Jnited States Patent

;ross et al.
54] SIMULATION PROCESS Inventors: OF CATALYTIC

[19]

[ 11]
[45]

4,187,548
Feb. 5, 1980

CRACKING

[58]
[561

Field of Search

235/151.12, 151.35, 235/150; 444/1; 208/113; 364/121, 200, 900,

578, 500-501

[75J

Benjamin Gross; Solomon M. Jacob, both of Cherry Hill; Donald M. Nace, Woodbury, all of N.J.; Sterling E. Voltz, Media, Pa. Mobil Oil Corporation, N.Y. 472,525 May 23, 1974 New York,

References

Cited
235/151.12 235/151.12 X 235/151.12

U.S. PATENT
3,591,783 3,702,003 3,725,653 7/1971 10/1972 4/1973

DOCUMENTS

[73J
[21] [22]

Assignee:

Zumwalt Ramirez, Jr. et aJ. Carr et aJ.

Appl. No.: Filed:

Primary Examiner-Edward J. Wise Attorney, Agent, 01' Firm-Charles A. Huggett; Michael

G. Gilman

[57]

ABSTRACT

Related U.S. Application Data [63]

Continuation doned. of Ser. No. 148,051, May 28, 1971, aban-

[51J [52J

Int. ct.2 U.S. C1

The specific disclosure is directed to a catalytic cracking model wherein the reactant and product species are lumped according to molecular type and boiling range. The specific invariant lumping scheme includes paraffins, naphthenes, aromatic rings, and aromatic substituent groups.

G06F 15/32
364/578; 364/121

5 Claims, 33 Drawing Figures

REGENERATOR

REACTOR

I I

36
----,

I"II Iff I
I

Air

10

&j

II II I 11

35

u.s.

Patent

Feb. 5, 1980

Sheet 1 of 33

4,187,548

FI G.1

REGENERATOR
Flue Gas To CO Boi ler

REAC10R

42
r
I

I I I

36
---II
I

I II II I II Air
I

II

10

i"~II
I

I II I II

II

35

u.s. Patent

Feb. 5, 1980

Sheet 2 of 33

4,187,548

FIG.2
LUMPED KINETIC SCHEME

u.s. Patent

Feb. 5, 1980

Sheet 3 of 33

4,187,548

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u.s. Patent

Feb. 5, 1980

Sheet 4 of 33

4,187,548

FIG.4

Computed Vs. Observed Time-Averaged Gasoline Yields

o o

FLUIDIZED

DENSE BED CRACKING

G LUMP (C5 - 43D Fl

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)(

30.00

Y COMPUTED

40.00

50.00

60.00

70.00

u.s.

Patent

Feb. 5, 1980

Sheet 5 of 33

4,187,548

FIG.5

computed Vs. Observed Time-Averaged

C Lump Yields

o
o o
(I')

FLUIDIZED
CLUMP

DENSE BED CRACKING

+

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COKE)

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10.00

Y COMPUTED

lS.00

20.00

25.00

30.00

U.S. Patent

Feb. 5, 1980

Sheet 6 of 33

4,187,548

FIG.6

computed Vs. Observed Time-Averaged LFO Yields

FLUIDIZED
0 0 0 ID

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F)

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20.00

30.00

COMPUTED

40.00

50.00

60.00

u.S. Patent

Feb. 5, 1980

Sheet 7 of 33

4,187,548

FIG.7

Observed

Vs. Computed

Time-Averaged As a Function

Gasoline of Charge

Yl.'elds (tc ~ 5.0 Minutes) Stock

FLUID CATALYST CRACKING

0

REACTOR TYPE

C?
0 0

FLUIDIZED DENSE BED TC 5.000 900.0 10.0 MIN

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5.00

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15.00

OIL/WT CATALYST - HR

20.00

25.00

SO.OO

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40.00

u.s.

Patent

Feb. 5, 1980

Sheet 8 of 33

4,187,548

FI G. 8

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Gasoline of Charge

Yields stock

(tc

1.25 Minutes)

FLUID CRTRLYST
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OIL/WT CATALYST - HR

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Sheet 10 of 33

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FIG.IO

Model Selectivity Plot for a Naphthenic Charge Stock (N3) tc = 5.0 Minutes, Temp = 900°F

FLUID
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CATALYST TYPE

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REACTOR

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Sheet 12 of 33

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FIG.12

Model Selectivity Plots for a Paraffinic Charge Stock tc = 5.0 Minutes, Temp = 900°F

(P3)

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Sheet 14 of 33

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FIG.14

Model Selectivity Plot for an Aromatic Charge Stock (PA33) tc = 5.0 Minutes, Temp = 90QOF

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0 0 0 Ln 0
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c.n
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'0 ~

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>-

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- "'-" Z
U 0:

(T')

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+

~'...I 0
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~
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...J u,

=>

u, 0 Ln 0
I

lLJ

o~

t-

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.j.J

o
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1-1

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(0

U lLJ

Ln

III

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W n,

(T')

I--

1-1 III 0.. X Iil

_,
0

•
_,

-z
0
U I ...J 0:

•
1:

0,~ !!!I--

°lLJ 0

0 ...I

~>
-1.&..1
U 0:

=>

I-U 0:

0
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c.n
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lL.

