ned by compar i ng t he SEC-GC anal yses and t he ele-
ment al analyses of t he charge st ocks and product s.
The objectives of t hi s research were to convert t hi s heavy, hi gh-oxygen-con-
t ent oil i nt o a l i ght er hydr ocar bon mi xt ur e to obt ai n a bet t er liquid fuel; dem-
onst r at e per f or mance and operabi l i t y of a t ri ckl e bed reactor; and obt ai n a
33
ki net i c and r eact or model . The Pt cat al ys t s used by Li n [ 2 ], as well as, sul f i ded
Co- Mo, Ni - Mo and Ni W were t o be used.
EXPERIMENTAL
Feedstock
Pyr ol yt i c oil pr oduced by t he Tech- Ai r Cor por at i on f r om pi ne s awdus t and
bar k was us ed i n t hi s research. The physi cal pr oper t i es of Tech- Ai r pyr ol yt i c
oil are l i st ed i n Tabl e 1. The pur i f i ed grade decahydr onapht hal ene ( decal i n)
f r om Fi sher Sci ent i fi c was us ed i n t hi s s t udy as a sol vent .
Catalyst
Det ai l s regardi ng t he char act er i st i cs of t he cat al ys t s used i n t hi s r esear ch
are given i n Tabl e 2. The 5% Pt / Al e 03 powder cat al ys t was mi xed wi t h Ludox
AS-40 bi nder (70% SiOe, 30% H2 0 mi xt ur e sol d by du Po n t ) in such a pr o-
por t i on t ha t t he fi nal cat al ys t cont ai ned 30% SiO2. A pas t e was made when t he
bi nder was added. I t was t he n t a ke n i nt o a syri nge wi t h a 1/ 16 i nch (0. 1588
cm) pl unger. The cat al ys t was ext r uded, dri ed, and cal ci ned in air at 756 K
TABLE1
Properties of pine pyrolytic oil
Property Result Method
Density 1.1415 g/cm 3
Water content 9.7%
Heating value
(wet basis) 27,800 kJ/kg
Solubility
(wt.%)
Water 39.7%
Acetone 99.6%
Methylene Chloride 93.5 %
Toluene slight
Hexane slight
pH 2.9
Filterable Solids
(wt.%)
Acidity (milli-
equivalents
acid per gram
ofoil)
0.3%
0.64
ASTM D-85-70
ASTM D-240-64
5% oil dispersed
in water
Acetone
insoluble
Titration by NaOH
34
TABLE2
Specifications of the hydrotreating catalysts
Catalyst Manufacturer Size Composition Surface Pore Pore size
area volume diameter
(m2/g) (cm3/g) {.~)
Pt/A1203 Strem{78-166) powder
Co-Mo Harshaw (HT-400) 1/16"E. b
Ni-Mo Harshaw (HT-500) 1/12"E.
Ni-W Harshaw (Ni-4301) 1/12"E.
5% Pt 100" 0.52" 100"
3% CoO, 15% MoO3 200 0.45 94
3.5% NiO, 15.5% Mo03 200 0.46 88
6% Ni, 19% W 230 0.37 104
"For the pellet catalyst.
bE: Extrudates.
(483 C) for four hours. I n order to obt ai n an active cat al yst , t he Pt / Al 2 Of f
Si02 pel l et was reduced in situ pr i or t o t he experi ment s. The reduct i on was
done by passi ng t he H2 t hr ough t he cat al yt i c bed at 673 K, 8,720 kPa at a flow
rate of 200 cm3/ mi n (21.2C, 1 bar) for one hour.
For Har shaw' s catalysts, t he sul fi ded form was t est ed. Presul fi di ng of t he
cat al yst s was done in situ pri or t o t he experi ment s. A mi xt ure of 90% H2 and
10% H2S by vol ume was passed t hr ough t he cat al yst bed at a flow rat e of 40
cm3/ mi n ( measur ed at 21.2 K, 1 bar) at 673 K and at mospher i c pressure unt i l
t he out l et gas showed no f ur t her sign of H2S consumpt i on.
Apparatus
A schemat i c di agram of t he t ri ckl e-bed react or syst em is shown in Fig. 1.
The react or consi st s of a 316 st ai nl ess steel t ube, 3/ 4 i nch (1.905 cm) O.D.,
0.065 i nch (0.1651 cm) wall t hi ckness, and 32 i nches (81.3 cm) long. The t op
20 i nches (50.8 cm) was packed wi t h cat al yst and t he bot t om 12 i nches {30.48
cm) was packed wi t h Pyr ex 3 mm di amet er glass beads (Cat. No. 7268-3 ).
An aut omat i c t emper at ur e cont rol l er ( Techne AC-40) was used t o cont rol
t he t emper at ur e of t he salt bat h. The heat i ng medi um was a Hi t ec heat t r ans-
fer salt whi ch is a mi xt ur e of 53% pot assi um ni t rat e, 40% sodi um ni t ri t e and
7% sodi um ni t r at e {Ameri can Hydr ot her m Co. ). Air was bubbl ed t hr ough t he
salt bat h to ensure a mor e uni f or m t emper at ur e profile.
