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Coke

Selectivity
Fundamentals

C
oke selectivity is a term that The Concept of Delta Coke
Charles C. Wear often means different things
to different people. So to lead The concept of delta coke is neither
off our discussion, let’s focus on a novel nor complicated. It is simply
definition: Coke selectivity is the rela- the difference between coke on
tive coke-making tendency of any spent catalyst (at stripper outlet)
given cracking catalyst. In the vernac- and coke on regenerated catalyst,
ular, a catalyst that has “good coke expressed as a weight percent of
selectivity” means it produces lower catalyst.
coke compared to some reference
catalyst. This is usually considered a More correctly, delta coke can be
favorable characteristic, since liquid thought of as the amount of coke
yields are preferred. formed on the catalyst for a single
pass of the catalyst through the
That seems fairly straightforward, but reactor which, in the continuous
the often misunderstood part is just steady-state operation of a com-
what the phrase “coke-making ten- mercial FCCU, is also equal to the
dency” really means. Many times it is amount of coke burned off the cat-
confused with coke yield as alyst in the regenerator.
expressed in say, weight percent of
fresh feed. However, the coking ten- Delta coke also has kinetic signifi-
dency of a catalyst in the context of cance, especially on the reactor-
“coke selectivity” is actually its ten- side of the process where it formed.
dency to produce delta coke. The coke on catalyst per pass is a

Catalagram 106 Fall 2009 3


function of many variables, includ- Figure 1
ing but not limited to: feed quality Simplified Overall Energy Balance
and dispersion at the nozzle, reac-
tor temperature and pressure, cata-
lyst activity and contact time, and
last but not least, catalyst coke
selectivity. Reactor Vapors

Therefore, when all other variables


affecting delta coke are more or
less constant, a catalyst that pos- Losses
sesses “coke selectivity” will exhibit Heat of
Reaction Flue Gas
lower delta coke at any given activi-
ty.

A “coke balance” around the regen-


erator results in a useful expression
for delta coke. The coke yield must Stripping Heat of
Stream Combustion
equal the difference in coke enter-
ing and leaving the regenerator.
Therefore,
Coke Yield = C/O (CSC-CRC)
or
CSC-CRC = Coke Yield = Delta Coke
C/O
Recycle
where: Air
Coke Yield is wt.% Feed
C/O is Cat Circulation,
lb. Cat/lb. Feed
Fresh Feed
CRC is Coke on Spent Catalyst,
wt.% Catalyst
CRC is Coke on Regenerated Catalyst,
wt.% Catalyst
ENERGY IN
Fresh Feed
= ENERGY OUT
Reactor Vapors
Recycle Flue Gas
Note that coke yield and cat/oil must Air Misc. Losses
be expressed on the same feed Stripping Stream
basis, fresh or fresh plus recycle, to
yield a meaningful number.
energy to heat the fresh feed, recycle The principle of energy balance
Since coke yield and cat/oil are feed and stripping steam to reactor holds for the individual reactor and
related to delta coke in the above- outlet temperature, to heat the air to regenerator as well as the overall
mentioned manner, it follows that a flue gas temperature, to supply the process, as shown in Figure 2.
coke “selective” catalyst can endothermic heat of reaction and any Table I lists the simplified compo-
decrease coke “yield”, but not nec- losses to the atmosphere--all of this nents to balance each vessel. By
essarily. For instance, in many must come from the coke’s heat of equating the regenerator heat pro-
cases, coke selective catalysts will combustion. A portion of the feed- duction to the heat transferred by
operate with higher cat/oil ratios stock is therefore “consumed” to sup- catalyst, a useful relationship can
with little or no change in coke yield. ply the energy requirements of the be derived:
An understanding of this requires process. Heat of Coke Combustion + Other Terms
examination of the FCCU heat bal- = Heat Transferred by Catalyst
ance and the interaction of process One consequence is that the coke
Coke Yield (ΔHc)
operating variables. yield as weight percent feed is deter-
~
= C/O Cp (TRegen - TRx)
Cat
mined by the sum of these energy
Heat Balance Effects requirements, not by the catalyst coke Delta Coke =
selectivity (or feed coking tendency Coke Yield ~ CpCat
C/O
= ΔHc (TRegen - TRx)
A commercial unit, like all steady- for that matter). This is the key concept
state processes, must be in energy that distinguishes delta coke, which is
balance. This means that the total catalyst and feed related, to coke Noting that the catalyst heat
energy coming into the process yield, which is not. We will return to capacity (CpCat) is constant for
must equal the energy leaving the this concept in a moment. any particular case, along with the
process, as shown in Figure 1. The coke’s specific heat of combus-

