Journal of Petroleum Science and Engineering 41 (2004) 233 242 www.elsevier.

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Feedstock characteristic index and critical properties of heavy crudes and petroleum residua
Suoqi Zhao *, Zhiming Xu, Chunming Xu, Keng H. Chung
State Key Laboratory of Heavy Oil Processing, University of Petroleum, Changping, Beijing 102249, PR China Received 26 July 2002; received in revised form 12 April 2003

Abstract Supercritical fluid extraction and fractionation was used to prepare narrow-cuts from a variety of petroleum vacuum residua. The narrow-cuts were subjected to comprehensive characterization and solubility class separation into saturates, aromatics, resins and asphaltenes fractions. Unlike the bulk property measurements, the narrow-cut characterization data show uneven distribution of key contaminants (with the concentration increasing) as the fraction becomes heavier. Narrow-cut data were used to develop a generalized feedstock characteristic index, KR, that correlates well with the feedstock hydrocarbon constituents and can be used to assess feedstock reactivity and process capability. Downstream refiners can use the narrow-cut data and KR index for process optimization by either cutting deep into the bottom of residua to increase yield or selecting appropriate process units for various residue fractions. Narrow-cut data were also used to develop critical properties of residue fractions, which can be used as input parameters for simulation studies in designing process units for heavy crude and residua. D 2003 Elsevier B.V. All rights reserved.
Keywords: Feedstock characteristic factor; Critical properties; Supercritical fluid extraction and fractionation; Heavy crude; Residua

1. Introduction The supply of light crude has diminished in recent years. Petroleum producers and refiners are forced to deal with heavier crudes, such as heavy oils, bitumens and residua (non-distillable material), as an inexpensive substitute. Heavy crudes are known to contain as much as 50 wt.% of residue fraction, and exhibit unique behavior in pipeline transportation and conventional refinery processes. Since the refinery processes are feedstock dependent and most of the conventional refineries built prior to 1980s are for

lighter feedstock, achieving efficient utilization of heavy petroleum feedstock is a challenging task facing the petroleum industry. Feedstock characteristics are the key design criteria for conventional refinery processes, which are commonly determined by UOP Watson K index (see Speight, 1998): p 1:216 3 Tb K 1 SG where Tb (K) is the average boiling point and SG is the specific gravity at 15.6/15.6 jC. Various correlations of feedstock properties have been developed based on the UOP K index, which has been the foundation for the petroleum science and technology. However, the UOP K index is not applicable to heavy crudes, since the boiling point of the residue fraction

* Corresponding author. E-mail address: sqzhao@bjpeu.edu.cn (S. Zhao). 0920-4105/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0920-4105(03)00157-8

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is undefined. It should be also noted that the UOP K index considers only feedstock physical properties that correlates with the paraffinicity of feedstock. However, it is known that the residue fractions are usually more naphthenic and aromatic in nature, and the reactivity of heavy feedstock, either thermal or catalytic, is strongly dependent on the feedstock chemistry. Hence, there is a tremendous incentive to develop a feedstock characteristic index for heavy crudes, in order to optimize the refinery processes. The need for this is even more critical to China, which has limited process options and imports much of their petroleum feedstock from a variety of sources. Due to the complexity of residue species, there is no standard analytical tool or database that predicts the characterization of heavy crudes. As a result, an ambiguous black oil concept is commonly used to describe heavy crudes. A number of methods are available for fractionating heavy petroleum feedstock. Conventional vacuum distillation is capable of topping distillates up to 524 jC. The use of high-vacuum, short path distillation has allowed the cut point to be extended to 700 jC. For non-distillable residua, sequential extraction fractionation is used to prepare subfractions based on solubility of residua in various solvents. Alternatively, the residua can be separated by gel permeation chromatography. While these methods are capable of separating the non-distillable residua, they are tedious and produce only small amounts of sample. These sample volumes are adequate for only limited characterization studies. Recently, Yang and Wang (1999) and Shi et al. (1999) described the use of a new tool, supercritical fluid extraction and fractionation (SFEF), to prepare narrow, deep cuts of residua. The characterization of these narrow cuts was used to develop a feedstock characteristic index for Chinese heavy crudes and residua, KH: KH 10 H =C 0:1236 q Mn 2

This paper is an extension of the work of Wang and his co-workers by incorporating various benchmark petroleum residua from Middle East and Athabasca bitumen pitch. A generalized feedstock characteristic index for petroleum residua from various sources is developed. Critical properties of residue fractions are also derived.