A t her mowel l [ 1/ 8 in. i.d. (0.3175 cm) ] was ext ended from t he bot t om to t he
t op of t he reactor. A 0.04 i nch (0.1015 cm) OD chromel -al umel t her mocoupl e
(Omega Model 4001KC1 ) was i nser t ed i nt o t he t her mowal l and moved up and
down to measure t he axial t emper at ur e profile of t he reactor. The react or t em-
per at ur e was noni sot her mal , because onl y t he bot t om 22 i nches (55.88 cm) of
t he react or was in cont act wi t h t he salt bat h. Fi gure 2 shows t wo t ypi cal t em-
per at ur e profiles i nsi de t he react or at t wo di fferent sal t - bat h t emper at ur e
settings.
By i mmer si ng 22 i nches of t he react or in t he sal t -bat h, t he t emper at ur e in-
side t he react or i ncreased gradual l y al ong t he react or l engt h. Thi s pr event ed
~ R .= = ~ _ -C
S - I I
- - c><3
I
Meteri ng Pump
Meteri ng Pump
Q
35
S-I
Fig. 1. Schematic diagram of the trickle-bed reactor system. BPR: back pressure regulator, C:
water cooled exchanger, F: filter, G: gas sample collector, L: liquid sample collector, MF: mass flow
meter, P: pressure gauge, R: regulator, TC: temperature controller, TI: temperature indicator, W:
wet test meter, S-I and S-II: separators.
t he vol at i l es i n t he pi ne pyr ol yt i c oil f r om f l ashi ng suddenl y i nt o t he gas phase.
Wi t h t he cat al ys t packed at t he t op sect i on of t he react or, t he pyr ol yt i c oil was
hydr ot r eat ed bef or e t he oxygen- cont ai ni ng compounds pol ymer i zed at hi gh
t emper at ur e. Tabl e 3 shows t ypi cal oper at i ng condi t i ons.
Af t er t he react i on, t he cat al ys t was r egener at ed wi t h air t o r emove t he coke
deposi t ed on t he cat al ys t dur i ng t he react i on. Then, t he cat al ys t bed was ac-
t i vat ed agai n for t he next run.
Analysis
Gas sample
The gas sampl e was anal yzed usi ng a Carl e Ser i es S, 111 H anal yt i cal gas
chr omat ogr aph, wi t h col umns and pr ogr ams as r epor t ed by Phi l i p et al. [ 11 ].
36
o
v
W
n-
I -
~ C
n"
W
O.
W
I -
400
3 80
3 40
3 00
260
220
180
Glass
C at al yst Bed = 1_ Bead ~ 1
0 4 8 12 16 20 24 28 3 2
R EAC TOR LENGTH (inc h)
Fig. 2. Temperature profile inside the reactor. Reaction conditions: Pt/A12OJSiO2 catalyst, 8,720
kPa, WHSV=2 h -1, salt bath temperatures: [] 623 K (350C) and o 673 K (400C).
TABLE 3
Typical reactor operating conditions
Gas feed (H2)
Liquid feed
Weight hourly
space velocity
(WHSV)"
Salt bath
temperature
H2 pressure
Catalyst bed
: 100 cc/min (at 60 F, i bar) per gram of pine pyrolytic oil input.
: at a ratio of 2 g decalin/gram of pine pyrolytic oil
: 0.5 to 3.0 h -1
: 623 to 673K
: 5,272 to 10,443 kPa (750 to 1500 psig)
: 60 g for each load
"WHSV = Gram of pine pyrolytic oil input per hour
Gram of catalyst in the reactor
A Hewlett-Packard 3385A Automation System integrator and printer was used
in conjunction with this GC.
Liquid sample
Size exclusion chromatography (gel permeation chromatography) (SEC)
combined with GC was used to analyze pine pyrolytic oil and its hydrotreated
product. The method separates the oil into fractions composed principally of
nonvolatiles, alkanes, phenols, and aromatics. Changes in composition during
the hydrotreating process were determined quantitatively by comparing the
SEC-GC analyses and the elemental analyses of the charge stocks and prod-
37
ucts. The det ai l s of t he SEC-GC anal yt i cal met hod have been descri bed by
Sheu et al. [ 10 ].
An el ement al anal ysi s was obt ai ned for t he t ot al feed and product s. Carbon
and hydr ogen bal ances were cl osed wi t hi n 2%, whereas, t he oxygen bal ances
failed t o close by 10 t o 20%. Thi s devi at i on was at t r i but ed t o t he i nabi l i t y t o
measur e t he oxygen cont ent of t he coke. The t ot al mat er i al bal ances on a mass
basis were cl osed wi t hi n 2%.
For addi t i onal i nf or mat i on on exper i ment al procedures, t he reader is referred
to Sheu [12].
