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Express estimation of crude oil TBP curves only from the viscosity of the crude oil

G. Argirov, S. Ivanov, G. Cholakov

Bulgaria, 8104 Bourgas, Lukoil Neftochim Bourgas AD, Heavy Residue Upgrading Complex-Project, e-mail: Argirov.Georgi.S@neftochim.bg

Key words: crude oil, distillation, TBP prediction, viscosity.

Abstract

Crude oil TBP curves are well recognized as an important characteristic, needed to determine the potential of fractions obtained by distillation, to monitor distillation units, to verify the identity of crude oil samples, etc. They can be obtained experimentally or calculated by a variety of methods, which have different precision. The precision of the particular method determines the applicability of the obtained TBP data. Riazi’s two-parameter distribution model and experimental crude assay data for 117 crudes from all over the world have been used to derive a model for prediction of true boiling point (TBP) curves from the kinematic viscosity of the samples at 37,8 o C. The model was tested by prediction of the cumulative mass fractions of all studied crude samples. It was found that the TBP distribution for fractions boiling up to 340 o C could be predicted with an average relative deviation of the order of 6 %. This is higher than the respective deviation of previously proposed models, e.g. - Riazi’s model, with an average deviation of 3.3 %. However, these models require experimental data for several properties, while in practical terms the precision of our model is sufficient to detect any significant upsets in the operation of refinery crude distillation units (CDUs), so its computerized procedure may be used as a quick tool for monitoring of the CDU operation.

INTRODUCTION

For modern refineries frequent crude oil switching and disturbances in crude distillation unit (CDU) operations often propagate into bigger issues downstream. Managing the change of crudes and diminishing disturbances require regulatory control of the daily performance necessary to respond quickly and adequately to setpoint changes. The quality and value of a crude

oil significantly depend on its TBP (“true” boiling point) distillation curve. Unfortunately, the experimental determination of TBP curves is costly and time consuming, so it is impractical to use them as a tool for daily monitoring

of CDUs. This calls for the development of TBP calculation methods, requiring

a minimum of experimental data, but having sufficient precision for daily

monitoring of CDU operations. Riazi developed a three-parameter distribution model, which is widely used for estimation of the boiling points and other properties of C 7 + fractions of petroleum fluids [1, 2]. It predicts TBP distributions with high precision, when at least three experimental points of the TBP curve of the crude are available [3]. Moreover, it can be used for predictions of the rest of the distillation curves, needed in petroleum processing (ASTM D 86, EFV, CD, etc.)

If distillation data are not available, the values of at least three crude oil

properties (molecular mass, density and refraction index) have to be known. Riazi’s method can not be used directly for daily monitoring of CDU operations, because of the need of significant amount of tests, but it gives the general lines along which this can be achieved. Stratiev et al. [4, 5] developed further Riazi’s ideas and showed that the boiling temperature and other

property distributions can be calculated when experimental density and distillation data up to 300 o C are an available. The Lukoil Neftochim Bourgas AD (LNB) refinery has developed a data base of potential feedstocks - 117 crude oil assays, characterized by TBP curves, density, sulphur, viscosity, metals, Conradson carbon, and asphalthene content of crude oils and TBP cuts. The crude oils originate from different parts of the world .

The aim of this work is to use the LNB database and Riazi’s ideas, for development of a model for crude oil TBP curve prediction from one routine measurement – the crude oil’s kinematic viscosity at 37.8 o C.

EXPERIMENTAL

The TBP distillation of all 117 investigated crude oil samples has been carried out in the AUTODEST 800 Fisher column apparatus, according to АSTM-D 2892 - for the atmospheric part of the test, and according to АSTM-D 5236 - for the vacuum one. The TBP distillation has been performed in the AUTODEST 800 Fisher column at pressure drop

from 760 to 2 mm Hg and in the AUTODEST 860 Fisher column from 1 to 0. 2

mm

Hg.

The

sulphur content has been analyzed according to АSTM-D 4294. Density

at 20 o C has been determined according to АSTM-D 1298. The viscosity has been measured according to АSTM-D 445. Table I characterizies the range of variation of the properties of the crude oils.

Table I. Characterization of the properties of the crude oils in the database.

