Aspholtenes rind Avphriln. 2.

Developnients in Perrrileuni Science, 40 B

edited by T.F. Yen and G.V. Chilingarian
0 2000 Elsevier Science B.V. All rights reserved 28 1

Chapter I0

CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF

CHINESE CRUDE OILS
WENJIE LIANG, GUOHE QUE, YUEZHU CHEN and CHENGUANG LIU

INTRODUCTION

Most of the Chinese crude oils are quite heavy, with a content of vacuum residues up
to about 40-50%. The heavy crudes recently produced have vacuum residue contents as
high as 60% or more. In China, because of the deficiency of petroleum, it is undesirable
to bum the residue directly. A considerable market of asphalt does exist, but it accounts
for only a small portion of the residue. Thus, great attention should be paid to the
upgrading of residue for meeting the increasing demand of light fuels. Inasmuch as the
properties and composition of various residues are quite different, it is necessary to have
a thorough understanding of them.
The residue of a crude oil is the fraction that has the highest boiling point, the highest
molecular weight, the highest contents of heteroatoms, and the most complex structure.
In the last several decades, many authors have been working fruitfully in this area [ 1-81.
In this chapter, the characterization of the vacuum residues from the Chinese crude oils
is reported.
For the separation of the residues, adsorption chromatography, ion-exchange chro-
matography, gel permeation chromatography, and solvent treatment are generally used
[9-121. The authors have used the adsorption chromatography with alumina as the main
separation technique [ 131.
Since the publication of the methods of Brown and Ladner [ l] and Williams [6],
average structural parameters based on nuclear magnetic resonance (NMR) spectra have
been widely used for the quantitative characterization of average residue structure. The
authors have obtained a series of structural parameters of the residues and their fractions
of the Chinese crude oils by the modified Brown-Ladner method with NMR spectra,
elemental composition, and average molecular weight [2].

EXPERIMENTAL RESULTS

Samples

The vacuum residues of twelve crude oils were used. Among them, Daqing, Renqiu,
and Zhongyuan crude oils are paraffinic, Shengli, Linpan, and Dagang crude oils
are intermediate, Gudao, Gaosheng, Xinjiang (Region No. 9), and Jinglou crude oils
are naphthenic-intermediate, and those of Shanjiasi and Huanxiling are naphthenic.
Properties of these crude oils are presented in Table 10-1.
282 W.-J. I.IAN(i. G.-li. ()LIE. Y:Z. CllEN ANDC.-G. LIU

TABLE 10-1

Properties of Chinese crude oils

Name of Gravity "API S N Ni V Wax Fraction ( w t 8 )

crude SG (Wt%) (wt8'c) (PPm) ( P P m (wt%r) <2*00C 20@350OC 35@500"C ,500"C
('I?')
Daqing 0.8554 33.1 0.10 0.16 3.1 0.04 26.2 11.5 19.7 26.0 42.8
Renqiu 0.8792 28.7 0.31 0.38 15.0 0.73 22.8 7.3 21.1 32.4 39.2
Zhongyuan 0.8466 34.8 0.52 0.17 3.3 2.4 19.7 19.4 25.1 23.2 32.3
Shengli 0.8829 28.0 0.73 0.44 30.0 1.8 15.8 7.6 27.0 23.0 42.4
Linpan 0.9004 25.7 0.34 0.12 - 0.1 12.2 12.0 20.5 25.0 42.5
Dagang 0.8697 30.4 0.13 0.24 7.0 0.1 11.6 14.5 24.0 28.8 32.7
Gudao 0.9495 17.0 2.09 0.43 21.1 2.0 4.9 6.1 14.9 27.2 51.8
Gaosheng 0.9472 17.3 0.56 1.06 122.5 3.1 5.8 5.6 10.6 19.7 64.1
Xingjiang" 0.9273 20.5 0.15 0.35 15.4 0.7 7.4 1.7 18.3 28.7 51.3
Jinglou 0.9531 16.4 0.32 0.74 22.2 3.3 9.6 0.3 9.1 33.2 57.4
Shanjiasi 0.9731 13.8 0.82 0.72 51.3 2.5 1.9 1.7 11.5 21.2 65.6
Huanxiling 0.9434 17.9 0.26 0.41 38.4 0.5 2.3 3.7 20.6 35.4 40.3

'' Xingjiang, Region No. 9.

Residue
I
I
ti-Heptane

I I
Heptane Soluble Heptane Insoluble
paltenes) (Asphaltenes)
I
I
I
I
Neutral Alumina Chromatography
(1% Water)
I
I
I 1 I
I I I
n-Heptane Benzene BenzeneEthanol
I I (5050)
I I I
I I I
Saturates Aromatics Resins
Fig. 10-1. Separation scheme for residues.

Separation methods

SARA method. The asphaltenes were precipitated by n-heptane. The maltenes ob-
tained were chromatographed on the alumina with 1% water. The saturated, aromatic,
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 283
Residue
I
I
I
n-Pentane
I

I I
Pentane Soluble Pentane Asphaltene
I
I
Neutral Alumina Chromatography
(5% Water)
I
I

n-C, n-C,&mne n-C,/Benzene Benzene BenzendAlcohol

I (85:15) (5O:SO) (5O:SO)
I I I I I
I I I I I
Fraction 1 Fraction 2 Fraction 3 Fraction 4 Fraction 5
I I Light Resins Middle Resins Heavy Resins
I I
I I
I
I
Neutral Alumina Chromatography
(1% Water)
I
I I I I
I I I I
n-C, n-C,/Benzene n-C,/Bemne Benzene
I (85:lS) (5O:SO) I
I I I I
I I I I
Saturates Light Aromatics Middle Aromatics Heavy Aromatics
Fig. 10-2. Separation scheme of residues, aromatics and resins.