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00'09

r<>
<.9
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00'09

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'lM 0131)"

OO'OZ

00'00

u.s. Patent

Feb. 5, 1980

Sheet 32 of 33

4,187,548

Fl G. 32
Predicted Vs. Observed Ethylene Yields in catalytic Cracking

FLUIDIZED DENSE BED CRACKING

-.
o o

LIGHT ENDS - C2=

x

\.
X ~fC

.'#x
Xx

.0

:s
CI LLJo LLJ
Cf.)

to-

>~
0::;0

CD C

>-~

o
o

~.OO

.+-----~~----~------~------~----~
0.20

Y COMPUTED WT. PERCENT

0.40

0.60

0.80

1.00

U.S. Patent

Feb. 5, 1980

Sheet 33 of 33

4,187,548

FIG.33
predicted Vs. Observed Normal Butane Yields in Catalytic Cracking

FLUIDIZED DENSE BED CRACKING

o o

LIGHT ENOS - NORMAL C4

• N

:E

lAJo

Q::lAJ
CI)

>~

CD

,_-?
'0

9:1.00

.~------~----------------------------0.80

Y COMPUTED WT. PERCENT

1.60

2.40

S.20

4.00

1
SIMULATION OF CATALYTIC CRACKING PROCESS

4,187,548

of hydrocarbon reactants in the reactor in accordance with:

<jg/dl=Q~Il.

This application is a continuation of application Ser. 5 where No. 148,051, filed May 28, 1971, now abandoned. Qjl/dt=rates of reaction, BACKGROUND OF THE INVENTION Q=catalyst properties and process variables, l\=matrix of reaction rate constants lumped kineti1. Field of the Invention The present invention is directed to a method and a 10 caiTyand according to boiling range, and a=composition vector of reactants and product spesystem for simulating a catalytic cracking process. ci~ lumped according to molecular type and boiling More particularly, the present invention is directed to a range. kinetic computer model for a catalytic cracking proThe processing means is further programmed to genercess. IS ate the composition vector ! as a function of reaction 2. Description of the Prior Art time. In a refinery operation such as a fluid catalytic cracking system, the number of different molecules involved BRIEF DESCRIPTION OF THE DRAWINGS runs into the thousands. Consequently, it is impossible, FIG. 1 is a block diagram of a catalyst section of a or at least greatly impractical, to investigate each of the thousands of molecules to determine the kinetics of a 20 fluid catalytic cracking process; FIG. 2 shows a kinetic scheme for a specific embodisystem or to characterize feed stocks or products. Howment of the present invention; ever, it is known to partition molecules into a number of FIG. 3 is a matrix of rate constants for a specific classes and then to consider each class as an independent entity. For example, it is possible to consider all 25 embodiment of the present invention; and FIGS. 4 through 33 are graphs of computer generoxygen molecules as "oxygen", even though the kinetic ated data. energies of the individual oxygen molecules are different. Such grouping or lumping is used in a standard DESCRIPTION OF SPECIFIC EMBODIMENTS petroleum processing analysis known as PONA, in FIG. 1shows the essentials of a typical catalyst secwhich all species are divided into 4 classes: paraffins, 30 tion control system wherein fresh hydrocarbon feed olefins, naphthenes and aromatics. which can include recycle oil from a fractionator (not shown) is applied by a line 35 to the lower end of a riser SUMMARY OF THE INVENTION line 36. Heated regenerated catayst from a standpipe 39 In accordance with the present invention, there is having a control 40 is combined with the oil in the riser provided a method for simulation of a catalytic crack- 35 line 36 such that an oil-catalyst mixture rises in an asing process for the conversion of the hydrocarbon feed cending dispersed stream to the lower end of a reactor stream wherein the stream is contacted with an active 31. In the reactor 31, there may be further fluidized catalyst in a reactor maintained under catalytic convercontacting between the oil and the catalyst particles sion conditions to provide reaction products which are within a relatively dense fluidized bed diagrammatically removed from the reactor. The catalyst in the reactor 40 represented below the dashed line 42. Generally, a becomes contaminated by the deposition of coke major portion of the necessary cracking and contact of thereon. The simulation method comprises programthe oil with the catalyst takes place in the riser 36. ming an automatic processing system to (a) generate At the upper end of the reactor, the catalyst particles rates of change of hydrocarbon reactants in the reactor are separated from the vaporous cracked reaction prodin accordance with: 45 ucts by cyclone separating means (not shown). The reaction products are transferred overhead by a line 37 <jg/dl=Qt,!!. to a products recovery section which includes at least one fractionator (not shown). A stream of spent or where coked catalyst is continuously passed from the reactor da/dt e rates of reaction, SO 31 to a regenerator 15 by a spent catalyst transfer line 29 Q = catalyst properties and process variables, having a control valve 28 such that the catalyst is transK=matdx of reaction rate constants lumped kinetiferred to the regenerator 15 at a controlled rate. catTyand according to boiling range, and In the regenerator 15, the carbonized or coked cata!=composition vector of reactants and product spelyst particles are subjected to oxidation and carbon cies lumped according to molecular type and boiling 55 removal in the presence of air being introduced to the range, and, regenerator by a line 10. A bypass line 11 having a (b) generate the composition vector! as a function of control valve 38 is connected to the line 10 to vent a reaction time. portion of the air being introduced into the regenerator In accordance with another aspect of the present 15 and thus regulate the flow rate of air. invention, there is provided a system for simulating a 60 In the lower portion of the regenerator 15, a fluidized catalytic cracking process for the conversion of a hydense phase bed diagrammatically represented as below drocarbon feed stream wherein the stream is contacted the dashed line 19 provides for contact between the with an active catalyst in a reactor maintained under coked catalyst particles and the oxidizing air stream. In catalytic conversion conditions to provide reaction the upper portion of the regenerator IS, a light phase products which are removed from the reactor. The 65 zone permits the separation of catalyst particles by suitcatalyst in the reactor becomes contaminated by the able centrifugal separating means (not shown) from a deposition of coke thereon. The system comprises proflue gas stream being discharged from the regenerator cessing means programmed to generate rates of change 15 by a line 17 having a control valve 24 therein. The