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Figure 2
Energy Balance of Reactor and Regenerator Involves Catalyst Circulation Rate

Reactor Vapors

Losses

Heat of
Reaction Flue Gas

Losses

Stripping Heat of
Stream Combustion
Spent Cat

Regen Cat
Recycle
Air

REACTOR REGENERATOR
Fresh Feed HEAT BALANCE HEAT BALANCE

Figure 3
tion (Hc) when hydrogen in coke Typical Effect of Delta Coke on FCC Operation
and degree of CO combustion are
constant, the following proportional- 1400
ity holds: 1380

Delta Coke (TRegen - TRx) 1360


Degrees ˚F

This implies that a coke selective 1340 Regen Temp, ˚F


catalyst will, for a constant reactor
1320
temperature, reduce regenerator
temperature. This is exactly what is 1300
observed commercially. Consider
the unit in full combustion that has 1280 Example:
changed to a catalyst with different
1260 Reactor Temperature
Routine Feed 980˚F
coke selectivity. Depending on the Feed Temperature 450˚F
Sample A
shift in delta coke, the changes No Recycle
shown in Figure 3 occur. FullSample B
Combustion
9.0 2 mol.% O2 in Flue Gas
Sample C
Wt.% Coke Yield or C/O

Of course, unit response to coke


selective catalysts is not limited to 8.0
regenerator temperature reduc-
tions. Consider the unit in partial CO C/O
7.0
combustion, where a drop in regen-
erator temperature could possibly
result in a undesirable increase in 6.0 Coke Yield, wt.%
regenerated catalyst carbon level.
For this case, it would be wise for
the operator to intervene--via 5.0
increased promoter additions 0.60 0.70 0.80 0.90 1.00
and/or air rate-to burn more CO to
Delta Coke, wt.%
Catalagram 106 Fall 2009 5
Table I A Check on Data Consistency
Energy Balance Relationship
The fact that delta coke can be
measured directly by comparing
Reactor Heat Regen Heat Heat Transferrred the difference in coke levels
Requirements Production by Catalyst
between spent and regenerated
+ Heat of Coke
catalyst samples was discussed
+ Heat of Reaction
Combustion earlier. Delta coke determined in
this manner, versus the calculations
+ Heat Up Feed - Heat Up Air
of delta coke from the unit heat bal-
+ Heat Up Recycle - Heat Up Coke
(C/O) Cp cat (TRegen-TRX) ance, can be a useful tool to check
+ Heat Up Strip Stream - Heat Up Rx
data consistency.
Entrainments

