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Calculating atmospheric residue FCC product slate

A set of atmospheric residues was cracked in a circulating riser pilot plant and the results interpreted with the help of a process simulation model. New heavy feed properties were identified as being important factors in product yield prediction
William Gilbert Claudia Baptista Marco Antonio Teixeira Petrobras

atalytic cracking feed conversion factors are useful tools for crude oil value estimates and FCC unit optimisation. Methods that calculate such factors for feedstocks boiling in the 320C to 550C range are available in 1,2,3 With the startup of the literature. Petrobras residue crackers, processing feedstocks with a substantial portion heavier than the VGO endpoint, it was necessary to use new analytical procedures for residue characterisation, capable of generating conversion and coke selectivity factors for extremely heavy feedstocks. Conversion of crude oil heavy ends to products of high value, such as light fuels and petrochemical starting materials, has been a continuing trend in the refining industry. This strategy is particularly challenging, since petroleum residues are difficult feeds to process, requiring special equipment and catalysts. The FCC route has been chosen by Petrobras as a means of upgrading residues, and a lot of experience has been accumulated in the past two decades, leading to several process innovations, and culminating in the design of three new grassroots residue FCCs. The first, in RECAP refinery, was started in December 1999, and is processing autothermal reforming (ATR) with carbon residue above 8 wt%. To take the full advantage of these new units, a programme for heavy feed physical-chemical characterisation, followed with FCC pilot riser cracking, was established, generating a database from which new correlations could be developed for the companys Simcraq process simulator. The precise chemical characterisation of heavy residues is a challenging issue in itself. Residues are complex mixtures of many thousands of components; their dark colour, high viscosity and boiling point, fall outside the range of most analytical procedures used for 4 hydrocarbons. Composition models regard ATR as two-phase systems, with asphaltene aggregates, solvated by resins

Figure 1 ATR chemical representation

and suspended in liquid large molecular weight hydrocarbons. In these models asphaltenes are described as multiple condensed aromatic ring macromolecules, with a relatively high content of hetero-atoms and metals. The flat polyaromatic sheets of several of these molecules tend to form stacks, with paraffinic hydrocarbon chains on the edges, in contact with liquid medium. Resins have intermediate levels of aromatics and hetero-atoms, lying between the asphaltenes and the heavy hydrocarbons that dissolve the mixture. In solvent extraction processes, the equilibrium that keeps asphaltenes in suspension is disturbed, leading to their precipitation. Figure 1 shows the chemical representation of species found in the mixture, with molecular weights (MW) and carbon/hydrogen (C/H) ratios of one of the feeds in the study. The feed characterisation scheme used in this work, started with ATR extraction with n-heptane, the soluble fraction was classified as maltenes. The insoluble fraction was then washed with toluene, the toluene soluble fraction was called asphaltenes and the insoluble fraction carbenes. Differential Scanning Calorimetry (DSC) of the asphaltene fraction showed that high molecular weight paraffins were present, by their heat of fusion.

Figure 2 Feed characterisation scheme

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The content of the paraffin portion in the asphaltenes was then determined by supercritical fluid extraction (SFE). The maltenes, n-heptane soluble fraction, were submitted to high pressure liquid chromatography (HPLC), being separated into saturates, aromatics and resins. The maltene-aromatics were further characterised into mono, di, tri and polyaromatics, through supercritical fluid chromatography (SFC). The molecular weight of the maltenesaturates was measured by vapour pressure osmometry (VPO). For the resin and asphaltene fractions not only was VPO molecular weight determined, but also carbon, hydrogen and nitrogen contents, by elemental analysis. The carbene fraction was too small in most feeds for any additional characterisation. ATR bulk properties were also measured, such as density, aniline point, basic nitrogen, carbon residue, NMR spectroscopy and Small Angle X-Ray Scattering (SAXS). Two parameters were obtained from SAXS spectroscopy: Inertial Radius (Ri), which measures the average volume of asphaltene polyaromatic nuclei, and NAC index, which is proportional to the number of asphaltene polyaromatic nuclei dispersed in the sample. Table 1, shows some of the results, where Ai stands for aromatic ATRs, Pi for paraffinic ATRs and Mi for intermediate ATRs. The feed characterisation scheme is outlined in Figure 2 (on previous page).

Selected ATR properties

Feed API A1 A2 A3 A4 M1 M2 M3 M4 P1 P2 P3 P4 12.2 12.3 12.4 13.6 14.8 15.6 16.3 16.7 18.8 19.2 23.1 28.6 RCR p% 9.9 13.0 13.3 9.7 10.8 12.0 7.3 5.6 3.4 8.0 4.9 1.9 Nbas ppm 2384 1370 1107 2005 792 1597 1788 1206 1136 1068 595 94 Saturates p% 24.3 25.5 23.2 27.9 28.5 36.3 34.9 39.8 43.6 40.9 57.0 65.0 Aromatic p% 26.0 27.5 25.7 24.7 28.9 16.2 26.2 24.4 26.2 23.0 18.5 23.2 Resins p% 41.5 34.9 34.3 32.8 31.8 41.1 35.3 28.9 25.3 27.0 16.1 10.1 Asphaltene Carbenes p% p% 6.8 11.7 11.5 5.1 8.1 0.5 2.6 3.2 0.5 4.2 2.5 0.1 0.2 0.2 0.3 0.2 0.2 0.9 1.0 0.7 0.6 1.5 1.2 0.2 NAC index 48 69 100 51 74 108 39 55 32 67 41 17