and resin fractions were eluted by n-heptane, benzene, and a mixture of benzene and
ethanol (50/50, v/v), respectively. The separation scheme is shown in Fig. 10-1.
Separation of aromatics. The aromatic fractions obtained by the SARA method were
further fractionated into so-called light, middle, and heavy aromatic subfractions, which
roughly correspond to the mono-, di-, and polyaromatics, by gradient elution with mixed
solvents, i.e., n-heptanelbenzene (95/5, v/v), n-heptanelbenzene (85/15, v/v), and
benzene, respectively, on the alumina column with 1% water.
Separation of resins. The resin fractions were separated into three subfractions, i.e.,
light, middle, and heavy resins, by the chromatography on the alumina column with 5%
water [ 131. The separation scheme is shown in Fig. 10-2.
284 W:J. LIANG. G.-ll. QUE. Y:%. CIIEN ANDC.-G LIU

TABLE 10-2

Assignments of proton bands in the NMR spectra chemical shift

Symbol Range Assignment

(ppm, from TMS)
HA 6.&9.0 Aromatic hydrogens
Ha 2.w.0 Hydrogens in saturated groups c( to aromatic rings
Hfi 1SL2.0 Hydrogens of methylene and methine groups or further to aromatic rings,
and hydrogens in p-methyl groups
HY 0.5-1 .0 Hydrogens in methyl groups y or further removed from ammatic rings

Separation of waxes. The dewaxing of the samples was carried out with a mixture of
2-butanone and toluene (50/50, v/v) at -20°C. The ratio of solvent to sample was 30 : 1
(ml/g).
Gel permeation chromatography (GPC). The aromatics and resins were separated
into fractions according to their molecular size using a GPC column with silylated silica
as packing. The eluent used was benzene with 10% methanol.
Supercritical Jluid extraction. The Shengli residue was fractionated by supercriti-
cal fluid extraction with pentane as a solvent at constant temperature with pressure
programming.

Elemental analyses

The determination of C, H, and N was carried out with a Carlo Erba microanalyzer.
The nickel and vanadium contents were measured by an atomic absorption spectrometer
after sample digestion.

Average molecular weight

The molecular weights were determined by a Knauer vapor phase osmometer in

benzene at 45°C.

Nucleur magnetic resonance spectroscopy

The 'H-NMR spectra were run in CCIa solvent with TMS as an internal standard us-
ing an RMN-250 Spectrometer. The spectra were divided into four bands as described in
Table 10-2, and the area under each band was determined by integration. The I3C-NMR
spectra were obtained on a WP-80 spectrometer using inverse-gated decoupling to
suppress NOE. The distortionless enhancement by polarization transfer (DEPT) pulse
sequence has been applied for the measurement of CH,, group abundances in residue
and its fractions.

Infrared spectroscopy

For IR, the samples were applied as films from CHCll solution. The spectra were com-
pared by making the relative intensity measurements of the 1460 and 1380 cm-' bands.
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 285

X-ray di'raction

Powder X-ray diffraction of asphaltenes was performed on a diffractometer, equipped

with a divergent I"-slit and a receiving 0.3-mm slit. The scanning rate was 2"/s, and
scanning width 2 0 = 5-105".

METHOD OF CALCULATION OF STRUCTURAL PARAMETERS

To simplify the calculation, it was assumed that the hydrogen to carbon atom ratio
of the saturated part of the average molecule of the samples equals 2 ( x = y = 2),
and the aliphatic quaternary carbons are absent in the chemical structure. As shown
in Table 10-3 [14], the first assumption has been confirmed by the DEPT "C-NMR
technique. The DEFT subspectra also show that the content of aliphatic quaternary
carbon in residue is negligible. Besides, the heteroatoms have not been considered
in calculation. The definitions of the symbols used in the calculations are listed in
Table 10-4.

Structural parameters by the modijied Brown-Ludner method

Based on 'H-NMR spectra (HAIHT,HJHT, HBIHT,H,IHT), %C, %H, and average

molecular weight, the average structural parameters of the residues and their fractions
were calculated by the following equations:

fA =
CIH - (Ha + Hfi + H,) / ~ H T (10-1)
CIH

( 10-2)

TABLE 10-3

H/C atom ratio of the structured part ( H s J C s )of vacuum residues and their fractions

Name of residue Fraction HslCs by DEPT H s / C s hy I3C and 'H-NMR

Daqing Residue I .97 2.03
Aromatic 1.97 2.14
Resin I .94 2.03
Shengli Residue 1.99 2.02
Aromatic 2.01 2.04
Resin 1.94 2.05
Gudao Residue 2.00 1.96
Aromatic 1.95 1.98
Resin 1.98 2.07
Huanxiling Residue 1.99 1.99
Aromatic I .97 1.99
Resin I .97 2.01
286 W:J. I.IANG. G -H. Q l ' t , Y:Z. C H E N A N D C . - G . LlU

TABLE 10-4

Designation of symbols 'I

Symbol Designation

CT Total number of carbon atoms in molecule

H-r Total number of hydrogen atoms in molecule
CA Number of aromatic carbons in molecule
CN Number of naphthenic carbons in molecule
CI, Number of paraffinic carbons in molecule
cs Number of saturated carbons in molecule
C, Number of carbons CY to aromatic rings
M Average molecular weight
n Number of unit structures in molecule
usw Unit structure weight
.fA Fraction of aromatic carbon
.fN Fraction of naphthenic carbon
f P Fraction of paraftinic carbon
R.1 Total number of rings in molecule
RA Number of aromatic rings in molecule
RN Number of naphthenic rings in molecule
I 1CA
HAL Hydrogen to carbon atom ratio of the hypothetical unsubstituted aromatic system
U Degree of substitution of the aromatic ring
L Average length of side chain (Cp/nCHq)

When symbols have an asterisk they represent the parameters for the unit structure in an average molecule.

