Ind. Eng. Chem. Prod. Res. Dev.
1905, 24, 489-491
wood and those in the hydrolyzed residue can be used to
calculate the hydronium ion concentration in the solution
during hydrolysis. Through the use of standard analytical
methods, two procedures were developed to determine the
quantity of cations in a wood or hydrolysis residue sample.
When the most accurate procedure was used, the hydro-
nium ion concentration calculated from cations released
into the solution agreed closely with that measured ki-
netically.
Appendix
Calculation of Hydronium Ion Concentration, [H?].
(Molal concentration units of mol/kg of water are used;
i.e., [XI = concentration of X in mol/kg of water.)
Basis: 100 kg of OD wood.
Given: concentration of added acid = CA, % H2S04;
liquid-to-solid ratio = LS, kg/kg; neutralizing capacity of
wood = EQW, mequiv/kg OD wood; neutralizing capacity
of residue = EQR, mequiv/ kg OD wood.
Then: EQ = equivalents of cations released to solution
= (EQW - EQR)/10; SS = sum of the concentrations of
sulfate and bisulfate ions in solution = CA/[9.8(1- 0.01
X CA)]mol/lOOO g of water; CS = concentration of cations
in solution = EQ/[LS X (100 - CA)]equiv/lOOO g of water.
Sulfur balance: [HSO,] + [SO:-] = SS; charge balance
([OH-]<<[S042-]),[HS04-] + 2[SO:-] - [H+] = CS; bi-
sulfate dissociation quotient, Q = [H+][SO:-]/ [HS04-].
These equations combine to the quadratic equation in
[H+.l:
[H+l2+ (Q + CS - SS)[H+] + Q(CS - 2 X SS) = 0
With numerical values for CS, SS, and Q the coefficients
may be evaluated and the equation solved for its one real
positive root that is the value of [H+]. The bisulfate
dissociation quotient, Q, is evaluated by using the following
relationships from Lietzke et al. (1961):
In Q = In K + 4s [ 1 :;Ill2]
where K = bisulfate dissociation equilibrium constant =
COMMUNICATIONS
High Activity and Selectivity of a “Poisoned” NIMo/Ai,O, Catalyst for a Desulfurization
Reaction
Studies at 220-300 O C and 10.1-MPa total pressure on a suiflded commercially produced NiMo/A1,03 catalyst
showed that the addRion of nitrogen compounds improved desulfurization acthri with high selectivity to a biphenyl
from dibenzothiophene.
For many years, hydrodesulfurization catalysts have
been said to be inhibited by nitrogen compounds. These
catalysts consist of molybdenum promoted by cobalt or
nickel and supported on alumina. For a sulfided Mo/Al,O3
catalyst, the addition of acridine decreased the conversion
rate of dibenzothiophene hydrodesulfurization at all tem-
peratures (Nagai and Kabe, 1980,1983). Acridine inhib-
ited hydrogenation activity but did not affect the desul-
0196-432118511224-0489$01.50/0
409
exp(-1283,108/T + 12.31995 - 0.0422322T); T = temper-
ature, kelvin; S = Debye-Huckel limiting slope at tem-
perature T, for a singly charged ion = 21/2 X 1.290 X
106/(DT)3/2;D = dielectric constant for water = 78.54(1
+
- 0.004579(t - 25) 11.9 X 10+(t - 25)’ 28.0 x 10-9(t +
) ; temperature, OC; I = ionic strength = 0.5([H+]
- ~ E J ) t~ =
+ [HS04-] + 4[SO:-] + CS); A = an empirical constant
= 0.4.
Acknowledgment
R. W. Scott, research chemist, Forest Products Labo-
ratory, performed the experiments on determining neu-
tralizing capacity of the wood and residue samples by
dry-ashing and titration.
Registry No. MzSO4,7664-93-9; H’, 12408-02-5.
Literature Cited
EeMiiier, J. N. A&. Carbohydr. Chem. 1987, 2 2 , 25.
Harris. J. F.; Scott, R. W.; Springer, E. L.; Wegner, T. H. “Progress in Eiom-
ass conversion”; Academic Press: New York, 1984; Voi. 5.
Kirby, A. M., Jr. M.S. Thesis, University of Wisconsin, 1948.
Krasowski, J. A.; Marton, J. TAPPI Proc. Res. Dev. Dlv. Conf. 1982,
129-138.
Liegei, E. A.; Simson, C. R.; Schulte, E. E., Eds. ”Proceedings for Soli Test-
ing, Piant Analysis and Feed and Forage Analysis, Soil Fertility Series No.