RESULTS AND DISCUSSION
Oxygen removal
The amount s of oxygen in pi ne pyrol yt i c oil and t he hydr ot r eat ed pr oduct s
were det er mi ned by el ement al analysis. The effect of react i on t emper at ur e,
pressure, and space vel oci t y on oxygen removal are shown in Figs. 3 (d), 4 (d)
and 5( d) . The poi nt s in t he figures are t he exper i ment al dat a and t he solid
lines were gener at ed by usi ng an oxygen removal model. A clear t r end of t he
effect of react i on t emper at ur e and pr essur e on t he oxygen removal in t he hy-
dr ot r eat i ng process is shown in Figs. 3( d) and 4( d) . Fi gure 5( d) shows t hat
changes in space velocities di d not affect oxygen removal. No dat a for t he sul-
t i ded Ni W/ AI203 cat al yst are i ncl uded. For all r uns conduct ed wi t h t hi s cata-
lyst si gni fi cant coki ng occurred whi ch rapi dl y pl ugged t he reactor.
Even t hough t he oxygen removal was not a f unct i on of space velocity, eqn.
(1) is used because t he exper i ment al dat a were dependent on t emper at ur e and
pressure. An Ar r heni us t ype equat i on and an nt h order pressure effect are
assumed in eqn. (1).
dCxy /~ Cm p n
clZ =' " ~oxy (1)
The cor r espondi ng i nt egr at ed equat i on is:
L
( R- ~ o ( 1 - T ~ d z f o r m l (2) (C~Ym- 1 ) - C m- 1 - vo~y -Pn koexp \ T( z ) ] ]
0
and
- I n (1--Xoxy) =pnl for m=l .
Where,
38
4O
35
3O
25
I- -
"I"
~ 2 o
1 0
4 0
3 5
3O
25
I- .
"I" 20
w
10
- ( a ) 40:
3 5
3O
~ 2 5
- - ~ 10
- - f i
I I 1 I I I 1 I
Z
0
I i I I
i
6O ~
55 ~
4 5 ~
4 o
3 5
3 o
2 5
2 o
1 5
1 0 -
5 -
l i i
6 0 0 6 2 s 6 5 0 6 7 5
I
700
R EAC TION TEMPER ATUR E (K)
Fig. 3. The effect of temperature on product distributions, heavy nonvolatiles, [] light nonvol-
atiles, phenolics,/x aromatics + alkanes, O coke + water + gases for (a) sulfided Ni-Mo/A1203,
(b) sulfided Co-Mo/A1203, (c) Pt/Al2OJSiO2, and (d) on oxygen removal for A sulfided Ni-
Mo/Al203, [] sulfided Co-Mo/A1203, and Pt/A1203/Si02. Pressure=8,720 kPa, WHSV=2
h- 1. Solid lines are model predictions.
Coxy
= concent r at i on of oxygen in pyr ol yt i c oil =
gr am of oxygen in hydr ot r eat ed oil
gr am of oxygen in raw pyr ol yt i c oil
C x y = i ni t i al oxygen concent r at i on (equal t o one)
L = t ot al cat al yt i c bed l engt h ( cm)
m = r eact i on or der
n = pr essur e effect or der
P = r eact i on pr essur e ( kPa)
To = reference t emper at ur e ( K)
Xoxy = oxygen conver si on
z = axial l engt h
Ea = act i vat i on ener gy
k = rat e cons t ant
39
40 40
3 0 ~ 3 0
o
20 20
10 - ~ 10
Q
3 0 " ~ ~ , - ~ (c )
~ 5o
1" 2O ~
~- ~: ,o
i l J
z
i ~ 20
4 . 5
PR ESSUR E, MPa
_
(b)

I I I
[ J I
6. 0 7,5 9. 0 10. 5
PR ESSUR E, MPa
Fig. 4. The effect of pressure on product distributions, heavy nonvolatiles, [] light nonvolatiles,
phenolics, Zk aromatics+alkanes, O coke+water+gases for (a) sulfided Ni-Mo/Al203, (b)
sulfided Co-Mo/A1203, (c) Pt/Al~0JSi02, and (d) on oxygen removal for /x sulfided Ni-Mo/
A1203, [] sulfided Co-Mo/Al20~, and Pt/A12OJSi02. Temperature=673 K. WHSV=2 h -1.
Solid lines are model predictions.
The i nt egr al I = fL ko exp ( Ea/ R To ( 1 - To~ T ( z ) ) ) dz was eval uat ed by usi ng
t he six poi nt Gauss quadr at ur e numer i cal t echni que [ 13 ].
The nonl i near regressi on pr ogr am f r om t he "St at i st i cal Anal ysi s Sys t e m"
( SAS) package [14] was appl i ed t o det er mi ne t he par amet er s , m, n, ko, and
Ea whi ch ar e l i st ed i n Tabl e 4.
No dat a usi ng Pt / AI 2OJ Si O2 cat al yst for hydr odeoxygenat i on ( HDO) has
been r epor t ed i n t he l i t er at ur e. The Pt cat al yst exhi bi t s t he best act i vi t y for
oxygen r emoval for pi ne pyr ol yt i c oil among t he f our cat al yst s t est ed.