( 10-3)

C A = CTfA ( 10-4)

RA = (CA- 2)/4 (for catacondensed aromatic system) ( 10-5a)

RA = (CA- 4)/3 (for pericondensed aromatic system) (10-5b)

RT = c~f 1 - H T /-
~CA/~ ( 10-6)

R N = RT - R A ( 10-7)

CN = ~ R N(for catacondensed 6 - membered ring system) ( 10-8a)

CN = ~ R N(for pericondensed 6 - membered ring system) (1 0-8b)

c s = CT - C A ( 10-9)

c p = cs - C N (10-10)

fN =CN/CT (10-1 1 )
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 287

fP =cP/cT (10-12)
The aromaticity fA can also be obtained from the H/C atom ratio using the empirical
equation, obtained by the authors, without important deviation [ 151:
fA = 1.132 - 0.560(H/C) (10-13)
In view of their high H A U / C A and the low molecular weight, it can be considered that
there exists only one catacondensed aromatic nucleus in molecules of aromatic fractions.
The molecules of the resins and the asphaltenes with large average molecular weights
are assumed to be composed of more than one substituted pericondensed nucleus, i.e.,
there are several unit structures in each average molecule of these two heavier fractions.
The number of the aromatic carbon atoms in each unit structure (Cl) of the resin or the
asphaltene molecule was calculated from HA"/ CA by the following equation, derived
by the authors, for the most compact pericondensed aromatic systems:

(10-14)

Then, the number of the unit structures per molecule (n) and the unit structure weight
(USW) can be obtained by the equations:
n =CA/Ci (10-15)

USW = M/n (10-16)

In this chapter, all the structural parameters of the resin and the asphaltene fractions
are given by unit structure, not by average molecule, and all the parameters of the unit
structure are denoted by symbols with an asterisk.

Average side chain length ( L ) based on IR

With the normal paraffinic model compounds, it was found that there is a linear rela-
tionship between the relative intensities of the 1460 and 1380 cm-' bands (A 1460/A 1380)
and the ratio of methylene to methyl group (nCH2InCH3) in the molecule. The relation-
ship is as follows:
nCH2/nCH3 = 2.93Al460/A1380 - 3.70 (10-17)
Assuming x = y = 2, the number of methyl groups in a molecule can be obtained by
the equation:
nCH3 = Cs/(nCHz/nCH3 + 2) (10-18)
Besides, the number of the methylene and the methyl groups in an average molecule
of samples have also been determined by 13C-NMR spectroscopy using the DEPT
technique. As shown in Table 10-5 [3], it is interesting that the results obtained using
these two different methods are very similar.
In this chapter, the number of side chains of the average molecule is considered to be
equal to nCH3, and the average chain length ( L ) is defined as CpInCH3. It appears that
the parameter Cp/nCH3 would be more representative than the parameter Cs/C,, which
is commonly used for the designation of the average chain length.
288 W.-J. L.IAN(;. G.-H QUE. Y -Z. CHEN AND C.-Ci. LIU

TABLE 10-5

nCH: and nCHl obtained by different methods

Name of residue Fraction DEPT method IR method

nCH2 nCHj nCH: nCH7
Daqing Residue 49.4 6.5 49.6 7.4
Aromatic 55.4 7.8 57.7 7.9
Resin 30.6 4.7 29.6 5.7
Shengli Residue 37.6 8.0 37.0 8.4
Aromatic 34.6 7.2 33.5 7.8
Resin 24. I 5.6 25.0 6.1
Gudao Residue 41.3 8.6 38.6 9.9
Aromatic 30.0 6.0 30.2 7.2
Resin 21.6 4.7 21.3 5.2
Huanxiling Residue 25.8 6.8 22.1 8.2
Aromatic 19.8 5.5 19.8 6.2
Resin 25.2 8.4 28.5 7.3

For resins, the parameters in each unit structure are listed.

TABLE 10-6

Elemental composition and properties of vacuum residues

Nameof C H S N H/C Ni V M Carbon Average

residue (wt%) (wt%) (wt%) (wt%) atom (ppm) (ppm) (VPO) residue molecular formula
ratio (wt%)
Daqing 87.0 12.7 0.14 0.53 1.74 8.5 0.1 1120 11.9
Renqiu 86.2 11.6 0.76 1.08 1.60 59.0 1.2 I140 18.6
Zhongyuan 85.6 11.6 1.18 0.60 1.61 15.0 5.7 1100 19.6
Shengli 84.4 11.6 1.95 0.92 1.63 47.8 4.0 I080 15.4
Linpan 87.2 11.8 0.60 0.80 1.61 36.0 - I000 16.7
Dagang 86.3 11.8 0.29 0.57 1.63 25.8 0.5 870 9.2
Gudao 86.5 10.8 2.86 1.18 1.49 35.2 4.4 I030 19.2
Gaosheng 85.8 11.4 0.77 1.19 1.58 144.8 5.0 I020 17.4
Xingjiang 86.9 11.7 0.45 0.79 1.61 34.3 1.3 I340 -

Jinglou 86.5 11.6 0.65 1.18 1.60 42.3 5.1 I170 16.2
Shanjiasi 86.0 10.8 0.87 1.42 1.50 67.7 - 960
Huanxiling 86.3 10.7 0.57 0.88 1.48 120.7 4.1 I030

Xingjiang Region No. 9.

RESULTS AND DISCUSSION

Elemental composition of residues

According to Table 10-6, the carbon contents of the residues studied are in the range
of 85% to 87%, and the hydrogen contents in the range of 11% to 13%. Their H/C
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 289

atom ratios are moderate, mostly in the range of 1.5 to 1.7. Most of the residues are not
refractory enough to be upgraded.
Unlike the crudes in many other countries, the sulfur content of the residues of most
Chinese crudes is not high, usually being below 2%, whereas their nitrogen content is
relatively high, about 1%. In reference to the number of atoms in the average molecule,
the number of nitrogen atoms is more than that of sulfur in most cases, and there exists
about one atom of nitrogen per molecule of residue. Since most of the nitrogen is in
heterocyclic structures with an aromatic character, it is more stable and more difficult to
remove than sulfur during upgrading.
The contents of nickel and vanadium in Chinese residues are moderate, and without
exception the nickel content is much higher than the vanadium content. Usually, the
nickel content is several tens of ppm, whereas the vanadium content is only several ppm.
The Ni/V ratios are higher than 10 in most cases, which is one of the peculiarities of the
Chinese residues.
The average molecular weight determined by the VPO method is about 1000 for all
the residues, containing 70-90 carbon atoms per molecule.
As shown by geochemists, such as Tissot and Welte [16] and Hunt [17], the metal
contents in the low-sulfur crude oils are generally low, and their nickel content exceeds
that of vanadium. It was also discovered that there is a good constant correlation between
the sulfur content and the vanadium content. This is also true for Chinese crudes.
Moreover, the low sulfur content, low metal content, and very high Ni/V ratio for most
of the Chinese residues indicate that they are derived from continental organic matter.