Property or TBP range

Number of crude samples in group/range of values in group

I

II

III

IV

Total sulfur, %

64/0.5

44/0.51 – 2.0

4/2.01 – 2.5

5/>2.5

Specific gravity @15 0 C range per group

0.7883-0.8886

0.8095-0.8970

0.8685-0.9047

0.8581-0.9024

Viscosity, 37.8 o C, mm 2 /s

88/10.00

17/10.01 – 20.0

7/20.01 – 30.00

5/30.01 – 40.00

TBP yields, %

I

II

III

IV

IBP – 70 o C

9/1 - 2 incl. 62/3 - 5 incl. 16/6 - 8 incl. 1/9 - 10 incl.

9/1 - 2 incl. 8/3 - 5 incl.

2/1 - 2 incl. 5/3 - 5 incl.

4/1 - 2 incl.

1/3

70 - 100 o C

5/1 - 2 incl. 73/3 - 5 incl. 10/6 - 8 incl.

8/1 - 2 incl. 9/3 - 5 incl.

2/1 - 2 incl. 5/3 - 5 incl.

5/1 - 2 incl.

100

– 150 o C

23/5 - 7 incl. 50/8 - 10 incl. 15/11-13 incl.

7/3 - 5 incl. 10/6 - 7 incl.

4/3 - 5 incl.

5/4 - 5 incl.

 

3/6

150

– 190 o C

47/5 - 7 incl. 38/8 - 10 incl. 3/10 - 12 incl.

1/3

7/4 - 6 incl.

5/3 - 4 incl.

 

16/5 - 6 incl.

190

– 235 o C

42/6 - 8 incl. 42/9 - 11 incl. 4/12 - 14 incl.

1/4

7/6 - 7 incl.

5/4 - 6 incl.

 

16/6 - 8 incl.

235

- 280 o C

62/7 - 9 incl. 17/10-12 incl. 6/13-15 incl. 3/16-17 incl.

14/6 - 8 incl.

1/5

1/5

 

3/9

6/6 - 7 incl.

4/6 - 7 incl.

1/8

280

– 343 o C

54/10 -12 incl. 20/13 -15 incl. 6/16 -18 incl. 4/19 -21 incl. 2/22 -23 incl.

1/26

14/10 - 12 incl.

6/9-11 incl.

1/7

 

2/13

1/12

4/9-11 incl.

1/15

343

– 565 o C

1/20

6/30 – 33 incl. 10/35 – 41 incl.

6/25 – 35 incl.

5/33 – 40 incl.

 

4/21 - 23 incl. 7/25 - 27 incl. 25/28 -30 incl. 33/31 -33 incl. 10/34 -36 incl. 4/37 -39 incl.

1/40

1/41

1/50

2/41

1/48

Above 565 o C

37/1 – 10 incl. 44/11 –20 incl. 7/21 –24 incl.

12/13 – 23 incl. 12/13 – 23 incl.

6/24 – 30 incl.

4/30 – 31 incl.

1/35

1/34

As would be shown later, we needed data also for the volume average boiling points (VABP) and the viscosities at 38 o C of the discrete fractions of the crude oils, presented in Table I. Some of these data were measured experimentally, others had to be calculated or approximated to known values. Table II summarizes the origin of the data.

Table II. Estimation of the volume average boiling points (VABP) and data for the viscosity at 38 o C (V 38 ) of the crude oil cuts.

TBP range,

TBP range,

o

C

VABP,

K

V 38 ,

mm

2 /s

Viscosity at 38 o C, mm 2 /s

IBP - 70

326.15*

0.32

estimated as decribed in [6]

70 - 100

358.15

0.46

estimated as decribed in [6]

100

- 150

398.39

0.64

estimated as decribed in [6]

150

- 190

442.57

0.96

estimated as decribed in [6]

190

- 235

485.85

1.47

measured at 38 o C

235

- 280

529.96

2.47

measured at 38 o C

280

- 343

584.29

5.11

measured at 38 o C

343

- 565

716.67

52.83

measured at 38 o C

565 +

949.47**

1.2x10 9

measured at 60 and 99 o C; converted to viscosity at 38 o C as described in [7]

*The initial boiling point, IBP was assumed to be 36 o C (the boiling point of n-pentane). **For calculation of the 565 0 C+ range, the mass average boiling points were calculated by Riazi’s two parameter method [3], and the VABP of the cuts was assumed to be approximately equal to the mass one.