Table 1
results. It is a common procedure to isolate the gasoline yield in a single lump; inefficiencies in the LPG/gasoline fractionation in the pilot riser led to a large scattering of the data, making it harder for the model to describe the experimental results. Lumping LPG and gasoline together gave the additional advantage of simplifying the reaction mechanism by despising the lumps contribution to coke formation and by considering gasoline overcracking as yielding exclusively LPG, therefore, not changing the overall LPG plus gasoline yield. The Dry Gas lump (C1, C2 and hydrogen) formation was attributed to noncatalytic thermal cracking and correlated to the post riser catalyst disengagement vessel temperature. The LCO lump rate of formation, (equation 7, in panel below), was derived from the empirical observation that LCO yield plotted against LCO plus bottoms (ATR plus LCO lump in Figure 3) was linear as (ATR plus LCO) tended to zero and that

DryGas = DGasAv + Adg.(Taverage) = expt(.t/CTO) d(ATR + LCO) = [k2 (ATR + LCO)2 + k4 (ATR + LCO)] dt
d(LPG + GLN) 2 = .k2 (ATR + LCO) dt d(Coke) = .k4 (ATR + LCO) dt d(GLN) = k6 k7.(GLN + LPG) d(GLN + LPG d(LCO) = k8 k9.exp[k10.(ATR + LCO)] d(ATR + LCO) x = exp [ k4 .CTO.[exp ( .t) 1 ]] CTO (ATR+ LCO) = k4.x .100 k2.x k2 k4

(1) (2) (3) (4)

(5) (6)

Pilot riser evaluation

The Petrobras pilot riser suffered a few adaptations for heavy residue processing, including changes to feed injection configuration, catalyst/feed mixing zone, and catalyst/product post riser disengagement. For the feedstock evaluation, a high activity equilibrium catalyst was used in order to enhance differences between the feeds. All runs were done with isothermal riser temperature of 540C. Catalyst-to-oil ratio was varied between 5 and 10, and at least four experimental points at different c/o ratios were used for every feed. Coke yield was calculated from flue gas chromatography. Dry gas and LPG were determined from gas product chromatography and gasoline, LCO and bottoms from liquid product simulated distillation, using 216C and 344C as cut points. Catalyst properties were as follows: 2 177 Specific area (m /g) 3 Micropore volume (cm /g) 0.066 1.98 RE2O3 % Ni (ppm) 2040 V (ppm) 1800 Modelling pilot riser results Figure 3 illustrates the lumps composition used in the modelling of the riser

(7)

(8)

(9)

Coke =

k2 + k4 k4 ln .100 k2 (ATR + LCO) k2 + k4 100

(10)

GLN = k6.(GLN + GLP) _ k7 (GLN + GLP)2 2 k9 k9 LCO = (lexp [k9]) . (ATR + LCO ) (lexp [k9.(ATR + LCO)]) k8 k8

(11)

(12)

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Nomenclature
DgasAv: T: Taverage: Adg: CTO: t: : Average dry gas yield Post Riser disengager vessel temperature Average Post Riser temperature Constant for all feeds Catalyst-to-oil ratio Riser residence time Catalyst deactivation temperature Lump mode kinetic constants (i = 280) Gasoline Atmospheric bottoms Carbon residue Density

Figure 3 Lump composition scheme used in the modelling

ki: GLN: ATR: RCR: d:

Figure 4 Comparison of experimental results and yields calculated from equations 8 through 12
LCO yield was zero for reaction time zero. Gasoline yield was derived from the (gasoline plus LPG) lump through equation 6. An exponential catalyst deactivation function was used, and the deactivation constant was correlated to the inverse of the catalyst-to-oil ratio (equation 2). With all these assumptions, one arrives at the equations 1 to 7 (in panel). Equations 3 through 7 can be integrated and solved for boundary conditions, yielding equations 8 through 11. These equations were then fitted to the experimental results, and the values of k2, k4, k6, k7 and k8 were calculated for each of the feedstocks, other parameters such as , riser residence time and Adg were held constant. Figure 4 compares the experimental results with those calculated from the optimised yield functions