SARA composition

In Table 10-7, it is clear that the contents of saturates of residues differ widely, from
15.7% to 40.8%, but the aromatics content remains about 30% for all residues studied.
It should be emphasized that for most of the Chinese residues the resin content is very
high, up to 50%, and there is a low content of heptane asphaltene, usually below 1%.
The wax contents of vacuum residues, which are presented in Table 10-7, were
obtained by dewaxing the saturated and aromatic fractions separately. It is shown that
the contents of wax are quite different: 30.7% for Daqing and only 5.4% for Huanxiling
residues. The ratios of the wax content in the saturated fraction to the wax content in
the aromatic fraction are also different. As for Daqing residue, 70% of wax is present in
the saturated fraction, whereas the waxes are equally distributed in the two fractions of
Gudao and Huanxiling residues.
The data presented in Table 10-8 show that the contents of light, middle, and heavy
aromatic subfractions range from 17.8% to 26.9%, 17.5% to 23.6%, and 53.5% to
64.7%, respectively, i.e., more than one half of the aromatics in residues are polynuclear.
There are more light aromatics in the Daqing residue, while there are more heavy
aromatics in the Gudao and Renqiu residues.
Inasmuch as the resins content constitutes about half of the residues, it is necessary to
separate them into subfractions for further characterization. The data in Table 10-9 show
the difference in the composition of the resins. In Daqing residue, there is more light
resin (42.0%) and less heavy resin (34.9%), whereas there is less light resin (24.3%)
290 W J LIANG. G -H QUE. Y -Z CHEN A N D C -G LIU

TABLE 10-7

SARA composition and wax content of vacuum residues

Name of Saturate Aromatic Resin Heptane Pentane Wax content (wt%)

residue (wt%) (wt%) (wt%) asphaltene asphaltene
(wt%) in saturate in aromatic total
(wt%)
Daqing 40.8 32.2 26.9 10.1 0.4 21.5 9.2 30.7
Renqiu 19.5 29.2 51.1 0.2 10.1 - -

Zhongyuan 23.6 31.6 44.6 0.2 15.5

Shengli 19.5 32.4 47.9 0.2 13.7
Linpan 21.2 31.7 44.0 3.1 13.8
Dagang 30.6 31.6 37.5 0.3 -

Gudao 15.7 33.0 48.5 2.8 11.3 4.2 4.1 8.3

Gaosheng 22.6 26.4 50.8 0.2 11.0 2.4 4.4 6.8
Xingjiang ‘I 28.2 26.9 44.8 <O.l 8.5 4.4 2.7 7.1
Jinglou 14.3 34.3 51.3 0. I 5.4 2.6 10.0 12.6
Shanjiasi 17.1 27.0 53.5 2.4 17.0 0.9 2.1 3.0
Huanxiling 28.7 35.0 33.6 2.7 12.6 2.6 2.8 5.4

J Xingjiang Region No. 9.

and more heavy resin (60.8%) in Zhongyuan residue. Undoubtedly, the composition of
resins will influence the processing of residues.
These separation data can be divided into eight fractions of residue (i.e., saturates;
light, middle, and heavy aromatics; light, middle, and heavy resins; and asphaltene)
(Table 10-10).
It is known that most of the Chinese crude oils have high wax contents (see
Table 10-1), and their resin contents are high as well. Several geochemists have reviewed
the probable environment of origin of some 500 high-wax crude oils worldwide and
have shown their occurrence to be genetically related to continental or near-shore
depositional facies. The high wax content is an inheritance from land-derived organic
matter as lipids of terrestrial higher plants and of microbial organisms.
Tissot and Welte [16] and Hunt [I71 have shown that there is a strong positive
correlation between the sulfur content and resin-asphaltene content for more than 300

TABLE 10-8

Subfractions of aromatics of vacuum residues

Name of residue Light aromatics Middle aromatics Heavy aromatics

(wt%) (wt%) (wt%)
Daqing 26.9 19.5 53.6
Renqiu 18.4 17.8 63.8
Zhongyuan 22.9 23.6 53.5
Shengli 23.7 21.1 55.2
Linpan 20. I 16.6 63.3
Gudao 17.8 17.5 64.7
Huanxiling 23.2 18.3 58.5
CHEMICAL COMPOSITION A N D CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 29 1

TABLE 10-9

Subfractions of resins of vacuum residues

Name of residue Light resins Middle resins Heavy resins

(Wt%) (wt%) (wt%)
Daqing 42.0 23.1 34.9
Renqiu 27.9 17.6 54.5
Zhongyuan 24.3 14.9 60.8
Shengli 30.0 16.3 53.7
Linpan 37.4 18.2 44.4
Gudao 34.5 17.7 47.8
Gaosheng 26.7 18.4 54.9
Xingjiang a 33.6 16.0 50.4
Jinglou 34.4 19.6 46.0
Shanjiasi 31.6 17.8 50.6
Huanxiling 38.9 20.9 40.2

Xingjiang Region No. 9.

TABLE 10-10

Eight-fraction composition of vacuum residues

Name of Saturates Light Middle Heavy Light Middle Heavy Pentane

residue (wt%) aromatics aromatics aromatics resins resins resins a asphaltenes
(wt%) (wt%) (wt%) (Wt%) (Wt%) (wt%) (Wt%)
Daqing 40.8 8.9 6.5 17.4 11.1 6.1 8.8 0.4
Renqiu 19.5 5.4 5.3 18.9 14.1 8.9 17.7 10.1
Zhongyuan 23.6 6.1 6.0 14.3 12.1 7.4 15.0 15.5
Shengli 19.5 7.8 6.9 18.3 14.2 7.7 11.9 13.7
Linpan 21.2 6.5 5.3 20.4 15.8 7.7 9.3 13.8
Gudao 15.7 6.2 6.1 22.8 16.0 8.2 13.7 11.3
Shanjiasi 17.1 6.3 4.9 15.9 16.9 9.5 12.4 17.0

Including the heavy resins in pentane maltenes.

crude oils worldwide. This is not the case for most Chinese crudes, which have a low
sulfur content and high resin content.
In addition, because most of the nitrogen in crude oils is concentrated in the resin
fractions of residues, there exists a good correlation between nitrogen and resin content.
Table 10-11 shows that for most of the Chinese residues, the nitrogen to resin ratios are
very close, ranging from 0.018 to 0.026.