line 17 vents the regenerator flue gas or feeds the flue gas to a carbon monoxide boiler (not shown) where the carbon monoxide is converted to carbon dioxide. A level controller 27 is connected by level indicating taps 25, 26 to the side wall of the reactor 31. A control line 43 from the level controller 27 is connected to the valve 28 in the transfer line 29 to control the flow rate of catalyst through the transfer line 29. Thus. the dense phase bed 42 level and quantity of catalyst in the lower portion of the reactor 31 are maintained at desired values. A temperature controller 32 is connected to a temperature indicating means 30 at the upper portion of the reactor 31, and generates a control signal on a line 33 to control the setting of the valve 40. Thus, a variable quantity of hot regenerated catalyst may be withdrawn from the standpipe 39 to the riser line 36 to maintain a predetermined reactor temperature as defined by the set point of the temperature controller 32. A pressure sensitive means 22 is positioned in the upper part of the reactor 31, and another pressure sensitive means 20 is positioned in the upper portion of the regenerator 15. The pressure sensitive means 20, 22 are connected to a differential pressure regulator 21 having an adjustable set point to maintain a desired differential pressure between the reactor 31 and the regenerator 15. The differential pressure regulator 21 is connected by a line 23 to the control valve 24 in the line 17 to regulate the flue gas flow through the line 17 and in tum vary the internal pressure within the upper portion of the regenerator 15 to thereby maintain the desired pressure difference between the reactor 31 and the regenerator IS. Generally. the pressure differential between the reactor 31 and the regenerator 15 is relatively low, for example. in the order of about 6 psi, and is necessary to permit the maintenance of suitable pressure differentials across the slide valves 28, 40 in the spent catalyst transfer line 29 and in the standpipe 39 to thus provide for a continuous circulation of catalyst particles between the reactor 31 and the regenerator IS. Temperature indicating means 13. 14 within the lower and upper portions of the regenerator IS are connected to a differential temperature controller 16. which in turn is connected by a line 18 to the valve 38 in the air vent line 11. Thus, when the temperature differential between the lower and the upper portions of the regenerator 15 varies from a predetermined differential as defined by the set point of the differential pressure controller 16. the valve 38 in the vent line 11 is adjusted to control the amount of air flowing in the line 10 to the lower portion of the regenerator 15. In accordance with an aspect of the present invention. there is provided a lumped invariant kinetic model for catalytic cracking processes. The model contains an invariant kinetic scheme of simultaneous and consecutive reactions to predict the product yields produced in the reactor such as that shown in FIG. 1. The yields predicted in this specific embodiment are gasoline, light fuel oil. and light ends + coke (C lump). Correlation methods based on certain kinetic principles are used to break the C lump into individual light ends and coke. The lumping scheme groups kinetically similar molecules or components according to boiling range of the molecules or components. The lumping scheme according to a specific embodiment is based on the concentrations of paraffins, naphthenes, aromatic rings, and aromatic substituent groups (paraffinic and naphthenic groups attached to aromatic rings) in the charge stock in line 35 and appears adequate to predict the major