2. Experimental A wide variety of vacuum residua were considered: Daqing and Shengli crudes from China, Saudi light and medium crudes, Iranian light and heavy crudes, Oman crude and Athabasca bitumen. The details regarding the preparation of narrow-cuts of petroleum residua using the SFEF have been described elsewhere (Wang et al., 1993; Chung et al., 1997). In summary, about 1 kg of residue was charged to the SFEF unit with n-pentane as supercritical solvent. The extraction and fractionation section of the SFEF unit was maintained at above 200 jC (critical temperature of npentane). The pressure of the SFEF unit was initially set at 4 MPa and was increased to 12 MPa at 1 MPa/h. About 50 g of narrow-cut samples were collected subsequently. The SFEF end-cut is the last fraction of residue, which is not extractable with pentane even under the most severe supercritical conditions. The narrow-cuts of each residue were subjected to various analyses. The elemental analysis was carried out on a Perkin-Elmer CHNS/O Analyzer 2400 (Perkin-Elmer, USA). Knauer vapour pressure osmometer (Knauer Instruments, Germany) was used to determine the number average molecular weight. VT500 viscometor (HAAKE, German) was for viscosity measurement. Saturates, aromatics, resins and asphaltenes (SARA) analyses were performed according to the procedures described by Liang (1995) using nheptane as solvent. Saturate, aromatic and resin fractions were collected from chromatographic separation of maltenes in an alumina column. The average boiling points of narrow-cut samples from the frontfraction of residua were determined using high temperature simulation distillation. Together with boiling points of various distillate narrow-cuts, a two-parameter boiling point correlation for heavy feedstock was derived by multi-variable, non-linear regressions (Xu, 1994).

where Mn is the number average molecular weight, q is the density at 20 jC (g/ml) and H/C is the atomic hydrogen-to-carbon ratio, which accounts for the feedstock chemistry effect. The new KH correlates adequately with various Chinese feedstocks, but it shows variability for feedstocks originated from other sources.

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3. Results and discussion 3.1. SFEF narrow-cut characterization The quality of heavy petroleum feedstock is commonly defined by the amount of contaminants such as sulfur, nitrogen and metals, and the nature of hydrocarbon constituents it contains. This information is crucial to the downstream refineries to route the heavy feedstock to the appropriate processing units and product optimization. The key bulk properties of residua are shown in Table 1. The data show a wide variation of properties for residua from various sources. Daqing residue is relatively paraffinic and has the largest amount of saturates, no asphaltenes and low sulfur and metal concentrations. Generally, heavy feedstock with these characteristics is considered premium feedstock, which can be easily processed. On the other hand, Athabasca residue is highly aromatic and has large amounts of asphaltenes, sulfur and metals. This type of feedstock requires complex and expensive processes to remove the contaminants prior to the refining steps. The contaminants are known to poison or deactivate catalysts that are crucial and used in converting large hydrocarbon molecules into useful products in refinery processes. The properties of Middle East residua vary between those of Daqing and Athabasca. The properties of Shengli residue from China are similar to those of
Table 1 Properties of residua from various sources Daqing Density (g/cm3) at 20 jC Viscosity (mPa s) at 70 jC Mn (VPO) H/C (atomic) S (wt.%) N (wt.%) Ni (ppm) V (ppm) CCR (wt.%) Aromaticity, fA Sat. (wt.%) Ar (wt.%) Re (wt.%) Asp (wt.%) 0.9392 5852 1051 1.79 0.145 0.44 7.6 0.066 8.2 0.139 41.9 32.7 25.4 0.0 967 1.58 3.01 0.95 55.7 3.3 16.0 0.248 16.1 30.6 51.1 2.2 Shengli 0.9724 Saudi light 1.0045 9722 804 1.47 3.99 0.45 23.0 60.6 19.9 0.317 16.5 49.5 26.8 7.3 1046 1.510 4.79 0.53 36.7 147.4 20.05 0.255 15.85 40.04 33.7 9.3