AVERAGE STRUCTURAL PARAMETERS OF VACUUM RESIDUES AND THEIR FRACTIONS

Residues

The average structural parameters of the Chinese residues are listed in Table 10-12.
It is shown that for Daqing residue the aromaticity f~is the lowest (0.16) and the paraf-
292 W - J L1ANG.G-ll QUI: Y - L CHENANDC G LIU

TABLE 10-1 I

Ratio of nitrogen content to resin content (N/R) of vacuum residues

Name o f residue Nitrogen (wt%) Resins (wt%) N/R x 100

Daqing 0.53 26.9 1.96
Renqiu 1.08 51.1 2.11
Zhongyuan 0.60 44.6 I .35
Shengli 0.92 47.6 1.92
Linpan 0.80 44.0 I .82
Gudao 1.18 48.5 2.43
Gaosheng 1.19 50.8 2.34
Xingjiang a 0.79 44.8 I .76
Jinplou 1.18 51.3 2.30
Shanjiasi 1.42 53.5 2.65
Huanxiling 0.88 33.6 2.62

'' Xingjiang Region No. 9.

TABLE 10-12

Structural parameters of vacuum residues

Daqing 0.16 0.11 0.73 5.2 3.0 2.2 1.3 0.69 0.52 6.6
Renqiu 0.23 0.18 0.59 7.8 4.2 3.6 1.2 0.57 0.29 5.1
Zhongyuan 0.23 0.16 0.61 7.1 4.0 3.1 1.3 0.62 0.44 -
Shengli 0.22 0.17 0.61 6.3 3.2 3.1 1.0 0.74 0.50 4.7
Linpan 0.23 0.18 0.59 6.7 3.5 3.2 1.1 0.70 0.55 4.3
Gudao 0.29 0.23 0.48 9.2 4.9 4.3 1.1 0.57 0.35 3.7
Xingjiang I' 0.23 0.14 0.63 9.0 5.6 3.4 1.7 0.58 0.53 3.9
Huanxiling 0.30 0.22 0.48 9.2 5.1 4.1 1.2 0.67 0.45 3.7
Xingjiang Region No. 9.

finity f p is the highest (0.73), whereas for the Huanxiling residue the f~is the highest
(0.30) and the f p is the lowest (0.48). The distribution of carbon atoms in different struc-
tures might reflect the average chemical nature of the residues. In their ring system, the
total number of rings ( R T )ranges from 5 to 9, the number of aromatic rings ( R A )from
3 to 6, and the R A / R Nratios are slightly higher than 1. The average side chain length L
is the longest for Daqing (6.6)and the shortest for Gudao and Huanxiling residues (3.7).

Saturates

Data in Table 10-13 show that the saturates are the fractions of the lowest molecular
weight (600-900) in residues, with the average number of carbon atoms about 40-60. It
is clear that the average structure of saturates is also different for crude oils of different
bases. For saturates of Daqing residue, the H/C ratio and fp are the highest, while the
f ~R N , ,and H,/Hp are the lowest. The opposite is true for the saturates of Gudao and
Huanxiling residues.
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 293

TABLE 10-13

Elemental composition and structural parameters and saturated fractions

Nameof C H H/C atom M f~ fp RN Branchiness Average

residue (wt%) (wt%) ratio (VPO) index molecular formula
( H v I HH)

Daqing 85.5 14.4 2.01 880 0.08 0.92 0.8 0.31 Cbl Hi 26
Shengli 85.7 14.2 1.98 650 0.18 0.82 1.6 0.32 CJ~HYZ
Gudao 85.6 13.9 1.94 710 0.25 0.75 2.7 0.39 Cs I H9x
Huanxiling 85.5 13.6 1.90 580 0.35 0.65 3.1 0.41 GIH ~ Y

Aromatics

The elementary analyses data in Table 10-14 show that the aromatic fractions ob-
tained by SARA separation do not comprise the purely aromatic hydrocarbons, but they
do contain a considerable amount of heteroatoms. This may be due to the presence
of heterocyclic structures condensed with the aromatic nuclei. The average molecular
weights of aromatic fractions are 700-1 100, slightly higher than those of corresponding
saturates. The GPC data in Table 10-15 [18] show that the molecular weight range of
aromatics in the Daqing residue is 700-2400, whereas the molecular weight ranges from
500 to 1500 for the other three residues. As mentioned previously, it may be considered
that the average molecule of the aromatic fractions is composed of only one unit struc-
ture. Their average structural parameters are as follows: H/C atom ratio = 1.5 to 1.7,
f A = 0.2 to 0.3, RT = 5 to 6, RA = 2 to4, RN = 2 to 3, RA/RN about 1, and L = 4 to 7.

Resins

Table 10-16 shows that the resin fractions constitute the main nonhydrocarbon part
of residues with high contents of heteroatoms, containing on the average 1.3-2.3 atoms
of nitrogen and 0.2-1.4 atoms of sulfur per molecule. The molecular weights of resins
range from 1100 to 2800, and the average number of unit structures calculated per
molecule is near 2 in most cases. Their structural parameters per unit structure are listed
in Table 10-16. When compared to the aromatics, the resins have a higher fA, Rf, R i ,
and R A / RN ratio, and a lower H/C ratio, fp, and L . The molecular weight distribution
data of resins obtained by GPC are shown in Table 10-17. The resin subfractions with
different molecular weights have been also separated from the fractions of Shengli
residue obtained by supercritical fluid extraction with pentane. The properties of the
resin subfractions of Shengli residue are listed in Table 10-18. As shown, the heteroatom
contents of the subfractions of resin are all high without significant variation. As the
molecular weight of the resin subfraction increases, the H/C ratio decreases, whereas
the aromaticity f A and nickel content increase. The heavy subfraction of resin with
lower H/C ratio and higher aromaticity f~will form more coke during processing. Data
also show that in the subfractions of resin with lower molecular weight the nickel is
mostly combined with porphyrin.
TABLE 10-14

