418 I n d . Eng. Chem. Res.

1989, 28, 418-421

Joint Symp. on Dry SO2 and Simul. SO,/NO, Control Technol.
1, EPA-600/9-86-029a (NTIS PB87-1204653, Oct 1986, p 8-1.
Lange, H. B. Experimental Study of Gas Use to Improve the Lime-
stone Injection Process for SOz Control on Utility Boilers. Gas
Research Institute Contract No. 5086-251-1232, 1987.
McCarthy, J. M.; Chen, S. L.; Kramlich, J. C.; Seeker, W. R.;
Pershing, D. W. Reactivity of Atmospheric and Pressure Hydrated
Sorbents for SOz Control. Proc. 1986 Joint Symp. on Dry SOz and
Simul. SOz/NO, Control Technol. 1, EPA-600/9-86-029a (NTIS
PB87-120465), Oct 1986, p 10-1.
Muzio, L. J.; Boni, A. A.; Offen, G. R.; Beittel, R. The Effectiveness
of Additives for Enhancing SO2 Removal with Calcium Based
Sorbents. Proc. 1986 Joint Symp. on Dry SOz and Simul. SOz/
NO, Control Technol. 1, EPA-600/9-86-029a (NTIS PB87-
120465), Oct 1986, p 13-1.
Newton, G. H.; Harrison, D. J.; Silcox, G. D.; Pershing, D. W. Control
of SO, Emissions by In-Furnace Sorbent Injection: Carbonates
vs. Hydrates. AIChE Annual Meeting, Chicago, IL, Nov 1985.
Overmoe, B. J.; Chen, S. L.; Ho., L.; Seeker, W. R.; Heap, M. P.;
Pershing, D. W. Boiler Simulator Studies on Sorbent Utilization
for SOz Control. Proc. First Joint Symp. on Dry SOz/NO, Control
Technol. 1, EPA-600/9-85-020a (NTIS PB85-2323533, July 1985,
p 15-1.
Simons, G. A. Parameters Limiting Sulfation by CaO. AZChE J .
1988, 34, 167.
Slaughter, D. M.; Silcox, G. D.; Lemieux, P. M.; Newton, G. H.;
Pershing, D. W. Bench Scale Evaluation of Sulfur Sorbent Reac-
tions. Proc. First Joint Symp. on Dry SO2 and Simul. SOz/NO,
Control Technol. 1, EPA-600/9-85-020a (NTIS PB85-2323533,
July 1985, p 11-1.
Slaughter, D. M.; Chen, S. L.; Seeker, W. R. Enhanced Sulfur Cap-
ture by Promoted Calcium-Based Sorbents. Proc. 1986 Joint
Symp. on Dry SOz and Simul. SOz/NO, Control Technol. 1,
EPA-600/9-86-029a (NTIS PB87-1204653, Oct 1986, p 12-1.
Ulerich, N. H.; O'Neill, E. P.; Keairns, D. L. A Thermogravimetric
Study of the Effect of Pore Volume-Pore Size Distribution on
the Sulfation of Calcined Limestone. Thernochim. Acta 1978,26,
269.
Received for review May 20, 1988
Revised manuscript received November 17, 1988
Accepted December 14, 1988

Structure and Properties of Sludges Produced in the Catalytic

Hydrocracking of Vacuum Residue
I s a o Mochida,* Xing-zhe Zhao, and K i n y a S a k a n i s h i
Institute of Advanced Material Study, Kyushyu University, Kasuga, Fukuoka 816, Japan
Shun-ichi Yamamoto, Hiro-aki T a k a s h i m a , a n d Sei-ichi U e m u r a
T h e Central Research Institute, Nippon Oil Company Ltd., Yokohama 231, Japan