4,187,548

10

15

20

25

product yields in the cracking of widely different charge stocks under a broad range of process conditions. Gas oils of wide boiling range have thousands of compounds of different molecular structures and molecular weights. However, the kinetic behavior of so many different molecules can be reasonably accounted for by such a relatively simple lumping scheme in accordance with this specific embodiment. The product yields of virgin gas oils can be adequately predicted by the simple lumping scheme of paraffins. naphthenes, and aromatics; however, it is necessary to split the aromatics into aromatic rings and aromatic substituent groups to include recycle feedstocks in the model. This is not unexpected, since the molecular compositions of recycle feeds are significantly different from those of virgin gas oils. Recycle feedstocks are generally recycled from the fractionator (not shown) downstream on line 37. and are combined with the fresh charge stock in the line 35. In addition to the lumping scheme, other factors have been incorporated into the model of the present embodiment to account for process variables and other related phenomena. A catalyst decay term is provided to account for the rapid deactivation of the catalyst which occurs during the catalytic cracking of gas oils in the line 36 and the reactor 31. Other features are an adsorption term for nitrogen poisoning. activation energies, molecular weight, residual carbon on regenerated catalyst in the line 39. and some catalyst effects. Lumping and Reaction Scheme

30

35

40

45

50

55

60

65

The lumped invariant kinetic model for fluid catalytic cracking such as shown in FIG. 1 consists of a kinetic scheme shown in FIG. 2. With reference to FIG. 2. ten lumps are provided to follow the cracking of virgin gas oils and recycle oil charge stocks. The lumps of FIG. 1 are: P/= Wt. % paraffinic molecules, (mass spec analysis). 430· -650· F. N/= Wt. % naphthenic molecules, (mass spec analysis), 430· -650· F. CAI= Wt. % carbon atoms among aromatic rings, (n-d-M method), 430·-650· F. AI= Wt. % aromatic substituent groups (430·-650· F.) Ph= Wt. % paraffinic molecules, (mass spec analysis), 650° F.+ Nh= Wt. % naphthenic molecules, (mass spec analysis), 650· F.+ CAh = Wt. % carbon atoms among aromatic rings. n-d-M method, 650· F.+ Ah= Wt. % aromatic substituent groups (650· F. +) G=G lump (Cs+-430· F.) C=C lump (CI-C4+coke) CAI+PI+NI+AI=LFO (430· F.-650· F.) CAh+Ph+Nh+Ah+HFO (650· F. +) Adapted Nomenclature for rate constants is detailed in the FIG. 2 for paraffinic molecules. Similar rules apply for the other reaction steps. This lumping scheme successfully treats gasoline (G lump. Cs+ -430· F.), Clump (H2. H2S, CI-C4.-l-coke), light fuel oil, LFO, (430·-650· F.) yields resulting from gas oil cracking. It will be noted that the total wt. % conversion is just the sum of the G and Clumps. Detailed composition changes resulting in the light fuel oil, LFO, (430·-650· F.) and heavy fuel oil, HFO, (650· F. +) are obtained by following the concentrations of paraffinic, naphthenic, aromatic rings, and aromatic substituent groups as the gas oil proceeds to crack. The

split of aromatics is necessary for the inclusion of recycle charge stocks in the model. This split permits closing of the recycle loop and iterating about a recycle composition until convergence is established. The kinetic scheme of FIG. 2 shows that a paraffinic molecule in HFO will form paraffinic molecules in LFO (Ph-PI) and molecules in G lump (Ph-+G) and C lump (Ph-C). Paraffinic molecules in LFO can only crack to molecules in G lump (Pf--+G) and in Clump (Pf--+C). Likewise a naphthenic molecule in HFO can form a naphthenic molecule in LFO and molecules in the G and C lumps. This is popularly designated as saying there is "no interaction" between the paraffinic, naphthenic, and aromatic groups. The side chains and naphthenic rings attached to the aromatic rings react similarly, except for a single "interaction" step which allows Ah-CAI. This is the only "interaction" reaction step in the model, and is designated by the rate constant Kahcal in a matrix of rate constants shown in FIG. 3. The aromatic rings in the HFO (CAh) and LFO (CAl) do not form gasoline, but result in the formation of the C lump and are primarily manifested as the coke contribution to the C lump. In the present model, no distinction is made between P, N, A molecules in the gasoline fraction; consequently, all the gasoline molecules are lumped together with a single cracking rate. The matrix of rate constants shown in FIG. 3 is lower triangular and is a consequence of the irreversible nature of the postulated cracking kinetic network. Irreversible reactions lend themselves to stepwise solution and considerable advantage is derived from this fact when determining the rate constants. Nomenclature for terms used in the present application is listed in Appendix I which forms part of the present specification. REACTOR MODEL FOR FLUIDIZED BED DENSE

