NATIONAL PETROCHEMICAL & REFINERS ASSOCIATION

1899 L STREET, N.W., SUITE 1000

WASHINGTON, D.C. 20036
AM-00-23
CORRELATION OF FEEDSTOCK CHEMICAL PROPERTIES WITH
CONVERSION AND COKE YIELD IN HEAVY ATMOSPHERIC
RESIDUE CRACKING
by
Claudia Baptista
Senior Process Engineer
Marco Antonio G. Teixeira, PhD
Chemist
William R. Gilbert
Senior Process Engineer
Publio Bonfadini
and
Emanuel Freires Sandes
Senior Process Engineer
PETROBRAS SA
Rio de Janeiro, Brazil
Presented at the
NPRA
2000 Annual Meeting
March 26-28, 2000
Convention Center
San Antonio, Texas
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This paper has been reproduced for the author or authors as a courtesy by the National
Petrochemical & Refiners Association. Publication of this paper does not signify that the contents
necessarily reflect the opinions of the NPRA, its officers, directors, members, or staff. NPRA
claims no copyright in this work. Requests for authorization to quote or use the contents should
be addressed directly to the author(s)
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CORRELATION OF FEEDSTOCK CHEMICAL PROPERTIES
WITH CONVERSION AND COKE YIELD
IN HEAVY ATMOSPHERIC RESIDUE CRACKING
Claudia Baptista, Publio Bonfadini, William Gilbert, Marco Antonio Teixeira.
PETROBRAS R&D Center
Abstract:
Catalytic cracking feed conversion factors are useful tools for crude oil value estimates
and FCC unit optimization. Methods that calculate such factors for feedstocks boiling in
320C to 550C range are available in the literature
[1,2]
. With the start-up of
PETROBRAS residue crackers, processing feedstocks with a substantial portion heavier
than the VGO endpoint, new analytical procedures for residue characterization, capable
of generating conversion and coke selectivity factors for extremely heavy feedstocks,
were necessary.
A set of fifteen atmospheric residues (ATRs), covering the whole range of crude oils
processed in PETROBRAS refineries was characterized by advanced and traditional
methods, and then ran in a circulating pilot riser with equilibrium catalyst. Kinetic
constants of a three lump catalytic cracking model were calculated with the pilot riser
results and correlated with the feed characterization parameters, allowing for conversion
and selectivity prediction based on feed properties.
1. Introduction
Refiners are obliged to produce higher quality transportation fuels and petrochemicals
while processing heavier feed rich in metal contaminants, nitrogen and Concarbon
residue. PETROBRAS is focussing on the improvement of residue cracking
technology
[3]
, increasing its profits on processing heavy feedstock, particularly in the case
of brazilian crudes.
PETROBRAS on stream FCC capacity is over 438,000 BPD. An expansion to 544,000
BPD is in progress through the construction of two new grass roots residue units with
PETROBRAS technology (PAC
RC
). The first PAC
RC
unit started up last December 1999
in RECAP refinery, in So Paulo. It is now successfully running, using as feedstock, an
atmospheric residue with 8.0 CCR from a blend of Brazilian crudes.
To take a full advantage of this hardware, a new residue catalyst system was developed,
and new heavy feed characterization methods and cracking factor correlations were
necessary for the PETROBRAS proprietary FCC process simulator (SimCraq
OT
).
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1.1 PAC
RC
Technology
The PAC
RC
technology is the result of more than 20 years of PETROBRAS experience in
processing heavy feedstocks in FCC. A combined effort of its R&D, Engineering and
Operating teams, covering several areas of knowledge, including: process and mechanical
design and catalyst development. Whenever necessary, PETROBRAS has used
technological partnerships with some of the industrys biggest global players, such as
Akzo-Nobel for catalyst technology and M.W . Kellogg for cat-cooler design, in order to
always assure the best solution available in each case.