Elemental composition and structural parameters of aromatic fractions

~~~

Nameof C H S N HIC M fA fu f~ Rr RA R\: RAIRu HA(I C A L Average

residue (wt%) (wt%) (wt7c) (wt%) atom (VPO) molecular formula
ratio
Daqing 87.3 12.1 0.31 0.20 1.67 1080 0.21 0.14 0.65 6.5 3.7 2.8 1.3 0.67 0.50 7.1 C ~ ~ J H I ~ISSO
[ J NIOO
Renqiu 85.5 11.5 - 0.41 1.61 830 0.23 0.14 0.63 5.7 3.6 2.1 1.7 0.62 0.50 5.2 C ~ C ) H C J2~~NSIx)
Shengli 85.5 11.6 1.83 0.56 1.63 850 0.23 0.21 0.56 5.6 2.4 3.2 0.8 0.80 0.57 5.3 c h i HsxNo.?qSom
Dagang 87.2 11.4 - 0.55 1.56 670 0.27 0.21 0.52 5.1 2.6 2.5 1.0 0.77 0.49 4.3 CJc,H7bNil:hSy
Gudao 84.7 11.1 3.66 0.44 1.56 760 0.26 0.23 0.51 5.9 2.8 3.1 0.9 0.75 0.59 4.6 C s H x ~ N i~i S x7I I
Huanxiling 87.4 11.0 - 0.93 1.50 640 0.32 0.21 0.47 5.2 2.8 2.5 1.1 0.76 0.44 3.5 C-I~~H~~INOA~SX

r,
f:
cc
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 295

TABLE 10-15

Molecular weight distribution of aromatics in residues (by GPC)

Name of residue GPC fraction number Yield M

of aromatics (wt%) (VPO)
Daqing 1 12.8 2340
2 8.3 1850
3 10.9 1640
4 13.2 1330
5 14.3 1010
6 14.1 850
7 10.3 720
8 15.6 810
Renqiu I 10.9 1440
2 9.4 1190
3 13.3 990
4 16.7 870
5 17.4 770
6 14.2 670
7 18.1 480
Shengli 1 12.1 1420
2 9.7 1130
3 14.7 lo00
4 18.7 780
5 18.1 690
6 12.8 600
7 13.9 650
Gudao I 11.7 1400
2 9.4 1090
3 13.6 960
4 17.4 810
5 18.0 650
6 13.4 590
7 16.4 610

Asphaltenes

Asphaltenes are the fractions with the highest molecular weight and polarity of the
residues. Their H/C atom ratios are the lowest (1.1-1.3), whereas their contents of
heteroatoms are the highest (about 5- 10%).The average molecular weight determined
by the VPO method usually reaches several thousand, partly due to the association of
unit structures of asphaltenes, which consist of condensed polycyclic naphthenoaromatic
nuclei with chains, heteroatoms and metals. The unit structure weights of asphaltenes
calculated from the NMR spectra are about 1000. As shown in Table 10-19, the unit
structure of asphaltenes has the highest fA (0.4-OS), RT (11--18), RA (7-14), and
RA/RN (2-3), and the lowest fp (0.35-0.45), H A U / C A (0.4-OS), and L (3-4) in the
residues. Besides, the crystallite parameters of pentane asphaltenes of Gudao, Shanjiasi
TABLE 10-16

Elemental composition and structural parameters of resin fraction

Name C H S N HIC M n USW f~ fu fp R; R,: R; RAIRN HA,,/CA G L Average molecular

residue (wt%) (wt%) (wt%) (wt%) atom (VPO) formula
ratio
Daqing 86.7 10.6 0.31 0.99 1.47 1780 2.1 850 0.31 0.15 0.54 8.1 5.1 3.0 1.7
Renqiu 86.3 10.4 - 1.42 1.44 2260 1.9 1190 0.32 0.13 0.55 9.6 6.5 3.1 2.0
Zhongyuan 85.4 10.0 - 1.07 1.39 2780 3.0 930 0.35 0.13 0.52 9.1 6.3 2.8 2.3
Shengli 84.3 10.2 1.61 1.44 1.45 1730 2.1 820 0.32 0.15 0.53 7.9 4.9 3.0 1.6
Linpan 86.9 10.4 - 1.40 1.43 1760 2.2 800 0.34 0.14 0.52 7.6 5.1 2.5 1.9 4
L
Dagang 86.3 10.4 - 1.47 1.44 1470 1.7 860 0.32 0.16 0.52 8.5 5.3 3.2 1.7
Gudao 85.8 10.0 3.31 1.49 1.40 1380 1.9 730 0.36 0.17 0.47 7.8 4.8 3.0 1.6
Xingjiang" 87.0 10.1 - 1.22 1.38 1810 2.8 650 0.36 0.16 0.48 7.2 4.6 2.6 1.8
Huanxiling 8.5.9 9.7 - 1.74 1.35 1070 1.1 970 0.37 0.14 0.49 10.6 7.4 3.2 2.3

Xingjiang Region No. 9 I

m

>
z
0
n
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 297

TABLE 10-17

Molecular weight distribution of resins in residues (by GPC)

Name of residue GPC fraction number Yield M

of resins (wt%) (VPQ
Daqing I 5.4 7460
2 12.5 5180
3 15.6 2840
4 17.6 1740
5 18.8 1160
6 17.4 1110
7 12.7 860
Renqiu I 12.8 4630
2 14.1 2770
3 11.0 2030
4 10.8 1680
5 10.8 1470
6 12.0 1200
7 22.0 1160
8 6.5 1080
Shengli I 5.6 4320
2 11.4 2890
3 13.0 1940
4 13.4 1620
5 17.0 1330
6 10.6 1200
7 15.0 1120
8 14.0 1050
Gudao 1 9.2 3310
2 10.0 2340
3 13.7 1550
4 19.6 I350
5 14.4 I290
6 12.2 I070
7 21.0 1020

TABLE 10-18

Properties of resin subfraction of Shengli residue (by supercritical fluid extraction)

No. of Resin yield N Basic nitrogen Ni

subfraction (wt%) (wt%) (wt%) (PPm)
I 9.05 850 1.54 2.82 1.39 0.44 54.5 54.5 0.27
11 12.24 910 1.52 3.28 1.36 0.39 62.3 58. I 0.28
Ill 8.09 1400 1.50 2.99 1.43 0.32 84.1 77.2 0.30
IV 5.84 2000 1.46 2.35 1.49 0.31 98.6 81.9 0.32
V 6.5 1 2880 1.44 2.74 1.48 0.28 89.1 50.5 0.33
VI 58.27 3550 1.30 2.24 1.76 0.28 112.4 9.4 0.40
TABLE 10-19

Elemental composition and structural parameters of heptane asphaltenes

Name of C H S N H/C M n USW .f.\ ,fx ff, R; R,: R; R,A/Rs H.aLl/C,\ IJ L Average molecular
residue (wt%) (wt%) (wt%) (wt%) atom (VPO) formula
ratio