4,187,548

where !=composition vector consisting of j lumped species (aj=moles jig gas) 5

10

15

reactor length. P=absolute pressure (atmospheres). R=gas constant (82.05 atm. cm3/g-mole OK.). T=absolute temperature CK.). MW = mean molecular weight of the mixture =
I I.aJ .

x = dimensionless

20

SWH=true weight hourly space velocity (g feed/g catalyst-hr). 25 K=matrix of invariant rate constants (g catalysVcm3)-1 (hr)-I. a function of T, catalyst type, residual carbon on regenerated catalyst, Basic N poison, pressure, metals, etc. The effects of temperature; Basic N poisoning, catalyst type and residual carbon on re30 generated catalyst on the K matrix are detailed in their corresponding sections. '" tc=time from start of run, hr. ~(tc)=catalyst decay as a function of catalyst residence time, 3S
1

+ f3tc"t

The rate of reaction for a mixture of hydrocarbons is a function of catalyst properties and process variables, and of charge stock composition. In accordance with the present invention, the rate of reaction can be represented as the following equation. 4S
1!!ldt=Q~!!.

40

where IJ and ")'are constants. KAh = adsorption term associated with the concentration of aromatic rings in the 650 F. + fraction, (CAh)- I A detailed development of the reactor model is ineluded in Appendix II, and a program listing is in Appendix III of the specification.
0

Determination of Rate Constants

A pattern search technique was used to determine the rate constants, K, from experimental data. The data where ~/dt=rates of reaction, 50 supplied to the program consisted of 63 sets of isotherQ=catalyst properties and process variables, mal cracking data at 900' F. in a fluidized dense bed. J5.=matrix of reaction rate constants lumped kinetiThese were obtained on 15 charge stocks with widely cally and according to boiling range, and different boiling ranges and compositions. The ranges .!!=composition vector of reactants and product speof charge stock composition, process variables, and cies lumped according to molecular type and boiling 55 resulting yields are given in Table 1. It should be noted range. that all the experimental data presented are timeA specific fluid catalytic cracking reactor model in accordance with the present invention includes non-linaveraged data. Further, it should be understood that ear differential equations which describe the behavior throughout this application "conversion" or "yields" of the feedstock composition vector in a plug flow imply "time-averaged conversion" and "time-averaged vapor phase, fluid catalyst reactor with time-decaying 60 yields". non-diffusion limited fluid catalyst at atmospheric presThe function used to measure "goodness of fit" is sure. Plug flow vapor phase assumes that there is no change in composition across any cross-section of the reactor. In matrix notation these equations are 65 _ ~ ucr + u2 + 0.3 UL2
fND Np da

RT

pl1W

"'(lcl
SWH

Ka
:::-

where

Plots of observed vs, computed yields of gasoline, C are the sums of the squares of the lump, and LFO are shown in FIGS. 4, 5 and 6. The best deviations over all experimental points for G lump, C fit occurs where f is a minimum. lump, and LFO, respectively. The economics of cracking suggest that more imporND is the number of data points. Nj-is the number of parameters used in the estimation. 5 tance be attached to the G lump and C lump fit as compared to the fit on LFO. Hence less significance is attached to the sum of the squares of deviations for LFO. Table I This allows the LFO, G lump, and C lump to be fitted Range of Charge Stock Composition, Process Variables, simultaneously, yet the deviations on the LFO fit will And Resulting Yields Used in Fitting the Model Parameters 10 not excessively sway the G lump and C lump fit. The Range best set of parameters is shown in Table 2. The reactions 30.5-82.1 Conversion (G lump + Clump) Wt. % have been grouped into four types of reactions to facili20.0-59.4 G lump (Cs + . 430' F.) WI. % tate further discussion. With a weighting of 30% ap9.1-25.2 Clump (H2, H2S, CI-C4, + coke) WI. % 14.0-43.0 plied to LFO deviations, it may be seen from Table 2 LFO (430-650' F.) 8.6-51.9 Total Paraffins in Charge Stock (Wt. %) 15 that the average and standard error for gasoline and 4.2-68.8 Total Naphthenes in Charge Stock (Wt. %) LFO are comparable. Heavier weighting on LFO will 6.1-45.0 Total Aromatic Rings in Charge Stock (WI. %) result in a better fit on LFO at the expense of the fit on 5.6-23.5 Total Aromatic Substituent Groups 206-402 gasoline and Clump. Molecular weight of charge stock
PL2

pd, pel, and

4,187,548

Table 2
Model Parameters G lump (Gasoline Kalg Kahg Knlg Knhg Kplg Kphg C Lump Formation Kale Kane Knle K"h,' Kplc Kphe Keaic Keane Gasoline Crackling Kgc LFO Formation Kana! Knhnl Kphpl Keaheal Kahe.! Heavy Aromatic Catalyst Formation
-I

Reactions

Best Parameters 18.50 63.00 66.15 84.70 23.85 55.00 3.63 34.20 8.18 14.87 9.44 7.85 1.00 14.63 X ]03 X ]Ol X ]Ol X 103 X IOJ X IOJ X 103 X 103 X ]03
X

