A compositional framework for feed characterization applied in the modeling of diesel hydrotreating processes

Jos Luiz de Medeiros, UFRJ, Rio de Janeiro, Brazil; Oflia de Queiroz F. Arajo, UFRJ, Rio de Janeiro, Brazil; and Raissa M. Cotta F. da Silva, PETROBRAS, Rio de Janeiro, Brazil

Introduction
Current refinery models devote little attention to composition-thermodynamic contexts and massive interest on plant logistics using relaxed unit models and lumped descriptions, where individual chemical species do not appear. Although satisfactory for management, this may occlude information for improvement of processes with important roles reserved in the future. Probably hydrotreating (HDT) and hydrocracking (HCC) figure among them. This work proposes a methodology for HDT modeling, consisting of: (i) Mixed discrete-continuous Compositional Model (CM) for HDT feeds; (ii) CM tuned to a given feed via reconciliation with raw oil data; (iii) Network of HDT chemical reactions on the continua of reagent and product species, allowing influence of species size on kinetics; (iv) Reactor model analytically solved; (v) Model parameters estimated with isothermal pilot data.

Compositional Model for HDT Feeds

The CM is conceived as a mixture of NF=27 continuous families of descendant species from 27 chemical ancestors (Table 1). Ancestors and rules for generation of descendant, were proposed with principles accepted in petroleum models1,2,3,4,5. Descendants are created via lateral attachment of paraffinic chains with length defined by a continuous variable, X, distributed positively according to scaled and shifted gamma Probability Density Functions (PDF) (Eq. 1). A given species, belonging to family i, is thus represented by the pair (i,X); F0(i,X-Di) is its molar density function per 100g of oil; U(X) is the unitary step function and (.) is the gamma function.

F0 (i,X Di ) = Ci

i (i+1 ) .( X Di )i . exp( - i ( X Di )).U ( X Di ) (i+1 )

(1)

Family i has four parameters: [ Ci , Di , i , i ] . Ci is its number of moles per 100g of oil; Di is its shift parameter; i , i are gamma PDF parameters. We assume that: (a) only the first 17 families exist in a given feed, other families are created by HDT; (b) only two pairs of PDF parameters [ L , L ] , [ H , H ] are assigned to the 17 families (Table 1), each with its own [ Ci , Di ] . To represent all families in the same species continuum, X is defined for the benzenic family (No.1). Parameters Di are pre-assigned to each family such that species (i,X) has the same number of carbons than a benzenic descendant (1,X-Di). Thus, D2 = D4 = D10 = 4 ;

D3 = D5 = D7 = D11 = 8 ; D13 = 2 etc. This assures, for instance, that benzothiophenic and
benzenic species, mapped with the same value of X, are correctly linked, as reactant and product, by a hydrogenating reaction.

Table 1: Chemical Ancestors

1 (L)

2 (L)

3 (H)

4 (L)

5 (H)

6 (H)

7 (H)
S

8 (H)
S

9 (L)
N H

10 (L)
N

11 (H)

12 (L)

13 (L)

14 (H)

15 (H)

16 (H)

17 (L)

18 (H)
N H

19 (H)
N H

20 (H)
N H

21 (H)

22 (H) L : Following Gamma PDF with

[ L , L ]

23 (H) H : Following Gamma PDF with

24 (H)

[ H , H ]

25 (H)

26 (H)

27 (L)

A feed CM is defined from first 17 Ci and parameters [ L , L ] , [ H , H ] . Physical properties can be predicted with F0(i,X-Di), thermodynamic models and group contribution techniques, like Jobacks method4,5: Species (i,X) properties are calculated from group frequency vector J ( i , X ) . is the vector of CM parameters and P( ) properties to be estimated, including sets of properties with varying degree of complexity as shown in Eqs. 2,3 and 4:

P1 ( ) P( ) = P2 ( ) P3 ( )

P1 ( ) =

0 A J ( i , X )F0 ( i , X Di )dX t 0 Q J ( i , X )F0 ( i , X Di )dX i 0 G( J ( i , X ))F0 ( i , X Di )dX t 0 Q i i i

(2)

P2 ( ) =

J ( i , X )F0 ( i , X Di )dX

(3)

P3 ( ) =

0 0 H ( J ( i , X ), J ( j ,Y ))F0 ( i , X Di )F0 ( j ,Y D j )dXdY i j

( 0 Q t J ( i , X )F0 ( i , X Di )dX )2
i

.... (4)

Tuning CM Parameters by Reconciliation

Typical oil data composes a vector of near 50 observed properties. Calling observations, CM can be tuned via a Maximum Likelihood estimation of

k
:

the kth vector replica of

Min ( 1 / 2 ) ( P( ) k )t W (( P( ) k )

{ }

(5)

where W is known weight positive-definite matrix. Figure 1-C shows reconciled results for 28 Diesel Feeds (database HDT2). Figures 1-A/B show prediction error dispersion and predicted versus observed distillation curves (Oil 106).