Shengli 84.1 9.0 2.27 1.73 1.28 3410 3.9 870 0.41 0.17 0.42 10.5 7.1 3.4 2.1 0.51 0.54 4.3 C?~C)H~~.IS?.-~NI?
G U ~ O 81.0 7.8 7.37 1.36 1.16 5620 5.8 980 0.47 0.18 0.35 13.5 9.5 4.0 2.4 0.46 0.57 3.4 C?~~H-~~~SIZCIN~~
Shanjiasi 85.1 9.0 1.53 1.86 1.27 9730 10.5 930 0.42 0.16 0.42 11.3 7.9 3.4 2.3 0.48 0.46 2.9 Ch~yH~hyS.17N124
Huanxiling 87.4 8.2 - 1.90 1 . 1 1 6660 5.3 1260 0.50 0.12 0.38 18.5 14.0 4.5 3.1 0.37 0.45 4.0 C~s?H?j:SxNsn
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 299

TABLE 10-20

Crystallite parameters of pentane asphaltenes (by XRD)

Sample & (A) Lc (A, L, (A) Me

Cs-asphaltene of Gudao residue 3.56 20.8 1131 5.8
Cs-asphaltene of Shanjiashi residue 3.56 19.1 13.7 5.4
Cs-asphaltene of Xingjiang gilsonite 3.56 18.4 15.4 5.2

residues and Xinjiang gilsonite have been obtained based on XRD spectra using Yen’s
method [19]. Table 10-20 [20] shows that the interlayer distance ( d ~of) the asphaltene
crystallite is 3.56 A. The average size of the aromatic cluster perpendicular to the plane
of the sheets ( L , ) is about 20 A; the average diameter of the aromatic sheets ( L a )ranges
from 11.9 to 15.4 A, and the effective number of aromatic sheets associated in a stacked
cluster ( M e )is 5-6.

Wares
The structural parameters and other properties of the waxes from the saturate and
aromatic fractions of Daqing and Gudao residues are presented in Table 10-21 [23].
Data show that the waxes from aromatics have a higher molecular weight, refractive
index, number of rings, and aromaticity, but a lower H/C ratio than that of saturates.
Moreover, the size of the crystallites of waxes in saturates is larger and the crystallinity
is higher. This is the reason why the waxes in saturates have a more negative effect on
the low-temperature performance of the paving asphalt than those in aromatics [21,22].
It is interesting that although the Daqing and Gudao residues are quite different in
composition, the structural parameters of their waxes in saturates or aromatics are very
close to each other.
In Table 10-22, the structural parameters of different fractions of residues are summa-
rized. The structural parameters of each fraction lie within definite ranges. From saturate
to aromatic to resin to asphaltene fractions, the parameters M , n, fA, RT, R A , and the
RA/RN ratio increase, whereas the H/C ratio, fp, and L decrease systematically. The
decrease in the H A ” / C A ratio indicates an increase in the compactness of condensation
of the aromatic nuclei from aromatic to asphaltene fractions. Table 10-22 also shows
that the unit structure weights are about the same (1000) for all the fractions of all the
residues.

DISTRIBUTION OF NITROGEN, NICKEL AND CARBON RESIDUE OF VACUUM RESIDUES

Nitrogen

The distribution of nitrogen among the six fractions of the residues, obtained
according to the separation scheme shown in Fig. 10-1, are presented in Table 10-23.
Data show that the nitrogen content of Fract. 1 is very low. From Fract. 1 to
Cs-asphaltene, the nitrogen content does not increase continuously with the maximum
 w
0
0

TABLE 10-21

Properties and structural parameters of waxes

Name of Sample M tlF H/C N f~ LY fp RI RA RN Dimension of Crystallinity

residue (VPO) (Wt7C) crystallite (nm) (%)

Daqing Wax in saturates 1070 1.4545 1.98 0 0 0.11 0.89 1.50 0 1.50 45.7 40.4 25.0
Wax in aromatics 2060 1.4910 1.80 0.25 0.08 0.20 0.72 9.86 2.45 7.41 21.6 19.4 17.5 4
i

Gudao Wax in saturates 860 1.4547 1.99 0 0 0.12 0.88 1.30 0 1.30 55.5 47.2 36.3
Wax in aromatics 1550 1.5021 1.75 0.40 0.11 0.23 0.66 8.70 2.50 6.20 14.6 16.2 13.6

0
‘3
m
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N
p:
I
m
z

p
r:
c
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 30 1

TABLE 10-22

Comparison of structural parameters of various fractions of vacuum residues

Parameters Saturated Aromatic Resin Heptane asphaltene

1.9-2.0 1.5-1.7 1.4-1.5 1.1-1.3
6W900 700-1 100 14W2800 35WlooOO
1 1-3 4-6
700-1 100 800-1200 8W1200
0 0.2-0.3 0.3-0.4 0.40.5
0.74.9 0.5-0.7 0.45-0.55 0.354.45
1-3 5 4 7-10 11-18
0 2-4 5-7 7-14
1-3 2-3 2.5-3.5 3.5-4.5
0.8-1.3 1.62.3 2-3
0.6-0.8 0.54.6 0.4-0.5
4-7 4-5 3-4

TABLE 10-23

Distribution of nitrogen in vacuum residues

Name of residue Fract. 1 Fract. 2 Fract. 3 Fract. 4 Fract. 5 Pentane asphaltenes

light resins middle resins heavy resins
Daqing N (wt%) 0.30 0.69 1.23 I .03 1.20 -
N/total N (%) 7.9 15.7 31.8 14.6 24.6 -

Renqiu N (wt%) 0.30 1.20 1.50 1.49 1.32 0.95

N/total N (%) 11.9 11.7 17.0 11.1 21.5 9.4