(g catalyst/cm-)

(hr) - 1

Reactions

X 103 X 103 X IOJ X IOJ X IOJ X X X X IOJ ]03 103 103

103

Reaction 4.4

Reactions 19.00 22.50 20.70 5.86 50.00 0.128

X 103

Ring Adsorption _...:..1_I + Pter

Constant

KAn, (Wt. % CAh)-1

Deactivation,

• dimensionless

«, in hours)
Absolute Absolute Absolute

162.15
Error (G lump), Wt. % Error (C lump), Wt. % Error (LFO). WI. % 0.76 1.26 0.69 1.41 1.78 ,Wt.

'Y Average Average Average

Standard

Error (G lump), ~

ND

fF

:!

NG

%
0.95

Standard

Error (C lump). ~

ND

fF

:!

Nc

,WI. % 1.90

Standard
N f) = No, N(i = No. Nc ': No, NJ• = No.

Error (LFO).
of of or of

""N,..,-DfF-:!"-:-:N,....L-. WI. %

data points parameters associated parameters associated parameters associated

with the G lump fit with the C lump fit with the LFO fit

Boiling Range ('F.) Catalyst Residence Time (Min.) Catalyst/Oil Ratio (Wt.) Temperature ('F.) Nitrogen Dilution (Mole %) Pressure (psig)

430-1000 1.25. 5.0 1.25-6.0 900 10

It is interesting to compare some of the rate constants listed in Table 2 with the known kinetics of the catalytic 65 cracking of pure hydrocarbons and classes of hydrocarbons. The.rate constants for the cracking of the heavy fuel oil fractions of the P, N, and A lumps to gasoline are greater than the respective ones for the light fuel oil

fractions. This is quite reasonable as the cracking rates Compositional Changes During Reaction of most paraffins and naphthenes increase with increasMost importantly. it has been demonstrated that with ing molecular weight. the model parameters shown in Table 2 the HFO and The aromatic substituent groups in heavy fuel oil (Ah) have the highest rate constant (Kahc) for Clump 5 LFO compositions are accurately traced as conversion proceeds. It must be remembered that these composiformation. This is consistent with the high cracking rate tional changes were not used in determining the model of side chain alkyl groups particularly C3 and C4and the parameters. Rather. the predictions of compositional high coking tendency of 3 and 4 membered ring arochange result as a pure prediction from fitting the model matic compounds. Consider the refractory aromatic rings in LFO (CAl). This lump should exhibit smaller 10 to the G lump. C lump. and LFO and as such provide considerable support for the validity of the kinetic coke forming and cracking tendencies (Kcalc) compared scheme. to the higher boiling aromatic fractions. The ratios of Detailed experimental analyses of the LFO and HFO the respective rate constants for gasoline formation to are shown for the single highly aromatic charge stock the corresponding ones for C lump formation are an approximate measure of the selectivity of each lump for 15 PA33 in FIGS. 17 and 18 as a function of conversion. The solid lines represent the kinetic paths traced by the gasoline formation. The cracking of gasoline to Clump model for each of the compositional lumps. The model (Kgc) is considerably smaller than the rate constants for accurately follows the increase and subsequent decrease formation as would be expected. in the wt. % of the kinetic lumps in LFO, and follows Further, significance of these rate constants may be gleaned from the next section where predicted and 20 the decrease in the wt. % of the kinetic lumps in HFO. It is especially important, from the viewpoint of recyexperimental yields are discussed for paraffinic. naphcle, to be able to predict the polynuclear aromatic rings thenic, aromatic, and recycle charge stocks. in the HFO % CAhas this lump primarily determines the Comparison of Predicted Product Yields with increased coke production from recycle charge stocks Experimental Results 2S and also reflects its cracking characteristics. At high Some comparisons of time-averaged predicted versus conversion (60-70 wt. %) the HFO is almost solely time-averaged observed product yields for the G lump. composed of polynuclear aromatic rings. Since the C lump, and light fuel oil are shown in FIGS. 4. 5. and lumped composition of these fractions is accurately 6, respectively. These data were used for the computapredicted, recycle situations (recycling HFO or LFO, tion of the rate constants given in Table 2. The agree- 30 or both) may now be treated with confidence. ment is extremely good for all 15 widely different charge stocks used in the calculations of the rate conExample of Predictive Capabilities of Model stants. The results represent wide ranges of charge The fluid catalytic cracking reactor model can be used to predict G lump (Cs+ -430· F. gasoline), C stock properties, reaction conditions, and conversion levels. 35 lump (H2. H2S, Cl-C4, coke), and LFO (430°-650. F.) Plots of gasoline yields versus space velocity are yields for charge stocks not used in determining the rate given for four different charge stocks in FIGS. 7 and 8. constants. Predictions are computed using the kinetic The catalyst residence times are 5.0 to 1.25 minutes, model based on kinetically invariant lumps of paraffins, respectively, in these plots. The points are the experinaphthenes, aromatic rings, and aromatic substituent mental data for each charge stock and the solid curves 4() groups and the model parameters presented in Table 2. The average and standard errors of the predictions are were calculated from the model. N3 is a highly naphthenic charge stock and gives the greatest yields of similar to those obtained when the model was fitted to gasoline. The highly paraffinic charge stock, P3, gives the original data. The model has good prediction capagasoline yields only slightly lower than N3. Both the bility as demonstrated by the following examples. highly aromatic (PA 33) and recycle (PA 37) charge 4S Amal gas oil (P3) was run at a catalyst residence time stocks give much lower gasoline yields. The side chains of 10 minutes to test the validity of extrapolating the catalyst deactivation function to longer catalyst resion aromatic rings crack quite readily. but aromatic rings dence times. The catalyst deactivation function was are very stable and are extremely resistant to cracking reactions. Recycle charge stocks consist largely of repreviously computed from the cracking results of 15 fractory aromatic molecules and as expected give very 50 charge stocks at 1.25 and 5 minutes on-stream periods. low yields of cracked products. FIG. 19 shows the deactivation function adequately Some detailed yield data for N3 are given in FIG. 9 predicts the cracking yields of gasoline, C lump, and which contains plots of gasoline, C lump, and light fuel LFO at longer catalyst residence times (tc= 10 min.). oil versus space velocity. The yield of gasoline goes FIG. 20 is a plot ofthe yields of gasoline, C lump, and through a maximum. The C lump increases with de- 55 light fuel oil versus space velocity for another gas oil creasing space velocity and the light fuel oil decreases. (PA38). This charge stock was not used in the determiThe agreements between the calculated and experimennation of the rate constants given in Table 2. The agreetal results are very good. ment between the experimental data and the predicted Selectivity curves for N3 are shown in FIG. 10. curves is excellent. Yields of gasoline, C lump, and light fuel oil are plotted 60 A similar plot in FIG. 27 is shown for a wide cut against total conversion. Gasoline yield goes through a mid-continent gas oil (WCMCGO) a new charge stock maximum whereas the C lump increases and light fuel not previously used in the model, and again the agreeoil decreases with increasing conversion. It is particument is very good. larly significant that the model Dot only fits the experiActivation Energies mental data well, but predicts the proper trends over 65 the entire range of conversion. It is assumed, in the present model, that a single actiSimilar data for charge stocks P3, PA33, and PA37 vation energy may be assigned to a group of reactions. are given in FIGS. 11-16. However, updated activation energies can be integrated