Al t hough t he exper i ment al dat a shows t ha t changes in space vel oci t y di d not
affect oxygen removal , t he "act i vat i on ener gi es" devel oped f r om t hi s oxygen
r emoval model for sul fi ded Co- Mo and Ni - Mo cat al yst s agree wi t h t hose re-
por t ed by ot her s [15, 16 ]. The "act i vat i on ener gy" for HDO usi ng sul fi ded Co-
Mo cat al yst agrees wi t h t he act i vat i on ener gy ( E, =8 4 . 4 k J / mo l ) r epor t ed by
40
~e
I- -
"1-
(. ~
IJJ
40
3 5
3 0
25
20
15
10
5
o
_ ~ o o
I 1 I l
40
3 5
3 0
~ e 25
I - -
~ 2o
10
5
I (b)
40
3 5
3 0
25
l. IJ . 20
15
10
( c )
I I I 1
SO
> 55
0
2~ 50
L D 4 5
40
Z
LU 3 5
(9
>-
o
~ o o
3 0
25
20 I
0 1
SPAC E V ELOC I TY (WHSV )
( d )
t
L I l
2 3 4
Fig. 5. The effect of space velocity on product distributions, heavy nonvolatiles, [] light non-
volatiles, phenolics, A aromatics+alkanes, coke+water+gases for (a) sulfided Ni-Mo/
A1203, (b) sulfided Co-Mo/A1203, (c) Pt/A12OJSi02, and (d) on oxygen removal for A sulfided
Ni-Mo/A1203, [] sulfided Co-Mo/Al203, and Pt/A12OJSi02. Pressure = 8,720 kPa. Tempera-
ture = 673 K. Solid lines are model predictions.
T A B L E 4
P a r a m e t e r s f o r o x y g e n r e m o v a l m o d e l ( e q n . 1 )
Catalyst m n ko E~
(cm- 1.kPa-") a (kJ/mol)
Pt/A12OJSi02 1.0 1.0 1. 50 _+ 0.02 10- 7 45.5 _+ 3.2
Sulfided
Co-Mo 1.0 0.3 1.07 _+ 0.07 X 10-3 71.4 _+ 14.6
Sulfided
Ni-W 1.0 0.5 7.00+0.2210 -5 61.7+7.1
"ko: e v a l u a t e d a t 6 4 8 K ( 3 7 5 C ) .
41
Ter nan and Br own [15]. No hydr ogen pressure effect on HDO of bi omass
liquids usi ng sul fi ded Co-Mo cat al yst s has been report ed.
The "act i vat i on energy" for HDO usi ng sul fi ded Ni - Mo cat al yst is 61 + 7.1
kJ / mol . Thi s value agrees wi t h t he act i vat i on energy for HDO of di benzofuran
usi ng sul fi ded Ni - Mo cat al yst [16].
Di benzof ur an , Bi phenyl , E, = 68.4 kJ / mol ;
Di benzof ur an , Cycl ohexyl benzene, Ea = 76.2 kJ / mol .
Effect of temperature on reaction products
The effect of t he react i on t emper at ur e on hydr ot r eat ed pyrol yt i c oil was
eval uat ed at 623, 648, and 673 K. All react i ons were r un at 8,720 kPa and
wei ght hourl y space velocity equal to 2 h- 1. One di fference in t he react i on
pr oduct s at di fferent react i on t emper at ur es was t hat t he liquid pr oduct s at 623
K di d not have a wat er layer separ at ed from t he hydr ot r eat ed oil. Thus, t he
liquid pr oduct at 623 K cont ai ned t he hydr ot r eat ed pyrol yt i c oil, sol vent s, and
water.
Fi gure 6 ( a ) - ( c ) shows t he gas chr omat ogr am for t he SEC phenol i c fract i on
of t he pi ne pyrolytic oil and for two di fferent react i on product s usi ng P t / A1 2 0 J
SiO2 at 623 and 673 K. Si gni fi cant changes in t he phenol i c fract i on is observed.