+ Account for Losses - Account for Most process engineers will calcu-
Losses
late coke yield using air rate and
- Heat from Regen flue gas composition, and then cal-
Entrainments culate catalyst circulation rate by
heat balance. These coke yield and
cat/oil results can then be used to
CO2 and thus return the dense bed have seen operators use Davison calculate a delta coke. If this “heat
to original temperature. coke selective catalysts to their fullest balance method” to obtain delta
extent, and thus alleviate operating coke differs substantially from the
In this example, these “external constraints and improve refinery prof- direct sampling method, it could
stimuli” from the operator directly itability: mean one or more of the following:
affect the overall heat balance by • Increase reactor temperature to
increasing the heat release per produce maximum gasoline • Incorrect flue gas analysis or
pound of coke burned (higher octane. air rate (the most common
CO2/CO). It therefore takes the com-
• Increase cat circulation for problem).
bustion of less coke to satisfy the • Nonrepresentative catalyst
increased conversion.
energy demand of the process. So,
for this partial combustion case, • Increase resid content for addi- samples (also a common
tional bottoms destruction. problem).
coke yield will drop at the same or
nearly the same reactor/regenerator • Increase feed rate to satisfy • Error in heat balance
temperatures (and therefore cat/oil). increased product demand. method, data or assump-
It has to, because the catalyst tions.
• Increase CO2/CO for lower
caused a reduction in the delta • Excessive entrainment of
coke, and by definition coke yield coke yield.
interstitial hydrocarbons
must be lower if delta coke drops at through the stripper.
constant cat/oil! As with many things in life, “more” cat-
alyst coke selectivity in all cases does
Types of Delta Coke
Remember earlier in this discussion not necessarily mean “better”. A thor-
it was stated that catalyst (and feed ough review of the base operation,
It is convenient to define compo-
quality) have a direct effect on delta including goals and constraints,
nents of delta coke as to source,
coke, but that the unit heat balance should be performed before any cata-
and several proposed breakdowns
determines coke yield. As the pre- lyst change is considered. For exam-
have been published. A sampling is
ceding example showed, some- ple, some operations are precluded
listed in Table II. The three compo-
times it’s difficult to separate what from the use of incremental catalyst
nents of delta coke defined below
changes were caused directly by coke selectivity. Consider the unit in
can be influenced by proper cata-
catalyst (or feed) as opposed to full combustion, at maximum catalyst
lyst design:
heat balance changes made by the circulation and feed temperature, that
operator. cannot “heavy-up” the feed nor
1.Catalytic-the coke deposit
accept a lower reactor temperature.
formed when hydrocarbon is
In reality, the difference is not very This obviously is not a unit that would
cracked via acid site cataly-
important in many cases. The profit from catalyst coke selectivity. it is
sis.
important point is that coke selec- a unit, however, which could greatly
2.Cat/Oil-adsorbed/unstripped
tive catalysts will, in more cases benefit by removing these limitations,
hydrocarbons entrained by
than not, allow an operator to have and many have done exactly that via
catalyst flowing through the
more flexibility in running his plant. revamps.
stripper.
Below are some of the ways we

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3.Contaminant-coke produced as Table II
byproduct of contaminant Typical Delta Coke Breakdowns (1, 2)
metal (V, Ni, Cu, Fe) dehydro-
genation activity. UNIT A B

Catalytic Delta Coke CATALYST Zeolite-Low Metals Zeolite-High Metals

FEED TYPE Gas Oil Resid


Most cracking catalysts have two
sources of acid sites, and therefore DELTA COKE TYPES Wt.% Cat % Total Wt.% Cat % Total
two types of activity-zeolite and
matrix. Zeolite is crystalline Catalytic 0.52 65 0.40 29
silica/alumina with a specific struc-
Cat/Oil 0.12 15 0.10 14
ture. In the usual case it is where
most of the overall catalyst activity Contaminant 0.12 5 0.40 29
resides.
Feed/Nondistillable 0.04 15 0.50 28
The balance of the catalyst particle TOTAL 0.80 100 1.40 100
is defined as the matrix. it may be
similar to the zeolite in composition
(silica/alumina), but does not have Differences in zeolite type also affect technology behind Davison’s cur-
the particular crystalline structure coke selectivity. The key issue is the rent octane catalyst product line.
unique to zeolites. Many of today’s chemical composition (Si/Al ratio) of The coke selective properties of
matrices resemble the amorphous the equilibrated zeolite, which is these octane catalysts have been
catalysts of the 1950’s and 60’s.† measured by X-ray as the unit cell thoroughly treated in earlier
size. Zeolites that equilibrate with high Catalagrams (Numbers 73 and 74).
The activity associated with the zeo- Si/Al ratios (low cell sizes) exhibit
lite and the matrix have very differ- retarded hydrogen transfer rates Cat/Oil Coke
ent selectivity patterns, especially in which, among other things (such as
regard to coke. This is illustrated in increasing gasoline octane), reduce Cat/oil coke is perhaps the most
Figure 4. As matrix activity relative catalytic coke make. Davison’s experi- insidious component of delta coke
to zeolite is minimized, delta coke at ence with these zeolites, generically because1 it is totally independent of
constant activity decreases--the referred to as “ultrastable” or USY any beneficial chemical reaction
catalyst becomes more “coke types, is unmatched in the industry. taking place, such as making gaso-
selective”. The premium form of USY, patented line, and2 it has the highest heat of
by Davison as “Z-14US”, is the core combustion (highest hydrogen con-
tent) which leads to high intraparti-
Figure 4 cle temperatures during regenera-
Effect of Zeolite/Matrix Activity on Catalyst Coke Selectivity tion.
1.4
A properly designed and operated
1.3
catalyst stripper will minimize the
1.2 Pilot Plant Data amount of hydrocarbons that flow
930˚F Reactor Temperature into the regenerator along with the
1.1 75 Sec. Contact Time
Ar
om circulating spent catalyst. Stripping
Relative Delta Coke