Results and discussion

The lump model kinetic constants thus obtained could be correlated with feed

Correlation coefficients for some feed properties

Correlation coefficients (R2) between model parameters and the feed properties: basic nitrogen, density (d), carbon residue (RCR), saturates, NAC index, the product of NAC index times Inertial Radius (from SAXS analysis), aromatic carbon and aliphatic CH2 (H)both from NMR Importance k2 GLN+LPG k4 Coke GLNMax GLN DGasAv Dry gas Basic.N 0.55 0.11 0.39 0.65 d 0.80 0.27 0.48 0.86 RCR 0.31 0.59 0.38 0.64 Saturates NAC InRad x C arom NAC NMR 0.78 0.05 0.65 0.07 0.73 0.27 0.70 0.27 0.65 0.26 0.25 0.43 0.89 0.24 0.68 0.28 H NMR 0.85 0.08 0.34 0.65

Table 2

properties measured in the characterisation scheme. In many instances more than one of the feed analytical data would correlate with a given kinetic constant, which is not surprising, since there was a strong correlation between several of the feed properties. In the case of k6 and k7, which appear in the gasoline yield equation 11, the best correlation was obtained for the maximum gasoline value, which can be expressed 2 as the ratio 1/4k6 /k7. Table 2 shows correlation coefficients for some of the feed properties. In Weekmans work and in subse1,2,5 dealing with lump quent papers, model kinetic constant estimates from feed properties, aromatic carbon content in the feed was the most important factor in catalytic cracking reactivity. For atmospheric bottoms, the accurate measurement of aromatic carbon is not feasible, and better correlations are found for saturate carbon content, which is easier to measure. Table 2 shows how k2, GLNmax and DgasAv correlate well with Saturates in the feed and aliphatic CH2. In the case of coke yield, constant k4, the best correlation was obtained for the product of NAC index times Inertial Radius, determined from SAXS analysis. The NAC, Inertial Radius product is proportional to the concentration of asphaltene polyaromatic nuclei, which may be interpreted as microscopic coke particles suspended in the feed even before any chemical reaction has taken place. These particles are the single most important factor in coke yield determination for atmospheric bottoms catalytic cracking. And the SAXS analysis is the best technique for their quantification. Carbon residue is affected by asphaltene polyaromatic nuclei, but there are other factors that may contribute to carbon residue formation which will mask its

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Advanced feed characterisation parameter estimate

Advanced characterisation NMR H Saturates NAC x Inert.Radius = = = Function of traditional methods F(density, Carb.Residue) F(density, basic Nitrog, Sulphur) F(Carb.Residue, Aniline Pt) R2 0.90 0.98 0.87

Table 3
contribution, explaining the inferior correlation between carbon residue and coke yield. Average errors of yield prediction from feed properties, using the lump model equations and the multivariable correlations for the lump model kinetic constants, are as follows: Dry gas 0.7 LPG+GLN 2.4 Gasoline 5.1 LCO 1.1 Coke 1.4 Conversion 2.4 Many of the analytical procedures used in this work are too elaborate for routine feed characterisation; nevertheless the correlations obtained can still be used since the properties measured in the advanced feed characterisation can be estimated from more familiar feed properties. Table 3 shows how the three most relevant feed properties, obtained from the advanced feed characterisation, can be calculated with reasonable accuracy from traditional analytical methods. In conclusion, the advanced characterisation of atmospheric residues has brought a deeper understanding of the chemical nature of these FCC feedstocks, leading to the development of semiempirical mathematical models capable of conversion and product yield prediction

PhD from Universidade Federal do Rio de Janeiro in 1998.

References
1.Nace D M, Voltz S E, Weekman V M, Applications for a Kinetic Model for Catalytic Cracking; Ind Eng Chem 45, 1186 (1953). 2.Yen, L C, Kinetic Modelling of Fluid Catalytic Cracking; AIChE Spring National Meeting, Session 84 (1989). 3.Torem, M A, Development of a new coefficient to predict FCC feedstock cracking; ACS 206th National Meeting Advances in Fluid Catalytic Cracking, Chicago, USA (1993). 4. Wiehe, I A, A Tutorial on the Phase Behaviour of Asphaltenes; AIChE Spring National Meeting, Houston, Texas, 54, (1999). 5.Anheyta-Juarez J et al, Correlations for Predicting the Effect of Feedstock Properties on Catalytic Cracking Kinetic Parameters; Ind Eng Chem, 37, 4637 (1998). 6.Mauleon J L, Sigaud J B, Characterisation and Selection of Heavy Feeds for Upgrading Through FCC, 12th World Petroleum Congress, 4, 71 (1987).

William Gilbert is a research engineer at the Petrobras R&D Centre, Rio de Janeiro, and is involved in FCC catalyst and feedstock evaluation. He gained a Bachelors degree in chemical engineering from Universidade Federal do Rio de Janeiro in 1984. Claudia M L Baptista is a senior research engineer in the R&D Centre and is in charge of process development activities in thermal and catalytic conversion areas, with technical assistance to Petrobras refineries. She obtained her Bachelors degree in chemical engineering from Universidade do Estado do Rio de Janeiro in 1984. Marco Antonio Teixeira is senior research scientist at the R&D Centre. He currently coordinates research in applied organic chemistry and is a professor at PUC university, Rio de Janeiro. He holds a Bachelors degree in chemistry from Universidade Federal Fluminense in 1988 and a

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