6”; Dept. of Soil Sciences, University of Wisconsin Extension: Madison,
WI, 1980; p 24.
Lietzke, M. H.; Stoughton, R. W.; Young, T. F. J. Phys. Chem. 1961, 6 5 ,
2245.
McLean D. A. I d . Eng. Chem. 1940, 32. 209.
Moore, W. E.; Johnson, D. E. I n “Procedures for the chemical analysis of
wood and wood products as used at the U.S. Forest Products
Laboratory”; TAPPI Standard Method T 211, 1967.
Phifer, L. H.; Maginnis, J. E. Tappl 1980, 43. 38.
Saeman, J. F. Ind. Eng. Chem. 1945, 3 7 , 43.
Schorger, A. W. “Chemistry of Cellulose and Wood”, 1st ed.; McGraw-Hili:
New York, 1926; p 50.
Scott, R. W.; Wegner, T. H.; Harris, J. F. J. Wood Chem. and Techno/.
.._
1883. 3. 245..
Springer, E. L. Tapp/ 1986, 49, 102.
Springer, E. L. Tappi 1968, 57, 214.
Springer, E. L.; Harris, J. F.; Neil, W. K. Tappi 1983. 46, 551.
Subramanian, R. V.; Somasekharan, K. N.; Johns, W. E. Holzforschung 1983,
3 7 , 117.
Veeraraghaven, J.; Chambers, R. P.; Myles, M.; Lee, Y. Y. presented at the
AIChE National Meeting, Orlando, FL, 1982.
Receiued for review November 19, 1984
Accepted April 29, 1985
furization activity below 320 OC whereas above 320 O C
acridine inhibited both activities because acridine was
decomposed on the desulfurization sites as well as hy-
drogenated on other sites. There were similar observations
with the addition of other nitrogen compounds such as
pyridine, quinoline, and piperidine. Cowley and Massoth
(1978) also found that pyridine inhibited benzothiophene
hydrodesulfurization over a sulfided Mo/A1203catalyst at
0 1985 American Chemical Society
490 Ind. Eng. Chem. Prod. Res. Dev., Vol. 24, No. 3, 1985
-.
220 240 260 280 300
Temperature ('C )
Figure 1. Change in the products in dibenzothiophene hydro-
desulfurization on a sulfided NiMo/A1203 catalyst with (-) and
without (- - -) acridine. ( 0 )Diphenyl; (A)cyclohexylbenzene; (0)
dibenzothiophene; (0) hydrogenated compounds, bicyclohexyl, and
other hydrocarbons.
345 "C. Moreover, Urimoto and Sakikawa (1972) reported
that ammonia did not enhance the desulfurization reaction
over a transition-metal sulfide catalyst, e.g., MoS,, WS2,
COS, or NiS at 400 "C. Thus, the addition of nitrogen
compounds to sulfided molybdenum catalysts not con-
taining a promoting metal did not improve hydro-
desulfurization activity. For sulfided molybdenum cata-
lysts containing a metal promoter, Satterfield et al. (1975,
1980) reported that pyridine inhibited the sulfided
CoMo/A1203 and NiMo/Alz03 catalytic activity for
thiophene hydrodesulfurization, and high catalytic activity
and selectivity for the desulfurization reaction were not
found. We found, however, that a sulfided NiMo/A1203
catalyst, poisoned by the addition of acridine, catalyzed
dibenzothiophene hydrodesulfurization with high activity
and selectivity. The observation was similar to those ob-
tained by adding other nitrogen compounds, e.g., quinoline,
pyridine, piperidine, and dicyclohexylamine. The exam-
ples of such a poisoned catalyst are the Lindlar-type
catalysts that are poisoned with quinoline (Lindlar, 1952;
McEwen et al., 1983) and the ammonia synthesis catalysts
which are transformed into bulk nitride during the reaction
(Ozaki and Aika, 1981).
Experimental Section
The experiments were carried out in a continuous-flow
microreactor a t a high pressure. Two grams of the
NiMo/Alz03catalyst (15% MOO, and 3 % NiO supported
on 7-A1203,Ketjenfine 153,14-20 mesh) were packed into
the reactor (i.d. 11 mm) and were oxidized a t 450 "C for
24 h. The catalyst was reduced in situ with hydrogen at
10 L/h, 400 "c, and 10.1 MPa for 4 h and was then sulfided
with 30 L / h of a H,S/Hz mixture (1/9) a t atmospheric
pressure and 400 "C for 3 h. The reactions were carried
out within the temperature range of 220-300 "C with a 30
L/h hydrogen flow rate, 10.1 MPa total pressure, and a
weight hourly space velocity of 7.5. A solution containing
5 wt % of dibenzothiophene in xylene was introduced into
the reactor. The solution was replaced by a solution
containing 5 wt % of dibenzothiophene and 0.5 wt % of
acridine after 3 h. The liquid products were separated by
a high-pressure separator into gaseous products and an-
alyzed by an FID gas chromatograph.