4,187,548

10

11

4,187,548

12

into the model, if necessary. The present model has six activation energies derived from temperature data at ---::-:""I~...."....,,- = 1/2.8 1 + 3600 0.1 900, 950, and 1000' F. on Amal and WCMCGO. The 100 2.0 results of titting these activation energies to the experimental data are shown in FIGS. 21 and 22 for Amal 5 Detailed results for WCMCGO with 0.1 wt. % and (P3) and in FIG. 29 for WCMCGO. The activation 0.2 wt. % addition of nitrogen as quinoline at 1000' F. energies thus obtained are associated with the following are indicated in FIGS. 23 and 24. groups of reactions: The model has been successfully tested on a gas oil ___________________ 10 (TK510) with 0.096% Basic N. The result provides a simultaneous test of lumping scheme, and the Basic N Activation Energies poison term. Comparisons between experimental and (cal/g-mole) predicted yields are shown in FIG. 2S for this charge I. Gasoline (G lump) formation reactions stock. 5,500 from Ph, P" Nit. NI 15 2. C lump formation reactions from CATALYST EFFECTS 8,500 Ph, PI, Nh, N,
3. Gasoline (G lump) formation reactions from Ah, AI 4. C lump formation reactions from Ah, A" CAh, CAl 5. Clump formal ion reactions from Gasoline 6. LFO formation reactions from P", Nh, Ah, CAh 14,500 17,500 20,000 8,100