ati
1.0
cF
ee
steam rates of at least two lb. per
d@
Pa 60 1000 lb. of catalyst circulated are
raf LV
0.9 fin
ic
%
Co
typically recommended. Increasing
Fe nv
ed
@
ers
ion
catalyst level (residence time) in the
0.8 75
LV stripper can also be effective in min-
%
Co imizing carry-over. The common
0.7 nv
ers
ion commercial practice is to increase
0.6 steam rate and/or stripper level until
0.5 no further reduction in regenerator
temperature is observed, providing,
0.4 of course, reactor-side catalyst
0.0 1.0 2.0 3.0 4.0 5.0 losses do not increase.
Relative Zeolite/Matrix Activity Ratio

†In the 1980's most high matrix catalysts were neither selective nor metals tolerant. Today's high MSA MIDAS® catalysts have been shown to improve coke selectivity
by eliminating and cracking coke precursors.

Catalagram 106 Fall 2009 7


Steam injection displaces hydrocar- Table III
bon vapor between catalyst parti- Effect of Surface Area on Hydrocarbon Stripping
cles-it is not very effective in revers-
ing surface adsorption or pore con-
densation. In some cases, higher Surface Area, M2/g 439 389 105
reactor (stripper) temperatures have 1.8 1.14
Pore Volume, cc/g 0.89
been found to reduce cat/oil coke.
The mechanism may involve volatiz- Volume Avg. Pore Diameter, A 72 184 436
ing and/or further cracking of des-
orbed material.3 Stripping Temperature Unstripped Coke (Wt.% FF) After 1 Minute

Cat/oil coke is also influenced by 900˚F 17.3 17.7 6.4


catalyst matrix pore size and sur- 990˚F 2.0 1.7 1.3
face area. Catalyst “strippability”
can be measured in the lab by sub- Unstripped Coke (Wt.% FF) After 15 Minutes
jecting an inert porous material to 900˚F 1.5 1.3 1.1
heavy oil, followed by nitrogen strip-
ping at typical reactor operating 990˚F 1.7 0.9 0.8
conditions. The results is shown in
Table III as a function of stripping Conditions: MAT REACTOR: 5 gm. Charge, 16 WHSV, 3 C/O,
time and temperature. WEST COAST FEED, N2 STRIPPING AT 30 SCCM,

Volume Avg. Pore Diameter: 40,000 (pore Volume)


High intraparticle temperatures
associated with adsorbed hydrocar- Surface Area
bon have been the subject of sever-
al studies,4,5 which showed that To summarize, catalysts designed to Contaminant Delta Coke
high surface area (hence, more minimize the cat/oil component of delta
adsorptive) catalyst particles are coke should have low surface area, The hydrogen-producing effect of
prone to deactivate rapidly when large average pore diameter matrices feed metals-particularly that of nick-
regenerated. Particle temperatures to discourage hydrocarbon adsorption el, copper, and vanadium-deposit-
several hundred degrees higher and enhance “strippability”. ed on the cracking catalyst is well
than average regenerator bed tem- known. Coke is a companion prod-
peratures were calculated. uct of dehydrogenation, and from
Table II it is clear that contaminant
Table IV
coke can be a substantial percent-
Metal Aging Study Results(10) age of the overall delta coke for
500 ppm Ni (Impregnated After
500 ppm Ni + Sb
metals-laden catalysts.
Steam Deactivation1)