Middle East residua, except for higher nitrogen and resins contents. Table 2 compares the properties of SFEF end-cuts from various residua. The results show that most of the contaminants in residua are concentrated in the end-cut fractions. The hydrocarbon constituents of residue end-cuts enrich with more aromatic species (low H/C ratio) such as resins and asphaltenes and have a high coke-forming propensity as indicated by high Conradson carbon residue (CCR) values. In most residue end-cuts, the concentrations of contaminants are so high that they are typically processed in cokers in which most of the contaminants are partitioned and removed as part of product cokes. A major advantage of the SFEF technology is that it can be used to prepare sufficient quantity of narrow, deep cuts of residua for characterization. Unlike the bulk properties shown in Table 1, this allows the distribution of key species to be determined, indicating the variation of residue properties as the fraction becomes heavier. These are important feedstock data which allow the refiners to increase yield by cutting deeper into the bottom of residua to produce more high-value feedstock. The distributions of sulfur, CCR and metals in various residua are shown in Figs. 1 3, respectively, indicating that these species are concentrated in the heavier fractions and are unevenly distributed. The refiners can fractionate the residua accordingly to meet the feedstock process criteria for

Saudi medium 1.0258

Iranian light 1.0057

Iranian heavy 1.0222

Oman 0.9637 2392

Athabasca bitumen 1.0596

1052 1.49 2.92 0.93 66.37 245.7 19.2 0.298 18.46 44.83 30.58 6.12

909 1.44 3.11 0.62 89.96 205.8 22.1 0.354 12.60 46.63 29.92 10.84

979 1.60 1.68 0.45 18.0 21.8 13.8 0.193 26.3 40.6 31.2 2.0

1191 1.34 5.29 0.66 160 422 27.13 0.342 6.26 32.97 29.37 31.4

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Table 2 Properties of SFEF end-cuts from various residua Daqing Yield (%) Density (g/cm3) (20 jC) CCR (wt.%) Mn (VPO method) H/C (atomic) N (wt.%) S (wt.%) Ni (ppm) V (ppm) Sat. (wt.%) Ar (wt.%) Re (wt.%) Asp (wt.%) 12.2 0.9654 40.3 2458 1.38 0.98 0.30 111.6 1.18 0.2 7.9 92.1 0.3 ShengliL 28.2 1.0002 Saudilight 19.8 1.0533 54.6 2952 1.16 1.09 5.94 88.6 299 0.2 11.1 34.9 53.9 Saudi middle 33.4 1.034 31.3 2882 1.276 1.28 6.5 96.1 547 0.58 41.9 34.10 23.1 Iran light 19.5 1.060 49.9 3964 1.19 1.76 4.3 25.6 449 0.46 16.6 33.9 49.0 Iran heavy 23.01 1.062 52.4 4254 1.15 1.18 5.33 258 536 0.31 11.11 22.79 65.78 Oman 12.9 1.0024 47.9 5681 1.39 1.11 3.24 105 103 0.1 7.0 78.4 14.5 Pitch VTB 34.2 1.0857 48.9 4185 1.22 1.05 6.51 339 877 0.0 2.19 9.38 88.03

5515

5.14 122.3 8.75 0.0 17.6 48.7 33.7

a given process unit such as the critical CCR and metals contents for fluid catalytic cracking (FCC) unit. Despite similar trend in sulfur, CCR and metals distributions in these residua, the individual data set for each residue is quite discrete. This is probably related to the distribution of residue hydrocarbon constituents. Fig. 4a and b compares the distribution of saturates, aromatics and resins in Daqing and Iran heavy residua. Saturates are concentrated in the front end of the residua, decreasing as the fractions become heavier. The amount of resins increases as the fractions become heavier. There are, however, obvious differences between Daqing and Iran heavy residua. Iran heavy residue has more aromatics, resins and asphaltenes than Daqing residue, as shown in Table 1.

In addition, as shown in Fig. 4a and b, the amount of aromatics in Daqing residue increases as the fractions become heavier, whereas the Iran heavy residue fraction is relatively constant with a maximum at the middle fraction. 3.2. Feedstock characteristic index Feedstock characteristic index is used to define the nature of feedstock hydrocarbon constituents and correlate it to its reactivity. In developing a generalized feedstock characteristic index for heavy petroleum feedstock, the work of Wang and his co-workers (Yang and Wang, 1999; Shi et al., 1999) was extended by incorporating and substituting additional properties

Fig. 1. Distributions of sulfur in various residua.