Methodology

Riazi’s three-parameter distribution model for the absolute boiling points can be presented in the following form [3]:

T

o

+

T

T

o

= ⎢

A log

1

1 x

⎞ ⎤

B

1

B

(1),

in which T is the temperature on the distillation curve in kelvin and x is the cumulative volume or mass part of the respective distillate, obtained up to that temperature. In order to distinguish cumulative concentrations of distillates in the crude oil from discrete concentrations, we shall further denote the former as “x C ”, and the latter – as “x D ”.

A, B, and T o are the three parameters, which have to be determined by regression of available distillation data. For atmospheric and vacuum residues the parameter B can be considered a constant with a value of 1.5.

T o is the initial boiling point (IBP, T at x C = 0). However, it should be lower than the experimentally determined IBP and can be determined by regression of experimental distillation data for x C > 0 and iterations for its value [3]. Alternatively, as shown by Stratiev et al. [5], T o might successfully be replaced by the normal boiling point of isobutane (-11.6 0C), the lowest-boiling component in the crude.

For our calculations it is convenient to transform equation (1) into:

U =

1

1 x

C

⎞ ⎤

A log

B

1

B

(2),

in which U is a normalized temperature, defined by:

T

o

+

T

T

o

= U

(3)

Solving equation (2) for x C (the cumulative mass fraction distilled up to temperature T, CDM) leads to the following relationship:

x

c

[

A B U

,

,

]

= 1

e

BU

B

A

(4)

For a complex continuous mixture, such as a crude oil, equation (4) can be represented as:

x

C

[A

,

U

B U =

,

][x

D

0

A , B , U ]dU

(5),

where the function x D [A, B, U] represents the mass of a pseudocomponent, distilled within a certain infinitely small temperature range (dU).

The function x C [A, B, 0] is equal to zero for T o = T, and Riazi’s two-parameter model can be differentiated in terms of the normalized temperature U:

x

D

[A

_,

B U ]

_,

= ∂

U

x [A B U ]

C

,

,

(6)

The output of (6) gives a relation between the concentration of a discrete pseudocomponent, distilled within a narrow temperature range (which for

practical purposes can be represented by its average boiling point) and the parameters of Riazi’s equation:

x

D

[

]

A , B , U =

2

B e

BU

B

A

U −+ 1 B

A

(7)

The parameters of (7) can be calculated from experimental data for discrete fractions (pseudocomponents) by an algorithm, described in [3], if the temperatures in U (T o and T) are defined for the respective discrete yields of distillate (x D ). However, for achieving the aim of this article, namely - development of a model for crude oil TBP prediction from crude viscosity, a combined approach including (7) and other suitable correlations needs to be developed.

Development

of

a

correlation

between

average

boiling

point

and

viscosity

A basic concept of the proposed model is that the properties of a petroleum

mixture are built-up by a linear or non-linear (depending on the particular

property) contribution of the pseudocomponents, contained in that mixture.

The viscosity contribution of a pseudocomponent can be expressed by its viscosity blending number (VBN), thereby applying the equation of Refutas [6]. According to this equation the crude oil viscosity could be calculated, knowing the viscosity of its constituent hydrocarbon fractions. The calculations are carried out in three steps:

1. Calculation of the VBN of each pseudocomponent (discrete fraction) of the

crude oil at the same temperature by:

VBN Di = 14.534 x Di ln [ln (v Di +0.8)]+10.975

(8),

where v Di is the kinematic viscosity of the crude oil pseudocomponent in mm 2 /s, and x Di – its mass %.

2. Additive calculation of the viscosity number of the crude oil, VBN crude by:

VBN crude = (x D1 VBN D1 ) + (x D2 VBN D2 ) +…+ (x Dn VBN Dn )

(9),

where x Di is the percentage mass part of each hydrocarbon fraction of the crude oil.

3. Once the viscosity blending number of a crude oil is obtained from equation

(9), the viscosity of the crude oil, v crude , can be determined by using the invert

of equation (8):

VBN crude 10.975

v

crude

=

e

e

14.534

0.8

(10)

where VBN crude is the viscosity blending number of the crude oil, determined by (9).