PAC
RC
reflects as a whole and in its main features the search for simple but highly
efficient solutions in FCC technology, such as:
Ultramist
TM
feed nozzles with high turnover, and improved feed dispersion
leading to low coke and gas make;
Special riser design - improving gasoline selectivity ;
PASS technology
TM
- PETROBRAS Advanced Separation System a riser
termination device which avoids overcracking in the disengager and reduces
the carryover of hydrocarbons to the stripper to extremely low values;
The unique design off high efficiency regenerator cyclones;
The IsoCAT system - An innovative approach to the FCC thermal balance,
based on the cooling of a slip stream of regenerated catalyst to the riser under
controlled conditions and its mixture with a major stream of hotter regenerated
catalyst prior to the contact with the feedstock.
1.2 New Resid Catalyst System
To face the expected high metal contamination, deactivation severity and allow for
improved bottoms conversion in the residue crackers, a new catalytic system was
formulated combining high accessibility for bottoms cracking, premium matrix for
maximum nickel tolerance and modified REUSY zeolite for vanadium resistance.
1.3 SimCraq
OT
The SimCraq
OT
process simulator was developed as a tool for optimization and process
design, its main features are:
Simulation, parameter estimation , process optimization and what if case studies;
Easy definition of new feedstocks and blends, catalysts and process unit
configurations;
On-line operation through automatic data acquisition of process variables, connected
with real time systems.
The present study was carried out to improve the simulator ability in predicting
conversion and coke yields from the chemical properties of heavy feedstock.
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2. Feed Characterization
Traditional residue evaluation parameters such as CCR, asphaltenes and API, are often
not sufficient and may even be misleading for cracking ability and selectivity prediction
of a given feed. On the other hand, dark color, high viscosity and complexity of ATRs
present a considerable challenge to most characterization techniques. The solution
adopted was to separate the ATR in three different fractions according to solubility in n-
heptane and toluene and quantify key properties in each fraction. Extensive analysis of
the complete ATRs was also done providing complementary information which was also
used in the correlations.
Figure 1 Residue characterization scheme:
ATR : atmospheric residue;
HPLC : high pressure liquid chromatography;
MW : molecular weight by vapor pressure osmometry;
CHN : elemental analysis of carbon, hydrogen and nitrogen;
d : specific gravity (ASTMD70);
AP : aniline point (ASTMD611);
Nbas : basic nitrogen (UOP269);
RCR : Ramsbottom Carbon Residue (ASTMD524);
NMR : proton and C
13
nuclear magnetic ressonance;
S : sulfur content (ASTMD2622).
DI, TRI and POLYAROMATICS are determined by supercritical fluid
chromatography;
PARAFFINS in asphaltenes was determined by supercritical fluid extraction;
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Table 1 Selected feedstock properties:
Feed API RCR
wt%
Nbas
ppm
Saturates
wt%
Aromatics
wt%
Resins
wt%
Asphalten
wt%
Carbenes
wt%
A1 12.2 9.9 2384 24.3 26.0 41.5 6.8 0.2
A2 12.3 13.0 1370 25.5 27.5 34.9 11.7 0.2
A3 12.4 13.3 1107 23.2 25.7 34.3 11.5 0.3
A4 13.6 9.7 2005 27.9 24.7 32.8 5.1 0.2
A5 13.9 12.0 1682 31.5 17.3 40.0 5.2 1.0
M1 14.8 10.8 792 28.5 28.9 31.8 8.1 0.2
M2 15.6 12.0 1597 36.3 16.2 41.1 0.5 0.9
M3 16.3 7.3 1788 34.9 26.2 35.3 2.6 1.0
M4 16.7 5.6 1206 39.8 24.4 28.9 3.2 0.7
P1 18.8 3.4 1136 43.6 26.2 25.3 0.5 0.6
P2 19.2 8.0 1068 40.9 23.0 27.0 4.2 1.5
P3 23.1 4.9 595 57.0 18.5 16.1 2.5 1.2
P4 28.6 12.4 94 65.0 23.2 10.1 0.1 0.2
P5 28.7 3.8 709 55.8 15.4 19.8 2.5 5.4
Feed tags: Pi=Paraffinic, Ai=Aromatic, Mi=Mid range.
3. Pilot Riser feed evaluation:
Petrobras circulating pilot riser, suffered a series of adaptations for heavy feed cracking.