CATALYST Fresh Aged2 Aged2 The passivation of nickel by antimo-


ny (licensed by Phillips Petroleum
Super-D (50 m2/gm)3 Co.) and of vanadium by tin addi-
MA, V% 68.5 69.5 69.0 tives is being practiced commer-
H2, Wt.% 0.21 0.08 0.075
2.6 2.5 2.45
cially.ƒ Claims of a 50% reduction in
Coke, Wt.%
hydrogen and coke produced by
Competitor B (115 m2/gm)3 contaminant metals have been pub-
MA, V% 70.0 68.0 69.5 lished.6,7,8,9
H2, Wt.% 0.42 0.38 0.145
Coke, Wt.% 4.15 4.2 2.8
We have found that the level of
Competitor A (220 m2/gm)3 hydrogen and coke production due
MA, V% 79.0 78.0 77.0 to contaminant metals is also a
H2, Wt.% 0.45 0.35 0.14 function of catalyst matrix composi-
Coke, Wt.% 4.0 3.9 3.8 tion. Matrices with low alumina con-
1Deactivation
tent and low surface areas are more
Conditions: 1350˚F, 100% Steam, 15 psig, 8 Hrs.
2Aged 13 Cycles in Cyclic Fixed-Fluid Bed Pilot Units; 40 WHSV, 3 c/o, 1000˚F
effective in minimizing contaminant
Reaction/1100˚F Regeneration metal dispersion and dehydrogena-
3Typical Matrix Surface Area tion activity√ (Table IV).

ƒTin passivation is no longer practiced in the industry. Integral vanadium traps, such as those in IMPACT, are much more effective for selectivity preservation in high
metals operations.
√See note on page 7.

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Coke Selective Catalyst Davison has used these principles for 4. Bondi, A., Miller, R.S., and Schlaffer, W.G.;
Properties years to design a wide range of cata- Ind. Eng. Chem. Process Des. Dev. 1(3); 962;
p. 196.
lysts. Current examples are members
As can be seen from the preceding of the Octacat, GXO, and Nova fami- 5. Wilson, W.B., Good, G.M., Deahl, T.J.,
discussion, catalyst design has a lies that have led the industry in coke Brewer, C.P., and Appleby, W.G.; Ind. Eng.
direct bearing on the formation of selectivity, as well as octane enhance- Chem.; 48(11), November 1956; p. 1982.
various components of the overall ment. Davison R&D is focused on a 6. Johnson, M.M. and Tabler, D.C.; US No.
“delta coke”. Certain catalyst prop- continuous program of improving 3,711,422.
erties, associated with the true these products, as well as on the
“coke selective” catalyst system, act design of new coke selective grades 7. Dale, G.H. and McKay, D.L.; Hydrocarbon
Processing; September 1977; p. 97.
to minimize delta coke for any given such as the DXB family.
activity level. The essential ingredi- 8. English, A.R. and Kowalczyk, D.C.;
ents are1 a zeolite that will equili- References O&CJ, July 16, 1984; p. 127.
brate at low unit cell size, while
1. Cimbalo, R.N., Foster, R.L., and Wachtel, 9. Barlow, R.C.: “Commercial Application of
retaining the appropriate activity Vanadium Passivation Technology”, NPRA
S.J.; O&GJ; May 15, 1972; p. 112.
level to dominate that of the matrix Spring Meeting, 1986.
and2 a matrix of controlled surface 2. Mauleon, J.L., and Courcelle, J.C.; O&CJ;
10. Ritter, R.E.; Catalagram No. 73; 1985; p.
area with large pores to maximize October 21, 1985; p. 64.
14.
strippability and control dispersion
3. Schuurmans, H.A.J.; Ind. Eng. Chem.
and dehydrogenation activity of Process Des. Dev.; 19(2); 1980; p. 267.
contaminant metals.

Catalagram 106 Fall 2009 9