The structure and properties of sludge produced in the catalytic hydrocracking of atmospheric residue
were investigated after the extractive fractionation of sludge-concentrated product. The product
consisted of major HS (hexane-soluble: 86 % ) and minor HI-BS (hexane-insoluble-benzene-soluble:
7%), BI-THFS (benzene-insoluble-tetrahydrofuran-soluble: 2 % ), and T H F I (THF-insoluble: 5 % )
fractions. The HS fraction was essentially paraffinic, carrying some long-chain alkylbenzenes, while
the hexane-insoluble fractions were aromatic and polar with a larger extent of aromaticity and polarity
which decreased their solubility in spite of their rather similar molecular weight distributions. 'The
H I fraction melted around 250 "C to give a homogeneous solution under hot-stage microscope, while
the THFI showed a softening point as high as 360 "C, producing some coke particles. Addition of
solvents such as 1-methylnaphthalene to the fraction provided a homogeneous solution above 80
"C. The brown flock substances and blue crystallines, which were sludge and wax, respectively, were
observed in the 350+ "C product. T h e addition of 1-methylnaphthalene dissolved and dispersed
the flock substance a t room temperature, leaving the crystallines unchanged, while ethanol dissolved
the crystallines to form blue droplets. Catalytic hydrogenation around 350 "C removed the flocky
substances, while the crystallines remained unchanged. Based on such results, the sludges are
produced through the hydrocracking of resin and light asphaltene fractions and dealkylation of heavy
asphaltene, which reduced their mutual solubility, leading to the sedimentation of the latter sub-
stances.

Demand for clean distillate from the bottom of the
barrel leads to severe hydrocracking of petroleum residues
a t higher temperatures (Saito and Shimizu, 1985). The
severe conditions cause problems of coke deposition on the
catalyst and sludge formation in the product oil (Symoniak
and Frost, 1971). Such troublemakers of both carbona-
ceous materials, of which formation may be intimately
related, shorten the life of the catalyst, plug the transfer
line, and deteriorate the quality of the products (Mckenna
et al., 1964).
Empirically, the dry sludge is believed to be produced
when the conversion to the distillate is beyond a certain
level (ca. 50%) regardless of the catalyst and feedstocks.
However, its structure, properties, and mechanism of
formation are not fully understood yet (Haensel and Ad-
dison, 1967). A better understanding of its structure re-
lated to its thermal behavior may lead to better catalysts
0888-5885/89/2628-0418$01.50/0
or schemes whichs can overcome the difficulty in the
present hydrocracking process. Since the dry sludge is
never a single species of a molecule, analyses of its fractions
and their mutual interaction may be most important to
define its properties, suggesting procedures for their re-
moval.
In the present study, dry sludge produced in a hydro-
cracked oil was analyzed chemically, and its solubility and
fusibility were observed under a hot-stage microscope. Its
reactivity was examined in the catalytic hydrogenation at
a relatively lower temperature than those applied in the
hydrocracking process.
Experimental Section
A vacuum residue of Arabian light oil (bp > 550 "C) was
hydrocracked by Chiyoda Chemical Construction Co. un-
der three different conditions (reaction temperatures: 395,
0 1989 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 28, No. 4, 1989 419

Table I. Solubility of the Concentrated Sludge Fraction

extraction wt%
methods HS HI-BS BI-THFS THFI
room temp 72 14 4 10
Soxhlet 86 7 2 5