The main changes were in feed injector design, feed preheating, feed-catalyst mixing
chamber, and rapid post-riser separation of spent catalyst and products. More then four
years of experience and continual improvements in heavy feed cracking have been logged
with the adapted pilot riser hardware, allowing it to process on a routine basis feedstocks
of 13% RCR.
A high activity, low metal equilibrium catalyst was chosen so as to enhance feedstock
differences. Feed evaluation was done in the specially adapted circulating pilot riser
[4,5]
,
at constant riser temperature (540C). Catalyst to oil ratios varied between 5 and 10. At
least four experimental points were determined (at different catoil ratios) for every feed.
Coke yield was determined from regenerator flue gas chromatography. Dry gas and LPG
from riser gas product chromatography and gasoline, LCO and bottoms from
chromatographic simulated distilation of the liquid product, using 216C and 344C as
cut points. A new equilibrium catalyst sample was used every time the feed was changed.
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Table 2 Catalyst properties:
BET surface area (m2/g) 177
Micropore vol. (cc/g) 0.066
Zeolite w% 30
RE2O3 w% 1.98
Ni (ppm) 2040
V (ppm) 1800
4. Pilot Riser model:
A three lump model based on the equations proposed by Weekman
[1]
was used to
describe the pilot riser data. Kinetic constants for conversion (K
0
), gasoline production
(K
1
) and gasoline overcracking (K
2
) were calculated for each feedstock. Catalyst
deactivation by coke is accounted for by a exponential deactivation function () and
coordinates are changed from a time base to riser length (x) through division by the space
velocity (S).
Figure 2 3 Lump model equations.
5. Results and discussion:
In Weekmans work and in several subsequent papers
[1,2,6]
dealing with lump model
kinetic constant correlation from feed properties, strong emphasis is given to aromatic
carbon determination as a dominant factor in feedstock susceptibility to the catalytic
cracking reactions. This may still be true for very heavy feedstocks, but in this case
accurate aromatic carbon determination may be extremely difficult in the very complex
mixtures present in ATR. In this work it was found that the saturate fractions of the feed
could be measured with greater precision and therefore resulted in better correlations with
the lump model kinetic constants.
One problem with the ATR characterization scheme used was that it was strongly based
in solvent extraction, which is not solely dependent on the chemical nature of the species
present in the mixture, but also on other factors such as molecular weight. As a result,
chemical species such as aromatics, saturates and polar compounds get distributed along
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Page 6
the several fractions and have to be measured in each one of them, often by different
techniques, and then added to give the ATR total for each group. The solubility
fractionation was necessary in the first place because the characterization of chemical
species could not be done on the whole ATR with the necessary precision.
So, saturate species in the maltene fraction were added to paraffins in the asphaltene
fraction and to the carbene fraction, forming a new group called total saturates. From all
determined properties, total saturates and the basic nitrogen contents were found to be
the statistically relevant parameters for correlation with the pilot riser cracking kinetic
constants, and for conversion prediction. Coke was correlated with second order
conversion, total saturates, resins and RCR. The comparison of predicted and
experimental conversion and coke yield are shown in figure 3. Standard deviation for the
residue distribution was 2.3 for conversion and 1.0 for coke yield.
Figure 3 Comparison of model prediction and experimental results.
Conversi on, wt %
- Prediction vs experime ntal results
60
65
70
75
80
85
90
60 65 70 75 80 85 90
Coke yield, wt %
- Prediction vs experime ntal results
0
2
4
6
8
10
12
14
0 2 4 6 8 10 12 14
Pilot results showed a considerable variation in conversion and coke yields. Some
paraffinic ATRs performing as well or even better than PETROBRAS average VGOs, in
spite of carbon residues in the 3 to 5 RCR range, indicating that most of the heavier part
of these feeds is cracked with relative ease, giving low coke yields. On the other hand,
the more aromatic feeds, as expected, behaved differently. Conversion was substantially
lower and a large part of it went to coke. One concludes from these results that carbon
residue, which is the product of hydrocarbon pyrolysis, does not depend entirely on the
chemical nature of the ATR heavy ends, and therefore is not sufficient for catalytic
cracking reactivity prediction.