The chr omat ogr am of t he phenol i c fract i on at 623 K (Fig. 6 ( b) ) has less vol-
atile phenol s t ha n t hose in pi ne pyrol yt i c oil (Fig. 6 ( a) ) , whi ch i ndi cat es t hat
t he smal l mol ecul ar wei ght phenol s, guaiacol, met hyl guaiacol, etc., have been
conver t ed i nt o ar omat i cs dur i ng t he hydr ot r eat i ng react i on. The volatile phen-
ols in pyrol yt i c oil decreased from 12.3% (before react i on) t o 6.9%, and t he
ar omat i c and al kane fract i ons i ncreased from 1.5 to 9.87 and 0 t o 1.9%, re-
spectively. The phenol i c peaks i dent i fi ed in Fig. 6 (c) are di fferent from t hose
i dent i fi ed in Fig. 6 (a). Thi s suggests t hat phenol i cs are i nt er medi at e pr oduct s
whi ch are pr oduced and cons umed dur i ng t he hydr ot r eat i ng react i on. Com-
par i ng t he t wo react i on pr oduct s, t he volatile phenol s i ncreased from 6.9 @
623 K to 10.6 wt.% @ 673 K. The l umped ar omat i cs fract i on also i ncreased
from 9.8 to 16.2 wt.%. The following react i on scheme is suggested:
k3 k4
Li ght nonvol at i l es , Phenol i cs , Aromat i cs
k2
Par t of t he phenol s in pi ne pyrol yt i c oil are hydr ogenat ed t o pr oduce aro-
mat i cs; phenol s, are pr oduced also from t he nonvol at i l es dur i ng t he react i on;
and some ar omat i cs are pr oduced from t he l i ght nonvol at i l e fract i on. The al-
kanes are pr oduced by hydr ogenat i ng t he est ers in t he pi ne pyrol yt i c oil.
42

I (a)
5
I L i I ~ I
(b)
t I i r I
I
9 ( c )
6 7 1 1
t I r i i i
15 25 3 5 45 55 65
R ETENTION TIME (rain. )
Fig. 6. Typi cal gas chr omat ogr ams of t he phenol i c f r act i ons (Size Excl usi on Fr act i on # 3) . GC
conditions: SP-2100 col umn, car r i er gas He: 40 ml / mi n , t e mpe r a t ur e pr ogr am; 50 t o 280 C/ mi n,
i ni t i al hol d 3 mi n.
( a) Pi ne pyrol ysi s oi l - number s cor r espond t o [ 1 ] m, p-cresol, [2 ] guaiacol, [3 ] di met hyl phenol ,
[4] 4- met hyl guaiacol, [5] 4- et hyl guaiacol, [6] eugenol, [7] isoeugenol.
( b) Phenol i c f r act i on f r om hydr ot r eat ed pr oduct usi ng Pt / A12OJ Si 02 a t 623 K, 8,720 kPa, and
2 h - ' .
( c) Phenol i c f r act i on f r om hydr ot r eat ed pr oduct usi ng P t / Al 2 OJ S i 0 2 a t 673 K, 8,720 kPa, and 2
h - ' . Number ed peaks are: [1] 1-decene, [2] o-cresol, [3] m, p-cresol, [4] a nd [5] C2-phenol, [6]
and [7] C3-phenol, [8] 2- phenyl phenol , [9] C+-phenol, [10] napht hol , [11] Cs-phenol, [12] C6-
phenol. 1-decene is t he i nt er nal st andar d.
Kinetic and reactor model
Because many species are contained in pine pyrolytic oil and its hydro-
treated products, the lumping together of constituents with similar functional
groups is a useful approach. Lumped kinetic models provide a means of quan-
tifying the effects of process variables on product yields and also of summariz-
ing large amounts of experimental data.
The following major "lumps" are used in the kinetic model.
Heavy nonvolatiles = nonvolatiles in SEC fraction 1
+ nonvolatiles in SEC fraction 2.
Light nonvolatiles
Phenols
Aromatics
Alkanes
Coke + H20
Outlet Gases
The liquid yield, YL, is
= nonvolatiles in SEC fraction 3
+ nonvolatiles in SEC fraction 4.
= volatiles in SEC fraction 3
(compounds detectable by GC).
= volatiles in SEC fraction 4
+volatiles in SEC fraction 5
(excluding solvents).
-- volatiles in SEC fraction 2
1 -- liquid yield.
defined as follows:
E (wt. of fractions by SEC) - (solvents in hydrotreated oil)
YL-
43
pine pyrolytic oil input
The ~ (wt. of fractions by SEC ) represents the weight of liquid product which
includes the hydrotreated oil and solvents.
Table 5 shows an example of the lumped fractions of the pine pyrolytic oil
and a hydrotreated product. Because the alkane concentrations were small,
alkanes and aromatics were combined for the kinetic model. A pseudo first
order kinetic model is used to relate the reaction rates of lumped species. The
proposed model consists of the following kinetic scheme
k l k3 k4
HNV ) LNV , Phenolics ~ [Aromatics+Alkanes]
TABLE 5
Typi cal lumped fractions for ki net i c modeling ~ ( Pt / A12OJSi 02, 673 K, 8,720 kPa, and 2 hr -1
WHSV)
Lumped Pi ne Hydr ot r eat ed
fraction pyrol yt i c oil pyrol yt i c oil
(wt. %) (Exp. No. 220)
(wt.%)
1 Heavy Nonvolatiles: 0.4932 0.2457
2 Li ght Nonvolatiles: 0.3690 0.2941
3 Volatile Phenols: 0.1232 0.1063
4 Aromat i cs: 0.0146 0.1625
5 Alkanes: 0.0 0.0327
6 [ Ga s e s +H20+Coke ] : 0.0 0.1587
1.0000 1.0000
aSheu [12].