405, and 418 "C), which were the conditions for no for-
mation, beginning of formation, and some formation of dry
sludge, respectively, using a commercial Co-Mo/A1203
catalyst (Shokubai Kasei Co.) in the two-staged fixed-bed
microreactors. The hydrocracked products were distilled,
and the 350+ "C fraction was further separated by using
a supercentrifuge (Hitachi-70P-72) to obtain the concen-
trated sludge fraction.
Solubility of the centrifugated sludge fraction was ex-
Wavelength (nm)
amined by successive extractions with n-hexane, benzene,
and tetrahydrofuran (THF) at room temperature or a t Figure 1. UV spectra of dry sludge fractions: (a) HS; (b) HI-BS;
(c) BI-THFS.
their boiling points using a Soxhlet apparatus. The original
sludge and its solvent-fractionated components (HS,
hexane soluble; HI-BS, hexane insoluble-benzene soluble;
BI-THFS, benzene insoluble-THF soluble; and THFI,
T H F insoluble) were analyzed by 'H NMR, elemental
analysis, IR and GPC spectroscopies, and gas chroma-
tography according to the properties and solubilities of the
components.
The 350+ "C fraction was observed under a transmission
microscope with or without the existence of solvent (de-
caline, l-methylnaphthalene, or ethanol).
Fusibility and solubilities of the HI and THFI in the
concentrated sludge fraction were observed when heated
a t a rate of 10 "C/min under hot-stage microscope with
or without the solvent (1-methylnaphthalene).
The hydrogenation of the 350+ "C fraction (10 g) was 4000 30'00 2000 1000
performed in a batch autoclave of 100-mL capacity
(heating rate: 8 "C/min), under 100 atm of hydrogen Wave number (cm-1)
pressure at 350 "C for 5 h using 1 g of commercial Ni- Figure 2. IR spectra of dry sludge fractions: (a) HS; (b) HI-BS;
Mo/A1203 catalyst (KF-840, Nippon Ketjen Co.). The (c) BI-THFS; (d) THFI.
catalyst was presulfided under 5% H2S/H2flow at 360 "C
Table I1 also shows the hydrogen distributions of the
for 6 h using a flow reactor. fractions revealed by 'H NMR. The HS fraction showed
a high content of aliphatic hydrogens, especially a t the /3
Results positions, suggesting long paraffinic chains. Many of them
Composition a n d S t r u c t u r a l Characteristic of t h e are not connected to the aromatic ring. In contrast, the
Centrifugated Sludge Fraction. Table I summarizes HI-BS and BI-THFS fractions carried fairly high amounts
the solubility of the centrifugated sludge fraction. It was of aromatic hydrogens to show fa (carbon aromaticity)
principally hexane soluble (HS) but carried some hex- values of 0.7-0.8. The aromatic hydrogen content in-
ane-insoluble substance (HI), whose content was 14% a t creased significantly when the solubility decreased. The
the refluxing temperature of the solvent. The HI consists major aliphatic groups may be short and attached to the
of HI-BS, BI-THFS, and THFI. aromatic rings, since large Ha (a-hydrogen content) was
Elemental analyses of the fractions are summarized in observed.
Table 11. The HS fraction exhibited a high H/C ratio of Figure 1 shows the UV spectra of the HS, HI-BS, and
1.59 with the least amount of heteroatoms. The insoluble BI-THFS fractions. The HS fraction exhibited a shoulder
fractions of HI-BS, BI-THFS, and THFI had much lower peak around 280 nm, indicating some presence of the
H/C ratios and higher contents of heteroatoms (N, S, and benzene ring. The other fractions showed much more
0) than those of the HS fraction. intense absorption around 350 nm, suggesting that the
Table 11. Elemental and 'H NMR Analysesa of Extracts and Residue in the Sludge Fraction before and after the
Hydrotreatment
~~ ~~