Our next task was to develop a correlation for prediction of viscosity blending numbers of the discrete fractions of the crudes from their volume average boiling points. For this purpose the data, presented in Table II were used. For our next steps in the algorithm, it was convenient to present the VABPs of the discrete cuts (Table II) as normalized temperatures (U), calculated by eq. (2) above. Like in [4], the Riazi’s IBP of the crude - T o , was assumed to be equal of the isobutane boiling point (261 K) – the lowest-boiling component in the crude.

The viscosities at 38 o C, determined as described in Table II, were used to calculate the VBNs of the respective discrete fractions of each of the 117 crude oil samples. Then the desired correlation, giving the dependence of pseudocomponent’s VBN from its normalized boiling point, was obtained by regression of the VBN and U data, in the following form:

VBN Di [U]=14.8567 (0.919903U+ln(0.919903U))

(11)

Table III summarizes the data for the volume average boiling points (VABPs, their transformation into normalized temperatures (U) and the viscosity blending numbers of the discrete fractions (VBN), calculated by (11).

Table III. Volume average boiling points, normalized temperatures (U) and viscosity blending numbers of the discrete fractions.

Discrete

Discrete

VABP, K

U,

VBNcalc

fraction

fraction

(normalized

boundaries,

boundaries,

 

VABP)

TBP range,

TBP

range,

0C

normalized

temperature

IBP - 70 70 - 100

0.0003 – 0.314 0.314 – 0.429

326.15

0.25

-20.04

358.15

0.37

-10.25

100

- 150

0.429 – 0.621

398.39

0.52

-3.58

150

- 190

0.621 – 0.774

442.57

0.70

2.76

190

- 235

0.774 – 0.946

485.85

0.86

8.17

235

- 280

0.946 – 1.119

529.96

1.03

13.48

280

- 343

1.119 – 1.360

584.29

1.24

19.41

343

- 565

1.360 – 2.211

716.67

1.75

30.90

565

+

2.211 – 3.887

949.47

2.64

49.05

The average absolute deviation of the resulting model was an acceptable 2,69%, and the R 2 correlation coefficient was higher than 0.999.

The right hand side of (11) can be decomposed as:

VBN Di 1[U]=14.8567x0.919903U= 13.6667U

(12)

VBN Di 2[U]=14.8567(ln(0.919903U)) = 14.8567ln(0.919903U)

(13)

In continuation of our study, we used Riazi’s two-parameter model (with T o fixed at 261 K), as transformed above for for discrete pseudocomponents, distilled up within a certain temperature range, eq. (7) and eq. (9) – for the linear calculation of the VBN of a blend, with the aim to define a dependence necessary for evaluation of Riazi’s model parameters A T (A) и B T (B). The mathematical notation is as follows:

VBN

Di

[A

,

B a b

,

,

]

=

b

a

x

Di

[A

,

b

B U ]VBN 1 []U dU + x

,

Di

a

Di

[A

,

B , U ]VBN 2 []U dU

Di

(14),

where a, b are temperature boundaries of the discrete fraction distilled up within temperature range, expressed by normalized temperatures.

The definite integral output gave the following expression for VBN of a discrete pseudocomponent, VBN Di in (9) :

14.8567

B

0.0834867

e

Ba B

A

+

ln(

a ) e

Ba

A

B

+

0.0834867

e

Bb

A

B

ln(

b ) e

Bb

A

B

Ei

a B ⎞ ⎟ +

B

A

Ei

b B ⎞ ⎟

B

A

B

+ 13.6667

⎛ ⎜ A ⎞ ⎟ ⎡ ⎢ Γ ⎛ ⎜ 1 +

1

B

B

1

B

,

a

B

A

B ⎞ ⎟ −

1.

Γ

1

+

1

B

,

b B ⎞ ⎤

⎠ ⎦

B

A

(15),

where Γ is Riazi’s gamma function and Ei is ExpIntegral – gives the exponential integral function Ei (z).