(A)

(B)

(C) Figure 1 : Reconciliation Results for 28 Diesel Feeds Database HDT2

HDT Reaction Network

Figure 2 shows a reaction network formulated according literature sources1,2,3,4,5. For reducing the number of kinetic parameters, similar reactions share same kinetic rule. Network encompasses NR=28 continua of reactions impelled by NK=12 kinetic rules. Symbols C1 to C27 (Table 1) represent species continua. A Kinetic rule assigned to reaction j is defined as a function of temperature K j ( T ) .

Figure 2: HDT Reaction Network

(i)= kinetic Rule, [j]= Reaction Continuum, Ci: ith Continuum of Species

Isothermal HDT Reactor Model

An isothermal reactor model is needed for estimating HDT kinetic parameters. It must be noted that the molar density function for species (i,X), after a reactor time t, is now expressed as F ( i , X Di ,t ) . Reaction rates are first order in hydrocarbon species and partial pressure of hydrogen (PPH2). Matric entities are defined below.

H = [ H ik ] : stoichiometric coefficient of family i in reaction k S = [ S ki ] = 1 if family i det er min es rate of reaction k [ S ki ] = 0 if not K ( T ) = Diag ( K 1 ( T ),... , K N R ( T )) , U ( X ) = Diag( U ( X D1 ) , ... ,U ( X D N F ))

Constant

dims influence of species size in the hydrogenation rate through matrix ( X ) = exp( Diag ( X D1 , ... , X D N F )) . Model equations for isothermal HDT5 follow:
( U ( X )F ( X ,t )) = ( PPH 2 )H K ( T )S ( X )U ( X )F ( X ,t ) t
(6)

Which must be solved for the vector of family density functions below.

F ( 1, X D1 ,t ) F ( X ,t ) = M F ( N F , X D N ,t ) F
Eq. (6) are solved analitically5. Defining WHSV as reactor spatial velocity (WHSV=1/t), we have :

U ( X )F ( X ,t ) = exp ( PPH 2 / WHSV )H K ( T )S ( X ) F0 ( X ,t )

(7)

Eq. (7) expresses isothermal reactor model. With it, any property of the treated Diesel can be predicted through formulae similar to Eqs. (2,3,4) for F ( i , X Di ,t ) .

Estimation of HDT Kinetic Parameters

An objective, similar to Eq. (5), is created to measure adherence of HDT model to pilot runs. HDT runs with several Diesel feeds are grouped in isothermal clouds. Using the CM of feeds in Eq. 7, and with the observed data, the NK kinetic parameters and may be estimated. Figure 3-A presents predicted versus observed properties for 54 HDT runs with 8 Diesel feeds (database HDT1). Figure 3-B present comparison of distillation curves for raw and treated Diesel in runs 4305/4407 (feeds 43/44). Figures 3-C,D illustrate conversion of some species continua (runs 2906/3907, feeds 29/39).

References
1. Altgelt, K.H., Boduszynski, M.M. Composition and Analysis of Heavy Petroleum Fractions. Marcel Dekker Inc., 1994. 2. Quann, R.J., Jaffe, S.B. Building Useful Models of Complex Reaction Systems in Petroleum Refining. Chem. Eng. Science, 1996, 51,1615. 3. Quann, R.J., Jaffe, S.B. Structure Oriented Lumping: Describing the Chemistry of Complex Hydrocarbon Mixtures. Ind. Eng. Chem. Res., 1992, 31, 2483. 4. Reid, RC; Prausnitz, J.M.; Poling, B.E. The Properties of Gases and Liquids, McGraw-Hill, N.Y., 1987. 5. Medeiros, J.L., Arajo, O.Q.F., Estimation of Kinetic Parameters and Simulation of Hydrotreatment of Diesel, PETROBRAS Internal Report, V.1, October 1998

(A)

(B)

(C)

(D)

Figure 3. Results of HDT Parameter Estimation