elemental anal., wt % hydrogen composition, ./,

sampleb C H N o+s ash H/C Ha H" H R H, f.
OR-1 88.2 10.6 0.36 0.84 1.44 9.2 12.9 54.6 23.3 0.40
HS 87.6 11.6 0.28 0.51 1.59 7.9 11.9 57.1 23.1 0.33
HI-BS 89.7 5.96 0.80 3.51 trace 0.80 31.1 19.3 37.8 11.8 0.74
BI-THFS 88.4 5.21 1.01 3.62 1.81 0.71 36.1 27.8 22.2 13.9 0.79
THFI 88.8 3.93 1.06 6.22 trace 0.53
OR-2 87.8 11.6 0.20 0.45 1.58 7.8 11.8 57.5 22.9 0.33
HT-OR2 87.7 11.8 0.16 0.34 1.62 5.5 10.5 60.1 23.9 0.30
'Ha, 6-9 ppm; H,, 2-4 ppm; Hp, 1.1-2 ppm; H,, 0.3-1.1 ppm; fa, carbon aromaticity. *OR-1, concentrated sludge fraction; OR-2, the
fraction of bp >350 "C containing sludge; HT-ORB, hydrotreated OR-2 (reaction condition: 350 "C and 5 h).
420 Ind. Eng. Chem. Res., Vol. 28, No. 4, 1989
. .
.I ./ ':!
.
f j !!
Elution vdume (ml 1
Figure 3. GPC spectra of dry sludge fractions: (- - -) original, (---)
HS; HI-BS;
(-a*-) BI-THFS.
(-**e-)
0 5 IO 15 20
Retention Tim (mm )
Figure 4. Gas chromatogram of HS in the dry sludge.
fractions carry fairly large aromatic rings.
Figure 2 shows FT-IR spectra of the fractions. The
spectra indicate the higher aromaticity of the fractions with
decreased solubility, as described above. It should be noted
that THFI still carried some aliphatic CH, although the
fraction was highly aromatic.
GPC spectra of the fractions are shown in Figure 3,
where a UV detector was applied. All the fractions were
in similar ranges of molecular weight distribution, less than
600, although HI-BS and BI-THFS contained a smaller
amount of larger molecules. It should be noted that HS,
HI-BS, and BI-THFS showed larger intensities in the
order given because of the aromaticity increase, being
consistent with Figure 2.
Some Detail Structures of the Fractions. Figure 4
shows a gas chromatogram of the HS fraction. The
chromatogram indicates that the fraction consists essen-
tially of paraffins ranging from Cll to C3* The majority
of them were straight in their chains; minor amounts of
isoparaffin also exist in the range Cl0-CzO. A broad peak
around 15-min retention time (corresponding to Cz5)may
correspond to alkyl aromatics.
Figure 5 shows the IR spectra of the diluted HI-BS
fraction in CS2. The absorption bands at 3610,3530, and
3454 cm-l indicated the presence of phenolic OH, car-
boxylic OH, and pyrrolic NH groups in the fraction.
Considerable polarity is suggested.
Microscopic Observation of the 350+ "C Fraction.
A microphotograph of the 350+ "C fraction under a
transmission microscope is shown in Figure 6a, where
brown flocks and blue crystallines were clearly observable.
Brown flocks are dry sludge, while the blue crystallines are
wax.
3800 3600 3400 3200
wave number (crri')
Figure 5. IR spectrum of HI-BS fraction in the dry sludge (in dilute
CS2solution): (a) 3610 cm-l (phenolic OH); (b) 3530 cm-l (carboxylic
OH); (c) 3464 cm-I (pyrrolic NH).
IC ' .u '
Figure 6. Micrographs of the 350+ "C fraction before and after
addition of solvent: (a) original 350+ "C fraction; (b) after addition
25 30 of decalin (10 wt %); (c) after addition of 1-methylnaphthalene (10
wt %); (d) after addition of ethanol (10 wt %).
Addition of decalin at room temperature did not bring
any change in the appearance, as shown in Figure 6b. In
contrast, 1-methylnaphthalenedecreased the amount and
size of brown flocks, while nothing happened to the definite
blue crystallines (Figure 6c). Ethanol dissolved the blue
crystallines, forming blue droplets, and some of the brown
flocks also formed brown droplets, while some of the others
stayed unchanged (Figure 6d).
Behavior of the Concentrated Sludge Fraction
When Heated under a Hot-Stage Microscope. The HI
fraction of the concentrated sludge fraction softened
around 210 "C under a hot-stage microscope and became
viscous liquid at 250 "C, no insoluble nor infusible portion
being observable. The THFI fraction showed some sof-
tening at 360-370 "C. Further heating produced black
particles like chars. Since such black particles were not
observed in HI, the THFS fraction may dissolve THFI at
elevated temperatures, suppressing the coke formation.
HI was almost completely insoluble in molten paraffin;
however, homogeneous liquid was observed at 150 "C. A
major portion of the HI fraction should be dissolved in the
molten paraffin. Decalin dissolved half of the HI fraction
at room temperature and dissolved all of it at 120-130 "C.
1-Methylnaphthalene dissolved 70% of HI fraction at room
temperature. At 150 "C, an orange solution was observed.
The THFI fraction was not completely soluble in 1-
methylnaphthalene at room temperature, black particles
of variable diameter being observed. At 1W120 "C, small
particles started to be dissolved, and major particles, re-
gardless of their diameters, were dissolved a t 160 "C, al-
though a few black particles were still observable in the
orange solution. The solvent started to evaporate a t 180
"C, black solids being to precipitate.
Hydrogenation of the 350+ "C Fraction. Figure 7
shows photographs of the 350+ "C fraction before and