However, in the definite integral output (15), both parameters A and B are unknown. Therefore, we used the relation obtained for a VBN of fraction (VBN Di ) with A T (A) and B T (B) originating from Riazi’s model and the pseudocomponent’s boiling temperature range (expressed as VABP) to form a system of two equations:

VBN Di [A, B, 0.000001, 3.877394]=VBN crude

(16)

VBN Di [A, B, 0.000001, 1.360153]=2.905

(17)

The first equation (16) is in fact equation (9) applied to equalize the VBN of the whole crude to the VBN of a pseudocomponent, obtained within the boiling range from IBP to 1000 o C (0 to 3.87, expressed as normalized temperature, U), which covers the crude distillation range up to T 98% , as suggested in [4, 5]. The second equation (17) does the same, equalizing to the constant 2.905, the VBN of a fraction distilled up to 343 o C (1.36 expressed as normalized temperature).

The above system empirically allows for the determination of Riazi’s coefficient. The fraction distilled up to 343 o C for equation (17) was chosen because it provided best agreement of the model with the available experimental data. Hence, with the known values of A and B, the prediction of

a crude TBP yields for discrete pseudocomponets expressed with normalized VABPs, as shown in Table III mathematically is as follows:

FractionsTemperatureBoundaries={0.0003,0.314,0.429,0.621,0.774,0.946,1.119,1.360,2.211,3.877}

FractionMass[A,B,n]=X C [A,B,FractionsTemperatureBoundaries[[n+1]]]–X C [A,B, FractionsTemperatureBoundaries[[n]]]

(18)

(19),

where an equation (18) defines the discrete fraction temperature boundaries in normalized temperature (U) while an equation (19) gives the mass of each discrete fraction. n is equal of the sum of the boundaries covering each discrete fractions (in this case n equals of 9 and it varies between 1 and 9).

Further, the obtained mass concentrations of the discrete fractions (i.e., in o С):

IBP - 70; 70 - 100; 100 - 150; 150 - 190; 190 - 235; 235 - 280; 280 - 343; 343 - 565; 565+, can be readily summed up for cumulative fractions: IBP - 70; IBP - 100; IBP - 150; IBP - 190; IBP – 235, etc.

RESULTS AND DISCUSSION

In order to test the validity and accuracy of the new proposed model (15), its predictions for discrete fractions were recalculated into predictions for the TBP yields of cumulative fractions of the 117 crude oil assays in the data base. They were compared with the measured TBP yields and with those predicted by Riazi’s model. The results are summarized in Table IV.

Table IV. Comparison of absolute deviations

TBP

Average absolute deviation of the TBP yields (%) from the 117 crudes, estimated by New model and Riazi’s model per group crude sample

cumulative fraction, o C

I

II

III

IV

 

Riazi’s

New

Riazi’s

New

Riazi’s

New

Riazi’s

New

model

model

model

model

model

model

model

model

IBP - 70

0.39

1.09

0.17

1.00

0.19

1.57

0.11

0.67

IBP - 100

0.33

1.57

0.16

1.59

0.22

2.72

0.10

1.23

IBP - 150

1.03

2.29

0.49

2.35

0.46

4.18

0.45

2.27

IBP - 190

1.02

2.23

0.50

2.74

0.45

4.88

0.18

2.23

IBP - 235

0.80

2.08

0.56

2.96

0.41

5.14

0.57

3.62

IBP - 280

0.96

1.95

0.65

2.97

0.63

4.83

0.87

4.10

IBP - 343

1.63

2.74

0.90

2.80

0.85

3.88

0.90

4.63

IBP - 565

1.42

2.83

2.06

1.81

1.57

3.32

2.08

3.49

Table IV shows that the average absolute deviations of the yields, predicted by Riazi’s method are several times closer to the experimental values than those estimated by the new method. This not surprising since the parameters of the Riazi model have been calculated from all available TBP data, while the parameters of new model involve estimated data. The calculated average

relative deviation was reasonably well for white oil fractions distilled up to 343 0 С, amounting of 5.95% against 3.30% - calculated through Riazi’s model. On the other hand, the deviations of the obtained by calculation by any method yields cannot be less than those which can be reproduced experimentally. For instance, the reproducibility of experimental yields, obtained by the ASTM D 2892 method is 1.2 % for atmospheric and 1.4 % - for vacuum fractions [9]. So, the deviations of the new method are comparable to the experimental and thus acceptable for its declared practical applications. Moreover, there are possibilities to improve the new method if more experimental data are available and/or other routinely determined properties of the crudes are used.

