Sekiyu Gakkaishi, 28, (5), 427-429 (1985) 427

Visbreaking Reaction of Atmospheric Residue (Part 5)

Structural Analysis and Reaction Mechanism
for Khafji Atmospheric Residue

Hajime YOSHIDA1), Kagoto NAKAGAWA, Shinichiro SUHARA2),

Takashi TATSUMI*, and Hiro-o TOMINAGA

Department of Synthetic Chemistry, Faculty of Engineering, The University of Tokyo

7-3-1, Hongo, Bunkyo-ku, Tokyo 113
1) Present address: Mitsubishi Oil Co., Ltd., 4-1, Ogimachi, Kawasaki 210

2) Present address: JGC Corporation, 1-14-1, Bessho, Minami-ku, Yokohama 233

(Received January 28, 1985)

Atmospheric residue from Khafji crude was subjected to thermal cracking at 420-460

in the presence of a diluent, namely, nitrogen, hydrogen, or tetralin as a hydrogen donor. The
feed and the product residues were separated into six fractions. The Khafji feed has the larger
share of asphaltenes and the smaller share of saturates and monoaromatics, compared with the
three other feeds, namely, Arabian Heavy, Iranian Heavy and Taching. The yield and struc-
tural change of the six fractions by thermal cracking were accounted for by the mechanism con-
sisting of unimolecular decomposition and radical chain reaction.

1. Introduction
Atmospheric residues from four topped crudes,
namely, Arabian Heavy, Iranian Heavy, Taching
and Khafji were subjected to thermal cracking at
420-460 in the presence of a diluent: nitrogen,

hydrogen or tetralin at 50kg/cm2. The details of

the yield of cracked distillate (343-) and some

physicochemical properties of the product residues

have been reported elsewhere.1) Observations on
Khafji atmospheric residue are summarized as fol-
lows. The Khafji topped crude was markedly sus-
ceptible to thermal cracking. The yield of distil-
: Feed : N2 : H2 : Tetralin
late, in which the share of kerosence was relatively
Fig. 1 Fraction Distribution in AR of Khafji Feed and
large, was 22wt%, at best. Significant changes in Its Visbroken Product
physicochemical properties of the visbroken residues
were observed, namely, the decrease in viscosity oil, the apparatus and reaction conditions employed
and the increase in Conradson carbon. for visbreaking, details concerning separation and
In order to gain some insight into the structures structural analysis of the feed and product oils have
of Khafji residue and its visbreaking reaction mech- been described previously.1),2)
anism, detailed structural analysis of the feed and
its visbroken product was carried out. Similar 3. Results and Discussion

studies on Arabian Heavy2), Iranian Heavy3), and 3.1 Distribution of Fraction

Taching4) residues have been described in the pre- Atmospheric residues (AR, 343+) of the feed

vious respective papers. and the product were separated by solvent extrac-
tion and subsequent column chromatography. In
2. Experimental Fig. 1, the proportions (wt% based on oil) of the
Inspection of general properties of Khafji feed fractions of Sa (saturates), MA (monoaromatics),
* To whom correspondence should be addressed. DA (diaromatics), TA (triaromatics), PP (polyaro-

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 428

a,a': Depolymerization
b-1: Cleavage of C-C bonds in alkyl groups
b-2: Cleavage of C-C bonds in paraflins
c: Dehydrogenation of naphthenic rings
d: Polymerization

Fig. 3 Visbreaking Pathways of Khafji Atmospheric

Residue

: Feed : N2 : H2 : Tetralin to occur by cleavage of -bonds such as PhCH2-

Fig. 2 Structural Change of Khafji MA Fraction CH2Ph, PhCH2-SPh, and PhCH2-OPh, as was
pointed out in the previous paper.3) For the other
matics and polars), and As (asphaltenes) were plot- aromatic fractions, similar depolymerization was
ted against cracked distillate (D, 343-) yield. also inferred from the similar changes in the struc-
The Khafji feed has the larger share of As and tural parameters.
the smaller share of Sa and MA, compared with In MA, the Cs/C ratio increased and the Ca/Ct

the three other feeds. The yield of the five frac- ratio decreased by visbreaking. This is peculiar to
tions derived from maltenes decreased rather lin- MA and DA of Khafji. Carbon-carbon bond scis-
early with increasing severity, while the yield of As sion in alkyl side chains should result in the dimuni-
increased slightly in the advanced stage. The de- tion of Cs/C and the growth of Ca/Ct, which was