Zhongyuan N(wt%) 0.25 0.61 0.88 1.01 I .22 1.09
N/total N (%) 16.7 10.2 17.7 12.5 30.5 20.2
Shengli N (wt%) 0.15 0.82 1.31 1.52 1.63 1.70
N/total N(%) 6.0 11.1 22.1 13.5 24.5 25. I
Gudao N (wt%) 0.55 1.15 1.50 1.66 1.75 1.62
N/total N (5%) 17.6 12.7 20.9 11.5 20.3 15.5
Xingjiang" N (wt%) 0 0.51 1.22 1.04 1.21 1.38
N/total N(%) 0 6.3 23.0 9.4 21.1 14.8
Jinglou N (wt%) 0.36 1.14 1.56 1.89 2.13 2.07
N/total N (%) 10.8 13.1 23.1 16.0 32.7 9.5
Huanxiling N (wt%) 0.26 1.24 1.56 1.48 1.68 1.78
N/total N (%) 16.6 14.2 21.5 10.9 12.1 18.0

Xingjiang Region No. 9.

content in Fract. 3, 4, 5 or Cs-asphaltene. About 70-80% nitrogen is present in the

resin-asphaltene fraction. Thus, there is a good correlation between nitrogen and resin
contents (Table 10-1 1).
302 W -I. LIANG. G -ti. QUL. Y:Z. C'IIEN A N D C:G. LIU

TABLE 10-24

Distribution of nickel in vacuum residues

Name of residue Fract. I Fract. 2 Fract. 3 Fract. 4 Fract. 5 Pentane asphaltene

Daqing 0.0 3.0 15.0 20.0 37.0 -
Ni/total 0.0 3.5 19.6 14.4 38. I -

Renqiu 0.9 3.5 44.2 51.1 83.3 101.6

Ni/total 0.9 1.1 16.7 12.2 39.5 27.5
Zhongyuan 0.3 1.7 16.5 27.7 22.0 34.6
Ni/total 0.7 1.2 13.3 13.7 22.0 35.8
Shengli 0.0 7.1 87.4 75.1 64.7 127.5
Ni/total 0.0 1.8 25.8 12.1 16.0 36.6
Gudao 0.7 6.3 34.3 55. I 46.0 115.4
Ni/total 0.8 2.3 15.6 12.8 17.9 37.0
Gaosheng 0.3 41.5 467.5 120.2 150.2 375.5
Ni/total 0.1 3.2 42.9 7.6 17.2 28.5
Xingjiang 0.0 10.8 19.5 35.5 80.4 171.6
Ni/total 0.0 3.2 8.5 7.3 32.4 42.6
Jinglou 0. I 7.0 54.7 35.9 85.0 176.1
Ni/total 0. I 2.3 22.6 8.5 36.3 22.5
S hanjiasi 0.5 48.5 140.4 59.4 80.5 206.5
Ni/total 0.3 8.0 27.8 6.4 10.0 46.7
Huanxiling 0.4 52.7 154.1 109.7 153.6 486.7
Ni/total 0.3 6.3 22.0 8.4 11.4 51.2

L' Xingjiang Region No. 9.

Nickel

The distribution of nickel in the six fractions of vacuum residues is presented in

Table 10-24. There is only a very small content of nickel in Fract. 1 (below 1 ppm),
and the nickel content of Fract. 2 is relatively low. More than 95% nickel is present in
the resin-asphaltene fraction. The content of nickel in the pentane-asphaltene fraction is
the highest. As in the case of the nitrogen content, the nickel content does not increase
continuously from Fract. 1 to pentane asphaltene, and the nickel content of Fract. 3
(light resin) ranks second in some cases. It appears that nickel in the lighter subfraction
of resin is more difficult to remove by deasphalting because of its higher solubility in
solvent.

Curbnn residue

Table 10-25 shows that the values of carbon residue of Fract. 1 are very low (about
1-2%), and they increase systematically from Fract. 1 to pentane asphaltene. The
carbon residues of middle and heavy resins and pentane asphaltenes are quite high
(about 30-50%), which means that they will tend to form more coke during processing.
CHEMICAL COMPOSITION AND CHARACTERISTICS OF RESIDUES OF CHINESE CRUDE OILS 303

TABLE 10-25

Carbon residues of fraction of vacuum residues

Name of residue Carbon residue (wt%)

Fract. 1 Fract. 2 Fract. 3 Fract. 4 Fract. 5 Pentane asphaltene
light resins middle resins heavv resins
Renqiu 1.7 12.8 21.2 31.1 40.1 41.1
Zhongyuan 1.1 15.1 27.4 33.1 34.6 43.9
Shengli 1.1 12.8 20.5 24.8 28.7 34.7
Gudao 2.4 16.2 21.9 27.0 29.5 48.8

CONCLUSIONS

Most of the vacuum residues of the twelve Chinese crude oils tested have high
nitrogen, nickel, wax, and resin contents, and low sulfur, vanadium and asphaltene
contents. This constitutes a convincing proof that they are of continental origin.
The structural parameters that were calculated using the NMR spectra with the
modified Brown-Ladner method might reflect the average molecular structure of
various residues from the crude oils of different types and the chemical nature of
their fractions. The structural parameters of each fraction lie within definite ranges
and vary systematically in the following order: saturates, aromatics, resins, and as-
phaltenes.
The resins, which are the main components of the Chinese residues and contain most
of the nitrogen and nickel, have a high propensity for coke formation during processing.

ACKNOWLEDGEMENTS

This work was funded by the Commission of Science Foundation of China. The
authors acknowledge the assistance of Prof. Lao Yongxin, Mr. Yang Jiamo, Mrs. Zhang
Yanfang, and Mrs. Wang Hong. The help extended by Professors George V. Chilinganan
and T.F. Yen is also greatly appreciated by the authors.

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