44
k5
[ Ar oma t i c s + a l k a n e s ] , [ C O K E + W A T E R + G A S E S ]
whe r e H N V a n d L NV r e f e r s t o " h e a v y " a n d " l i g h t " nonvol at i l es .
Th e r a t e e xpr e s s i ons f or t h e a p p e a r a n c e o f t h e l u mp e d speci es ar e:
rl = - ki p, ( 3)
r2 = kl f l l - k2p2 - k3p2 ( 4)
r3 = k3p2 - k4P3 ( 5)
r4 -~ k2p2 + k4P3 - k5P4 ( 6)
r~ = k5fl 4 ( 7)
a n d t h e s ubs c r i pt s " 1 " = h e a v y nonvol a t i l e s , " 2 " = l i g h t nonvol at i l es ,
" 3" = vol at i l e phe nol s , " 4 " = [ a r o ma t i c s + a l k a n e s ], a n d
" 5 " = [coke + H2 0 + o u t l e t gases ].
Eq u a t i o n s ( 8) t h r o u g h ( 12 ) a r e t h e ma t e r i a l b a l a n c e s wi t h a xi a l di s per s i on f or
e a c h l u mp e d r e a c t i on speci es occur i ng i n t h e pr ocess.
d2 Y1 - d Y 1 -
dZ- ~- PeM ~ + PeM Da
d2Y2 - dY2 -
--dZ 2 - PeM ~ + PeM Da '3
exp ( 0 1 ( 1 - - ~ - ) ) Y I =O
exp ( 0 2 ( 1 - ~ - ) ) Y2
+Pe M Da'~ exp (y3(1 - - ~ - ) ) Y2
=Pe M Da~ exp (01 ( 1 - - ~ - ) ) Y1
d2Y3 - dY3 - To
dZ----~--PeM-d~- + PeM Da~ exp ( 0 4 ( 1 - - ~ - ) ) ]13
=Pe M Da~ exp ( 0 a ( 1 - - ~ - ) ) ]12
d2Y4 dY4 ( 0 5 ( 1 - - ~ - ) ) Y4
dZ----- ~ - PeM ~ + PeM Da ~ exp
=P e MDa ~ e x p ( 0 4 ( 1 - - - - ~ ) ) ]I3
+Pe M Da`3 exp ( 0 2 ( 1 - - ~ - ) ) Y2
(8)
(9)
( 10)
( 11)
45
d 2 Y5 d Y5 _~_
dZ 2 P e M~ =P e MDa ~ e x p (~5(1-- )) Y4 (12)
where
Damkohl er number (Da ) = Lkio/Ua, Pecl et number ( Pe M) .= ULL/ D. (13)
~i =E J R T o (14)
kio =Ai exp ( - 7 i )
Ai = frequency fact or ( mi n -1)
D = di spersi on of t he react i ng species in liquid phase ( cm2/ mi n)
Eai = act i vat i on energy ( kJ / mol )
UL = superficial velocity of t he pyrol yt i c oil ( c m/ mi n)
densi t y of react i ng fract i on i
Y i =
densi t y of pi ne pyrol yt i c oil
Z = di mensi onl ess cat al yt i c bed l engt h.
The boundar y condi t i ons for eqns. (8) t hr ough (12) are:
-- PeM ( Yi - yo) at Z = 1.
dZ
- 0
dZ
at Z= 0 . ( i =1 t o 5)
A met hod [17-19] of combi ni ng quasi l i neari zat i on wi t h or t hogonal collo-
cat i on was appl i ed to est i mat e t he par amet er s PeM, Da o, and ?i in eqns. (8) to
(12) si mul t aneousl y. The me t hod was originally devel oped for model i ng t he
l i quefact i on of coal in a bubbl e col umn reactor.
The par amet er est i mat i on was per f or med on a single r un basis. Thus, for
each react i on run, a set of l umped fract i on dat a from t he SEC-GC anal ysi s
pl us t he t emper at ur e profile i nsi de t he react or were given. Equat i ons (8) to
( 12 ) were solved si mul t aneousl y and t he par amet er s PeM, Da , and ~i for each
r un were obt ai ned. The act i vat i on energy (Ei ) and frequency fact or (Ai ) of
t he l umped ki net i c model were deri ved from t he est i mat ed par amet er s Da
and Yi by eqns. (13) and (14). The average act i vat i on energies for di fferent
cat al yst are given in Tabl e 6 al ong wi t h t he average frequency fact ors for t he
vari ous st eps in t he react i on net work. Also l i st ed in Tabl e 6 is t he Pecl et num-
ber (PeM). The average frequency fact ors l i st ed in Tabl e 6 were eval uat ed at
8,720 kPa. The pressure effect on react i on rat es will be di scussed later.