The adequacy of the model was verified, also for predicting the TBP distribution of a test set of three crude oil samples, not included among the 117 samples used to develop the model. The results obtained are given in Table V.

Table V. Absolute deviations of the predictions with the new method for the test set

Properties

Crude oil

 

Mellitah

Western

REBCO

 

Desert

Visc. at 38 o C, mm 2 /s

2.07

2.51

8.25

Specific

0

@15 C

gravity

0.8132

0.8200

0.8680

TBP range, o C

Absolute deviation, %

IBP - 70

0.50

1.64

0.58

IBP - 100

3.72

3.44

1.04

IBP - 150

1.42

4.08

1.25

IBP - 190

1.70

2.87

1.07

IBP - 235

0.77

1.58

0.34

IBP - 280

1.68

1.12

0.05

IBP - 343

1.10

3.62

0.51

IBP - 565

5.00

3.48

0.96

The deviations with the test set fall within those for the 117 samples used in the development of the model.

CONCLUSIONS

The main aim of this work was to develop a method for express prediction of crude true boiling point (TBP) curves, that would be suitable for daily monitoring of the operarion of crude oil distillation units (CDUs). The main results achieved in the realization of this aim can be summatrized as follows:

- The developed new model requires only data from the routine laboratory

analysis of the kinematic viscosity of crude oil at 38 o С. In its development assay data for 117 crude oils from different parts of the world have been used. The precision of the predictions of the new model, though somewhat worse

than those of the original Riazi model, are comparable to the experimental reproducibility of the standard methods for laboratory distillation. The adequacy of the model was verified, also for predicting the TBP distribution of a test set of three crude oil samples, not used in the development of the model. The results of this test showed the consistency of the model predictions.

- In practical terms the reported deviation is sufficient to detect any upsets in

the operation of refinery CDUs. The method requires only data for the viscosity of crude oil at 38 o С, and uses a computerized calculation algorithm,

easily realized in Excel or other popular statistical software.

- An integral part of the new model is a sub model describing the dependence of the viscosity blending numbers (VBNs) of crude oil pseudocomponents from their average boiling boiling points. The submodel allows for subsequent calculation of other integral parameters for each narrow cut of crude oil, such as: molecular mass, specific gravity and refractive index, including proxy on TBP-distillation curve at known VBNs.

- In terms of mathematics, it can be assumed that Riazi’s model can be

reduced to an essentially one-parameter model, taking into account eq. (17) which allows to estimate its property parameters from only one laboratory measurement. The Riazi’s model, which is originally in integral form, can be subjected to differentiation in order to identify the properties of pseudocomponent.

REFERENCES

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[2] Riazi, M.,”A Continuous Model for C7+ Fraction Characterization of Petroleum Fluids”, Ind. Eng. Chem. Res., Vol. 36 (1997), pp 4299-4307

[3] Riazi, M. “Characterization and properties of petroleum fractions”, ASTM Manual Series: MNL 50, 2005. ASTM

[4] Stratiev, D. et. all,”Method Calculates Crude cut Properties,” Oil and Gas Journal/Jan.7, 2008, pp.48-49.

[5] Stratiev, D. Dinkov, K. Kirilov, ”Evaluation of Crude oil data,” IPC 2007- 43rdInternational Petroleum Conference, September 24-26, 2007, Bratislava.

[6] Abbott, M. M., Kaufmann, T. G. and Domash, L., "A Correlation for Predicting Liquid Viscosities of Petroleum Fractions," Canadian Journal of Chemical Engineering, Vol. 49, No. 3, 1971, pp. 379-384.

[7] Singh, B., Miadonye, A., and Putagunta, V.R., “Heavy oil viscosity range from one test,” Hydrocarbon Processing”, August 1993, pp. 157-160.

[8] Robert E. Maples (2000). Petroleum Refinery Process Economics (2nd ed.). Pennwell Books.

[9] ASTM Manual series 37, ”Fuels and Lubricants Handbook”, 2003.