Fig. 2. Distributions of CCR in various residua.

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Fig. 3. Distributions of metals in various residua: (a) Ni and (b) V.

Fig. 4. (a) Distributions of saturates, aromatics and resins in Daqing residue. (b) Distributions of saturates, aromatics and resins in Iran heavy residue.

that could be easily determined, and revising the functional form of Eq. (2). After extensive data regression analysis, a new feedstock characteristic index, KR, is proposed, consisting of H/C, molecular weight (Mn) and viscosity (g): KR 10 H =C 2 0:1236 g0:1305 Mn 3

The narrow-cut characterization data, H/C, Mn and g, for various residua that used in deriving KR in Eq. (3), are shown in Figs. 5 7, respectively. The characteristics of feedstock hydrocarbon constituents were used to validate the chemical significance of KR index. Figs. 8 11 show the goodness of fit of CCR, saturates, aromatics and resins contents as a function of KR, respectively. In general, the data in Figs. 8 11 are strongly correlated with KR. The CCR,

Fig. 5. Hydrogen-to-carbon (H/C) atomic ratios of various residue narrow-cuts.

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Fig. 6. Molecular weights of various residue narrow-cuts. Fig. 8. CCR as a function of KR index.

saturates, aromatics and resins contents can be expressed as a function of KR as follows: CCR wt:% 65:685=KR 5:810 r 0:909 4 r2 0:922 5 r2 0:867 6 r2 0:700 7
2

Saturates wt:% 10:885KR 28:391 Aromatics wt:% 92:464 7:575KR for KR > 4
1:528 Resins wt:% 225:504=KR

for KR > 4

The lack of fit data for aromatics and resins at KR below 4 is likely due to separation difficulty

encountered in analytical procedure, in which heavy aromatic fractions are known to overlap with resins. The linear relationship of saturates versus KR and the inverse relationship between CCR, aromatics and resins versus KR are consistent with feedstock reactivity. Feedstock with high saturates content is easier to process; conversely, that with high CCR, aromatics or resins contents is difficult to process. Based on the previous feedstock reactivity studies (Long, 1990; Zhao, 1992; Chen,1992; Wang, 1994), the processability of various heavy

Fig. 7. Viscosities of various residue narrow-cuts.

Fig. 9. Saturate content as a function of KR index.

S. Zhao et al. / Journal of Petroleum Science and Engineering 41 (2004) 233242

o 4:8721 0:24434610 102 fpc Pc

239

0:43087800 104 f2 pc =1 0:16088038 101 fpc 0:20717865 102 f2 pc SGo 0:62621 0:66878721 101 fsg 0:59212241 102 f2 sg =1 0:062791972 101 fsg 0:42682682 102 f2 sg 11 10

Fig. 10. Aromatic content as a function of KR index.

o 0:18792102105 1 0:89331074 101 fvc Vco Tc

0:43087800 103 f2 vc =1 0:20935548 102 fvc

o o qo c Mn =Vc

feedstock can be classified according to KR in three categories:

1st category 2nd category 3rd category KR>6 4 < KR < 6 KR < 4 adaptable to processing intermediate difficult to process

12

13

3.3. Critical properties Critical properties are parameters that are commonly used by process simulators in the unit operation design. The methodology used to derive the critical properties of heavy petroleum fractions was similar to that reported elsewhere (Kesler and Lee, 1976; Riazi and Daubert, 1980; Twu, 1984; Brule et al., 1982; Maslanik et al., 1981; Lin and Chao, 1984). A set of correlations for alkane system up to C 24 were obtained:
o Tb 111:6361 0:1369646ftb 0:92635220 1 102 f2 tb =1 0:44162923 10 ftb

where T, P and V are temperature in K, pressure in MPa and volume in cm3/mol, respectively. The superscript o and subscript c denote the ideal and critical states, respectively. The parameter f used in Eqs. (8) (13) are defined as follows:
o ftb Mn 16:04262=3 o ftc Mn 16:04262=3

14 15

0:73097615 103 f2 tb
o o Tc =Tb 1:70711 0:207576019 101 ftc

0:98431965 103 f2 tc =1 0:23293035 101 ftc 0:16839807 103 f2 tc 9

Fig. 11. Resin content as a function of KR index.