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Figure 4 Effect of total saturates and basic nitrogen on conversion.
Figure 5 Effect of total saturates on coke yield.
Figure 4 illustrates the effect of total saturates and basic nitrogen on ATR conversion
obtained from the model equations. The importance of total saturates is greater than that
of basic nitrogen in conversion. In the case of coke yield, the total saturates , resins and
RCR are all statistically significant, the total saturates, again, being the most relevant. In
figure 5, the coke yield is correlated with the total saturates.
Total saturates is also a determining factor in gasoline selectivity (figure 6). Pilot riser
results showed substantial gasoline overcracking which may have been caused by the
catalyst used in the study, a LPG maximizing type.
Conversion vs Catoil - Effect of saturates
(contant basic nitrogen):
60
65
70
75
80
85
5.0 7.0 9.0 11.0 13.0
catoil
c
o
n
v

w
%
T. SAT=60
T. SAT=30
T. SAT=45
Conversion vs Catoil - Effect of basi c
nitrogen (constant saturates):
60
64
68
72
76
80
5.0 7.0 9.0 11.0 13.0
catoil
c
o
n
v

w
%
Nbas=600
Nbas=2100
Nbas=1350
Coke vs conv/(100-conv) - Effect of
saturates
4
6
8
10
12
1.5 2 2.5 3 3.5 4 4.5 5
conv/(100-conv)
c
o
k
e

w
%
T. SAT=60
T. SAT=30
T. SAT=45
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Figure 6 Gasoline (IBP-216C) experimental results:
Many of the ATRs advanced characterization results correlate with bulk properties
determined by traditional methods (figure 7 ). The two most significant parameters for
feed conversion and coke selectivity: total saturates and resins, can be reliably estimated
from equations (1) and (2) below:
Total Saturates = 300 265 d 2.51 S 0.0045 Nbas = 1.4 R2 = 0.98 (1)
Resins = -17.56 + 29 d + 0.009 Nbas = 2.4 R2 = 0.94 (2)
Figure 7 Correlation of Total Saturates with other properties:
ATR bulk properties vs Total Saturates
40
50
60
70
80
90
100
110
120
20 25 30 35 40 45 50 55 60 65 70
0
5
10
15
20
25
30
AP (C) API
Gasoline vs Conversion
CONVERSION (% wt)
G
A
S
O
L
I
N
E

(
%
w
t
)
28
30
32
34
36
38
40
42
44
46
62 68 74 80 86 92
TOTAL SATURATES
25-35 %
35-45 %
55 %
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6. Conclusions:
To optimize the current Residue FCC operation a process simulator well tuned to the
heavy feedstock processed will be essential. Feed properties such as total saturates, the
sum of saturate species in maltene, asphaltene and carbene solubility fractions, and basic
nitrogen can be used to define catalytic cracking feed conversion and coke selectivity
factors. Total Saturates, was the most important factor in all pilot riser cracking results.
Although RCR did have a small effect on coke selectivity, this effect was not enough to
justify its use as key heavy feed characterization parameter, as is the case in residue
processing today. Simple ATR bulk properties, as density, sulfur, and basic nitrogen can
be used to estimate total saturates and resins which would otherwise have to be
determined by more elaborate analytical procedures.
7. Literature cited:
1. Nace,D.M., Voltz,S.E., Weekman, V. M., Ind .Eng. Chem, 45, 1186 (1953).
2. Yen, L.C., AIChE Spring National Meeting, Session #84 (1989).
3. Chang, T., Oil & Gas Journal, Mar. 22, 63 (1999).
4. Baptista, C.M., Pinho, A.R., Bol.tec. PETROBRAS, 40(2/4): 173-180, (1997)
5. Schlosser, C.M., Castillero, J.M., Baptista , C.M, Rogers, J., Leung, P., NPRA AM-99-
50, (1999)
6. Anheyta-Juarez , J. et al, Ind. Eng. Chem, 37, 4637 (1998).
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