crease in the PP fraction was pronounced. Diluents actually the case for the TA and PP fractions.
do not seem to affect greatly the yield of each However, if the aromatic molecules with short alkyl
fraction. side chains formed by visbreaking were eliminated
3.2 Structural Change of Fractions as D, the average chain length of the molecules
Extensive structural analyses of AR fractions from (Cs/C) remaining in the residue could become
the feed and the product oils were performed ac- relatively long.
cording to the procedures described in the previous 3.2.3 Asphaltenes
papers.2),3) The following observations were made. The average molecular weight Mn of Khafji As
3.2.1 Saturates is relatively large. It was reduced from 3,500 for
The Cn/Ct ratio of Khafji feed Sa is 0.133, which the feed to 2,800-1,800 for the visbroken products.
is much smaller than that of Sa of Arabian Heavy The unit sheet weight was scarcely changed during
(0.234) and Iranian Heavy (0.208) feeds. The aver- visbreaking, while the degree of polymerization was
age molecular weight Mn and Cn/Ct of Sa slightly reduced from 3.4 to 2.9-2.1. This suggests the
decreased with increasing cracking severity, as was depolymerization by scission of some weak bonds
observed on Iranian Heavy residue.3) The decrease of carbon chains connecting unit sheets, as has
in Cn/Ct could be due to dehydrogenation of naph- been already proposed.2),3)
thenes to produce aromatics.
3.2.2 Aromatics 3.3 Reaction Mechanism
Fig. 2 illustrates the changes in the structural The observations and discussions described above
parameters of the MA fraction. The values of un- lead to the formulation of a reaction scheme shown
saturation number USN and peripheral carbon in Fig. 3. "Polymeric Aromatics" mean aromatic
number Cp of the feed MA exceeded the values molecules in which carbon chains connect two or
calculated for benzene derivatives, namely 4 and more aromatic sheets, including asphaltenes.
6, respectively. Upon visbreaking, USN and Cp In the initial stage of the reaction, unimolecular
were reduced to the calculated values and Mn de- decomposition of the polymeric aromatics at its
creased, suggesting the decomposition of polym- weak bonds takes place to give radical fragments.
erized aromatics to give monomeric aromatic com- The radicals are stabilized by abstracting hydrogen
pounds. This was also observed on the Arabian atoms from hydrogen-donating compounds such as
Heavy and Iranian Heavy residues and considered naphthenes in the feed and tetralin when added.

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 429

Some of the stabilized fragments are transformed
directly to D fraction (a'). However, in com-
parison with the Iranian Heavy feed, the Khafji
feed contains smaller share of MA which would
produce D most easily by the a' route among all
the aromatic fractions. This may account for the
finding that the yield of D is smaller than that in
the case of Iranian Heavy. Hydrogen abstraction
from the naphthenic compounds in saturates will
lead to the formation of aromatics (c). In the case
of Khafji, this path should be insignificant in view
of the small Cn/Ct ratio of Sa. The naphthene
content in the Khafji aromatic fractions is also
relatively small as shown in Fig. 2. This could
result in the stabilization of the radicals by ab-
stracting hydrogen from alkyl side chains, which
may produce distillates (b-1).
In the advanced stage of cracking, the scission
of alkyl chains in aromatics (b-1) and paraffins
(b-2) by way of radical chain mechanism together
with undesirable polymerization and/or condensa-
tion of aromatics (d) may prevail, since hydrogen-
donating compounds are deficient.
References
1) Tominaga, H., Tatsumi, T., Yoshida, H., Suhara, S.,
Ihori, S., Nakasuka, A., Sekiyu Gakkaishi, 27, (5), 399
(1984).
2) Yoshida, H., Ishikawa, K., Suhara, S., Tatsumi, T.,
Tominaga, H., Sekiyu Gakkaishi, 27, (5), 406 (1984).
3) Suhara, S., Tatsumi, T., Yoshida, H., Tominaga, H.,
Sekiyu Gakkaishi, 28, (1), 90 (1985).
4) Tatsumi, T., Nakasuga, A., Yoshida, H., Suhara, S.,
Tominaga, H., Sekiyu Gakkaishi, 28, (4), 318 (1985).

(5)

1), , 2), ,

, 113 7-3-1
1) : (), 210 4-1
2) : (), 233 1-14-1

, (Fig. 2)
, , , ,

2) , (D), (343+, AR) , Fig. 3
, AR (Sa), (MA), (a, a')
(DA), (TA), (PP), , MA
(As) ,
, ,

, AR (c), (b-1) ,
, As , (c)

(Fig. 1) (Cp), (USN) (d) , b-1, (b-

(Mn) , , 2)
MA, DA, TA -

Keywords

Hydrogen donor, Khafji crude, Reaction mechanism, Structural analysis, Thermal cracking, Visbreaking

Sekiyu Gakkaishi, Vol. 28, No. 5, 1985