(b)
Figure 7. Micrographs of the 350+ O C fraction after the addition
of catalyst a t room temperature and the hydrotreatment a t 350 "C:
(a) after the addition of catalyst a t room temperature; (b) after the
hydrotreatment with the catalyst at 350 "C and 5 h.
after the hydrogenation at 350 "C with a Ni-Mo/AI2O3
catalyst. The catalyst did not do anything with brown
flocks and blue crystallines at room temperature (Figure
7a). However, the hydrogenation at 350 "C removed al-
most completely the brown flocks, although some fine
brown spots were still observed in high dispersion. In
contrast, blue crystallines remained almost unchanged
(Figure 7b).
Table I1 summarizes the elemental and lH NMR
analyses of the hydrogenated product. A slight increase
of aliphatic hydrogens and decreases of aromatic hydrogen,
nitrogen, and sulfur were noticed. A very small amount
of the heavier fraction may be selectively hydrogenated.
Discussion
Solvent extraction of the sludge-concentrated fraction
revealed that a significant amount of hexane-insoluble
substance stayed in the major hexane-soluble product.
About half of its content was insoluble in benzene, im-
plying decreased solubility of a part of the asphaltene in
the vacuum residue during the hydrocracking process, since
no benzene-insoluble substance was present in the feeds-
tock. Such an insoluble substance can be recognized as
the dry sludge in the hydrocracked product.
Structural analyses of the extracted fractions indicated
that the HS fraction in the product consists essentially of
long-chain paraffins and long-chain alkylbenzenes. In
contrast, the insoluble substances are fairly aromatic with
much less and shorter alkyl groups and are rather polar,
carrying a considerable amount of heteroatoms. Solubility
Ind. Eng. Chem. Res., Vol. 28, No. 4, 1989 421
decreased with increasing aromaticity and polarity, the
molecular weight varying rather slightly among the frac-
tions. Such a contrast in structural characteristics of the
HS and HI fractions may not allow for mutual miscibility,
precipitating or segregating the insoluble substances from
the HS matrix at room temperature.
In spite of the low solubilities of the sludge components
at room temperature, they melt or are dissolved in the light
component a t elevated temperatures above 80 "C, de-
pending on the content of lighter fractions. Thus, the
sludge may disappear at elevated temperatures such as the
reaction temperature, although its limited solubility in the
matrix may enhance its adsorption or longer residence on
the catalyst surface, leading to the severe catalyst deac-
tivation.
An aromatic additive such as 1-methylnaphthalene ac-
celerates the disappearance of sludge, especially on heating.
Hence, the addition of suitable aromatic solvent can sta-
bilize the hydrocracked product by dissolving the sludge
fraction.
Hydrogenation with a commercial Ni-Mo catalyst under
rather mild conditions converted the sludge fraction
miscible with the HS matrix. Reducing its aromaticity and
removal of polar heteroatoms can increase its solubility.
Sludge appears to be slightly adsorbed on the catalyst a t
room temperature. In addition to brown flocks of the
sludge, bluish crystallines, very probably long paraffinic
waxes, were observable under the microscope. Hydro-
genation at low temperatures cannot deal with such com-
ponents. They should be handled at the hydrocracking
stage.
Conclusions
According to the above results and discussions, several
proposals to reduce the sludge formation come to mind;
(1)addition of aromatic solvent; (2) hydrogenation after
the hydrocracking; (3) two-stage hydrotreatment-
extensive hydrogenation of the aromatic rings and heter-
ocycles in the asphaltene at a lower temperature and hy-
drocracking at a higher temperature.
The first two proposals intend to dissolve the sludge
after its formation. Hence, no increase of conversion is
expected. However, the third one can provide higher
conversion without sludge formation. Such a process re-
quires a katalyst which can extensively hydrogenate the
asphaltene before dealkylation. A preliminary result re-
vealed that the two-stage hydrocracking was very effective
for achieving higher cracking conversion without sludge
formation. The details will be reported later.
Acknowledgment
The authors are very grateful for the financial support
from the Ministry of International Trade and Industry
through the Petroleum Institute of Japan. They also ap-
preciate the Committee of the Institute for the Study of
Heavy Oils for its cooperation in the present research.
Literature Cited
Haensel, V.; Saddison, G. E. Adu. Catal. Reforming, 7th World Pet.
Congresss 1967, 4 , 113-119.
Mckenna, W . L.; Owen, G. H.; Mettick, G. R. Oil Gas J. 1964,62(20),
106-111.
Saito, K.; Shimizu, S. Petrotech (Tokyo) 1985, 8(1),54-60.
Symoniak, M. F.; Frost, A. C. Oil Gas J. 1971, (March 15),76-81.
Received for review May 13, 1988
Revised manuscript received November 9, 1988
Accepted December 11,1988