Figure 1 shows that major desulfurized compounds were
biphenyl and cyclohexylbenzene in the dibenzothiophene
hydrodesulfurization reaction. Cyclohexylbenzene was
3 0 I
I
3 1 2 3 6 5 6
Time ( h )
Figure 2. Transit study of the catalytic activity on the addition of
acridine at 260 O C . The symbols are the same those in Figure 1.
produced through hexahydrodibenzothiophene, and bi-
phenyl was produced by fission of the C-S bond in di-
benzothiophene. The addition of acridine increased the
concentration of biphenyl and decreased that of cyclo-
hexylbenzene a t all reaction temperatures. Dibenzo-
thiophene conversion was about 2 times greater than that
for the reaction of dibenzothiophene alone. The mass
balance remained almost unchanged before and after the
addition. The observation was similar to those obtained
by adding other nitrogen compounds. Hence, the addition
of nitrogen compounds improved desulfurization activity
with high selectivity to a biphenyl. Figure 2 shows the
change in the products of dibenzothiophene hydro-
desulfurization at 260 OC when acridine was added. The
addition of acridine resulted in an increase in the biphenyl
concentration and a decrease in both cyclohexylbenzene
and dibenzothiophene concentrations; although the un-
reacted dibenzothiophene concentration slightly increased
for a short period of time after the addition as shown in
Figure 2. Furthermore, the solution's color changed from
colorless to orange when the solution cooled to a low tem-
perature. This was followed by the precipitation of a sulfur
powder (mp 115-120 "C). The orange color was caused
by the complexes of the amines such as hydrogenated
acridine (Nagai et al., 1979) with sulfur (Pryor, 1962).
There were no observations over a short period of time
after the addition of nitrogen compounds to the sulfided
NiMo/A1203catalyst nor were there for a sulfided Mo/
A1203 catalyst (Nagai and Kabe, 1980,1983). These results
indicate that there are two different aspects of the poi-
soning effect of nitrogen compounds on the hydro-
desulfurization of dibenzothiophene.
In the initial stage of the addition (a small amount of
a nitrogen compound on the surface of the catalyst), the
poisoning effect on the catalyst suggests that the poisons
block the active sites and thus prevent the hydrogenation
of dibenzothiophene (Nagai et al., 1984). As the amount
of nitrogen compounds increases over the surface, it ap-
pears that the poisons rearrange the surface structure
[active sites Ni-Mo-S type structures on the edge of MoS2
(Topme et al., 1981; T o p s ~ and
e Tops~e,198311 to become
more active for the desulfurization of dibenzothiophene.
In addition, the poisons might help in the desorption of
sulfur adsorbed on the desulfurization sites of the catalyst.
This phenomenon was also observed for a sulfided
NiW/Al2O3catalyst but not for a sulfided CoMo/AlzO,
catalyst (Nagai, 1985).
Registry No. Acridine, 260-94-6; dibenzothiophene, 132-65-0;
cyclohexylbenzene, 827-52-1; biphenyl, 92-52-4.
 Ind. Eng. Chem. Prod. Res. Dev., Vol. 24, No. 3, 1985 491

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Nagai, M.; Kabe, T. J. Jpn. Pet. Inst. (Seklya Gakkaishi) 1980, 23, 82.
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Nagai, M.; Sawahiraki. K.; Kabe, T. Nippon Kagaku Kalshi 1979, 1350. T o k y o University of Agriculture and
Nagai, M.; Aiba. A.; Satoh, T.submitted for publication In J. Catal.
Ozaki, A.; Aika, K. I n "Catalysis-Science and Technology"; Anderson, J. R.; Technology
Boudart, M., Ed.; Springer-Verlag: Berlin, 1981; Vol. I , Chapter 3. Koganei City, Tokyo 184, J a p a n
Pryor, W. A. "Mechanisms of Sulfur Reactions"; McGraw-Hill: New York,
1962; p 11. Received for reuiew November 28, 1984
Satterfield, C. N.; Modell, M.; Mayer, J. E. AIChE J. 1975, 21, 1100. Accepted April 4, 1985