46
TABLE 6
Ki net i c and r eact or par amet er s (Ai are at 8,720 kPa)
Pt / A12OJ Si 02 Sul fi ded Sul f i ded
Ni -Mo/ A1203
Co-Mo/ A1203
E, ( k J / mo l ) 74.0 _+ 2.9 a 74.5 __ 3.2 82.2 _+ 2.9
E2 91.8 _+ 4.3 96.4 _ 3.4 105.8 _+ 3.0
E3 80.6 _+ 2.6 81.8 _+ 3.6 90.4 _+ 3.0
E4 62.3 _+ 2.6 69.0 _+ 2.9 68.4 _+ 3.4
E5 69.6 __ 2.8 55.8_+ 3.6 74.9 __ 2.7
A1 ( mi n - ' ) 3,860 _ 500 3,500 + 280 8,800 _+ 1000
A2 75,400 _+ 12,000 218,000 _+ 8,400 654,000 __ 59,000
A:~ 8,300 + 1,100 7,700_+ 460 30,600 _+ 3,600
A4 950 _+ 160 3,100 + 560 1,920 __ 50
A5 4,000 __ 650 450 _+ 47 16,400 _+ 160
PeM 10.2 _ 1.1 9.86 _+ 0.05 9.63 __ 0.38
aMean _-2-st andar d devi at i on.
The exper i ment al and pr edi ct ed val ues of t he l umped species in t he ki net i c
model at vari ous react i on condi t i ons are di scussed in t he following subsect i ons.
Effect of temperature
Figures 3 ( a ) - ( c ) shows t he compar i son of exper i ment al and pr edi ct ed con-
cent r at i on profiles for t he vari ous species in t he l umped ki net i c model. The
poi nt s in t he figures are t he exper i ment al data. The solid lines were cal cul at ed
from t he l umped ki net i c model usi ng t he par amet er s l i st ed in Tabl e 6. Figures
3( b) and 3(c) for sul fi ded Co-Mo and Pt / A12OffSi 02 show an 8% to 10%
decrease in t he "heavy nonvol at i l es" and "l i ght nonvol at i l es" by an increase
of react i on t emper at ur e from 623 t o 673 K. The l umped fract i ons, "Phenol s",
"Aromat i cs + al kanes", and "coke + wat er + out l et gases", increase wi t h hi gher
react i on t emper at ur e.
Even t hough t he react i on rat es i ncreased wi t h t he react i on t emper at ur e, t he
t emper at ur e effect on t he per f or mance of sul fi ded Ni -Mo cat al yst was not sig-
ni fi cant . Fi gure 3 (a) shows t hat t he l umped fract i ons onl y change about 1 t o
4% bY i ncreasi ng t he react i on t emper at ur e from 623 to 673 K.
Effect of reaction pressure
The effect of react i on pressure was eval uat ed at 5,272; 6,996; 8,720 and 10,443
kPa at 673 K and wei ght hourl y space velocity equal t o 2 h- 1. A rel at i onshi p
47
bet ween t he frequency fact or in t he l umped ki net i c model and t he react i on
pressure of t he following f or m was assumed
At (:~ phi
The cal cul at ed val ues of n~ and are l i st ed in Tabl e 7. All of t he frequency fact ors
i ncreased wi t h react i on pressure except for t he Pt / A1203/ Si O2 catalyst. The
effect of pressure refl ect ed by t he par amet er s, n~, for t he di fferent cat al yst s is
di fferent for each cat al yst , because of t he di fference in cat al yt i c activity. Since
t hi s is a t wo phase syst em i ncreasi ng pressure will increase t he concent r at i on
of hydr ogen in t he liquid, whi ch appar ent l y i ncreases t he rates of t he react i ons.
Hence, t he rat es in t he l umped ki net i c model increase wi t h hi gher react i on
pressure except for t he following react i on when usi ng Pt/A12OffSiO2:
k5
"Aromat i cs + al kanes" , "Coke + H20 + out l et gases"
whi ch decreases wi t h hi gher react i on pressure.
The exper i ment al and pr edi ct ed profiles for t he vari ous react i ng species at
673 K are shown in Figs. 4 ( a ) - ( c ). The agr eement bet ween t he exper i ment al
resul t s and model pr edi ct i ons appears t o be reasonabl y good. Overall, t he in-
crease in react i on pressure pr oduced fewer "Heavy nonvol at i l es" and "Li ght
nonvol at i l es", and more "Aromat i cs + al kanes" and "phenol i cs". Hi gher
"Coke + H20 + out l et gases" are pr oduced wi t h sul fi ded Har shaw Co-Mo and
Ni - Mo cat al yst s, but less "Coke + H~O + out l et gases" are pr oduced wi t h P t /
A12OffSi02.