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o fpc Mn 30:06942=3 o fsg Mn 72:14862=3 o fvc Mn 16:0426

16 17 18

Properties of other hydrocarbons or heavy petroleum fractions can be correlated as perturbations of those of n-alkanes with same boiling point temperature as follows (Zhang et al., 1998):
o Tc Tc 17985:731 27924:736

=SG 10655:703=SG2 DSGT 121794:13 82527:92=SG 68835:678=SG2 DSG2 T 248433:99 405746:33=SG 68835:678=SG
2

Fig. 13. Critical temperatures of various residue narrow-cuts.

o 1:7454987 0:21527818 104 lnMn lnMn

DSG3 T

=Tc 0:63682878 106 =Tc2 DTCM 19 0:52774857 0:65871831 103 =Tc

2 0:19785982 106 =Tc DTC2 M

o o o Pc Tc =Vc Pc Vc =Tc 0:11893861 165:35472=Tc 2 55837:029=Tc DTCP 0:78087709 103 2 1:0397575=Tc 307:23148=Tc DTC2 P 20

0:036689969 0:45890527 102 =Tc 0:13987772 105 =Tc2 DTC2 M 23

Vc Mn =qc qc qo c 0:89687121 10
4

21
1:1908482 :5158375 Tb DSG0 d

where the parameters used in Eqs. (19) (23) are defined as follows: DSGT SG SGo =SG 24 25

22

DSGd ASG SGo A=SG

Fig. 12. Boling point curves of various residua.

Fig. 14. Critical pressures of various residue narrow-cuts.

S. Zhao et al. / Journal of Petroleum Science and Engineering 41 (2004) 233242 Table 3 Absolute average deviations of various critical property prediction methods Properties Number of data points (refs. a e) AAD (%) This work 0.42 2.90 1.90 2.78 Kesler and Lee (1976) 1.38 5.08 7.11 5.11 Riazi and Daubert (1980) 1.38 5.08 7.11 5.11 Twu (1984) 0.75 4.21 4.46 4.21 Brule et al. (1982) 1.35 17.2 17.3 11.3 Maslanik et al. (1981) 1.24 6.11 8.42 Lin and Chao (1984) 1.62 12.7 9.10

241

Jalowka and Daubert (1986) 0.61 2.81

Tc Pc Vc Mn

318 311 309 318

Note: (a) Marsh (1992), (b) Danner and Daubert (1992), (c e) Lin et al. (1980a,b,c).

o DTCP Tc Tc p oA DTCM ATc Tc

26 27

The most adequate correlation for the average boiling point Tb of various petroleum residue fractions7 in Eq. (22) is:
0:3709 0:1326 Tb 79:23Mn q

28

Figs. 12 14 show the values of Tb, Tc and Pc of various residue narrow-cuts, respectively. The models proposed in this work have been compared with various thermodynamic models for hydrocarbon systems in another paper (Zhang et al., 1998) as shown in Table 3, using a number of database most available (Marsh, 1992; Danner and Daubert, 1992; Lin et al., 1980a,b,c). Absolute average deviation, as defined in Eq. (29), is used as a criterion to determine the goodness of fit of data.   Ndata X   exp exp   ycal i y i =y i   i1  AAD % 100 29 Ndata The results in Table 3 show that the correlations derived in this work gave more accurate predictions than other models. This is likely due to the use of residue narrow-cut data in deriving the correlations, which are not available before.

(2) Characterization data of SFEF narrow-cuts shows the uneven distribution of key contaminants, indicating increased concentration as the fraction becomes heavier. (3) A generalized feedstock characteristic index KH was developed, which correlates well with the feedstock hydrocarbon constituents and can be used to assess the feedstock reactivity and processability. (4) Narrow-cut data were used to develop critical properties of residue fractions.

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4. Conclusions (1) SFEF is an important tool to prepare narrow-cuts from a variety of petroleum vacuum residua.

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