Ef f e c t of space velocity
The effect of wei ght hour l y space velocity on t he react i on pr oduct s was eval-
uat ed at 0.5, 1.0, 2.0, and 3.0 h - 1. The exper i ment al and pr edi ct ed concent ra-
t i on profiles for t he vari ous react i ng species are shown in Figs. 5 ( a ) - ( c ) . By
compar i ng Figs. 5 ( a ) - (c), one observes:
TABLE 7
Ef f ect of r e a c t i on pr es s ur e on t he f r equency f act or (Ai = A P n~)
Pr es s ur e Pt / A12OJ Si O2 Sul f i ded Sul f i ded
ef f ect Co- Mo/ Al 203 Ni - Mo/ AI 203
nl 1.35 0. 83 0. 16
n2 0. 40 0.71 0. 17
n3 1.58 0. 93 0. 31
n4 1.08 0. 73 0. 25
n~ - 0. 64 1.34 0. 30
48
( 1 ) The wei ght per cent age of t he phenol i c fract i on does not vary wi t h differ-
ent space velocities. Hence, t he react i on rat e of "Li ght nonval at i l es
Phenol s" is equal to t he react i on rat e of "Phenol s
Aromat i cs al kanes".
(2) The pr oduct i on of ar omat i cs and al kanes favors low space velocity for t he
Pt / A1203/ Si 02 cat al yst .
(3) The sul fi ded Co-Mo cat al yst forms more "Coke H20 out l et gases"
dur i ng t he hydr ot r eat i ng react i on t ha n Pt / A120f f Si 02 or sul fi ded Ni -Mo
catalyst.
(4) For sul fi ded Ni -Mo cat al yst , t he most si gni fi cant effect of space velocity
is t he change in t he concent r at i ons of "Li ght nonvol at i l es" and
"Coke H20 out l et gases" fractions.
CONCLUSIONS
Al t hough t he exper i ment al dat a for oxygen removal shows t hat changes in
space velocity do not have a si gni fi cant effect on oxygen removal , t he "acti-
vat i on energi es" devel oped from t he oxygen removal model for sul fi ded Co-Mo
and sulfided Ni -Mo cat al yst s agree wi t h t hose r epor t ed in t he l i t erat ure. No
ki net i c dat a usi ng Pt / A12OJ Si 02 as cat al yst for oxygen removal have been
r epor t ed in t he l i t erat ure.
Dat a obt ai ned from t he SEC-GC anal ysi s were model ed wi t h pseudo-fi rst
order ki nt et i cs descri bi ng t he react i on rat es of l umped species. The model was
composed of five fractions: (1) heavy nonvol at i l es, (2) l i ght nonvol at i l es, ( 3 )
phenol s, ( 4 ) [ aromat i cs + al kanes ], and (5) [ coke H2 out l et gases ]. An Ar-
r heni us model was used to describe t he t emper at ur e dependence of t he rate
const ant s. A clear t r end of t he effect of react i on t emper at ur e, wei ght hourl y
space velocity, and react i on pressure on hydr ot r eat i ng pyrol yt i c oil usi ng P t /
Al2OffSi02, sul fi ded Co-Mo, and sul fi ded Ni -Mo cat al yst were observed. The
agr eement bet ween t he exper i ment al dat a and model predi ct i ons are good.
Small t ri ckl e -bed react ors such as t hose used in l aborat ori es and pi l ot pl ant s
have some axial di spersi on. The Pecl et number est i mat ed from t he l umped
ki net i c model is about 10.
The SEC-GC analysis of hydr ot r eat ed pyrol yt i c oil shows t hat par t of t he
phenol s in pi ne pyrol yt i c oil have been hydr ogenat ed and conver t ed i nt o aro-
matics, and phenol s have been pr oduced also from t he nonvol at i l es duri ng t he
reaction. Some ar omat i cs were conver t ed from t he l i ght nonvol at i l e fract i on
directly. The al kanes were pr oduced by r emovi ng t he oxygen at oms from t he
est ers in t he pi ne pyrol yt i c oil dur i ng t he hydr ot r eat i ng reaction.
Pt / A12OJSi O2 cat al yst has t he best hydr ot r eat i ng ability among t he four
cat al yst s t est ed. Dur i ng t he upgr adi ng process, some oxygen f unct i onal groups
in t he pyrol yt i c oil have t o be r emoved ( hydr ot r eat ed) first, ot herwi se t he ox-
ygen- cont ai ni ng compounds in pyrol yt i c oil pol ymeri ze at hi gh t emper at ur e.
49
The hydr ot r eat ed pr oduct at t he react i on condi t i ons appl i ed in t hi s research
still cont ai n a cer t ai n a mount of oxygen and nonvol at i l es. I n order t o remove
mor e oxygen and conver t t he nonvol at i l es i nt o volatiles, a hi gher react i on t em-
per at ur e and pressure or a new mor e effi ci ent cat al yst shoul d be applied.
ACKNOWLEDGMENT
The fi nanci al suppor t from t he U.S. Depar t ment of Agri cul t ure under t he
Special Research Gr ant s Program, Agr eement No. 59-2481-0-2-089-0 is greatly
appreci at ed. Special acknowl edgement is also ma de to t he Cent er for Ener gy
and Mi ner al Resources, t he Texas Agri cul t ure Exper i ment al St at i on, and t he
Texas Engi neer i ng Exper i ment al St at i on, all par t of Texas A&M Uni ver si t y
Syst em.
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