Nitrogen

Poisoning

Basic nitrogen compounds are known to poison acidic cracking catalysts. It has been determined that RESIDUAL CARBON ON CATALYST quinoline added to WCMCGO gives the same effects The reactor model was prepared for fresh catalyst. on conversion and selectivity as the natural occurring 30 However, since residual coke on the regenerated catanitrogen bases which occur in a typical FCC feedstock. lyst in the line 39 (FIG. 1) affects the catalytic properThe effects of nitrogen poisoning have been incorpoties of the catalyst, the effect of such residual coke on rated into the lumped invariant kinetic model for catalytic cracking by the addition of a catalyst deactivation 35 catalyst on the rate constants of the model are provided for experimental data for 0 through 0.5 weight % residterm related to nitrogen adsorption and the use of a ual coke on a regenerated catalyst. A single matrix scalar quantity on gasoline formation rate constants. scalar cannot be used. Therefore, different factors must Catalyst deactivation is accounted for by a deactivabe applied to two groups of rate constants. For example, tion function f(N), given by: 40 a 0.3 weight % of residual coke on regenerated catalyst requires that the gasoline formulation rate constants be I decreased by 43%, and that the C lump formation rate J(N) = I + Kn Nigms of catalyst constants be decreased by 35%. The model linearly 8 interpolates these losses in activity between 0.3 wt, % of Wt. % Basic N in charge CATIOIL 45 residual coke on catalyst and a completely regenerated or fresh catalyst. where N = gms of BASIC N to which the catalyst has Light End and Coke Yields been exposed at catalyst residence time, te. The deactivation function chosen has the form such that at high Correlations are provided in the model to predict the CAT AL YST lOlL ratios there are small quantities of 50 yields of light ends from catalytic cracking. The correlation is based on gasoline and C lump yield and the Basic N per cracking site and the deactivation is insiglumped composition of the charge stock, and is in the nificant. 8 is the normalized catalyst residence time. following form. A slight increase in selectivity is incorporated amounting to a scalar increase of all gasoline formation Li=(aiG+liq (a,tPIo+an!NIo+aaiAIo+actlicalo reactions. 55 +aplr'PIto+a•• 'N/to+aah'AIw+arsh'Ca/to) Fourteen sets of data were titted to give a SE= 1.98 on the G lump and SE= 1.16 on the C lump. The Basic Li=]ight end i (wt. 9'() N deactivation co~tant is Kn=~600.0 ~s Basic i=CI, C]. C2", C30 C;". nC4- iC4- C4", nCs, iCs, N/gms of catalyst) and the gasoline formation reac- 60 Pia. Nlo ... , Caho= Wt. % composition of the charge tion scalar is such as to increase gasoline formation stock reactions by 8% for each 0.] wt. % Basic N in the feed. G. C=Wt. % G lump and Wt. % Clump Basic N eff~ts are neglected, if the concentration is less ai, hi, a/ . . . acahi= correlation constants used to fit 95 than 0.04% m the feed. sets of data on each light end i, The deactivation function is such that at the end of an 65 The results are summarized in Table 3, and some typical experimental run (8= I) where the Cat/Oil =2.0 and the results for the individual light end yields are shown in Basic N in the feedstock is 0.1 wt. % the catalyst activFIGS. 32 and 33. Computed yields for Cr-Ca are generity is reduced by a factor= any within 10% or less of the observed values.

Rate constants listed in Table 2 were generated for a 10% rare earth exchanged zeolite Y aluminosilicate on a silica-alumina base. Catalysts will vary in both activity 20 and selectivity. For example, a similar zeolite Y catalyst having a slightly different activity level was determined to require an alteration of the rate constants of Table 2 by increasing the gasoline formation rates by 20%, and by increasing the gasoline cracking rates by 2.5%. FIG. 25 26 shows comparisons between experimental and predicted yields for the similar zeolite Y catalyst with the altered model.

c«

13

4,187,548
Table 3
Light End Correlation Constants and Results Standard Error Absolute ae/ 0.0294 0.0294 0.0415 0.1199 0.1727 0.2687 0.2329 0.5726 0.3557 0.8779 0.2829

14

a;
CI C2 C2= C3 C3= nC. iC4 nC5 iCs Cs= -0.0551 -0.0551 -0.0258 -0.1673 0.2540 -0.0394 0.0012 0.1288 0.0510 0.1803 0.0896

bi 0.3270 0.3270 0.2060 1.0780 0.3564 0.3620 \.3950 -0.0063 -0.0011 -0.0013 -0.0670

ae.hi
0.0659 0.0659 0.1622 0.1033 0.2424 0.3199 0.1774 0.7972 0.2114 0.7797 \.1540

anhi

aah; 0.2005 0.2005 0.2683 0.1356 0.1690 0.1333 0.1297 0.5440 0.1379 0.3467 0.6362

acahi 0.2263 0.2263 0.0785 0.0069 0.1299 0.0031 0.0041 0.5866 0.1608 0.2749 \.0965

Average Error Absolute

Average Values

Range of Values

a.1
0.0817 0.0817 0.2828 0.2655 0.0798 0.3804 0.3271 0.2469 0.0831 0.5228 0.0499

aal
0.0737 0.0737 0.4451 0.1921 0.1597 0.4823 0.2382 0.5466 0.\380 0.9388 0.7844

aeal Wt.%
0.3570 0.3570 0.0772 0.0087 0.1602 0.0091 0.0065 0.4226 0.4561 0.3287 0.5349 0.0738 0.0738 0.0445 0.1339 0.1618 0.0862 0.2450 0.1720 0.1080 0.875 0.204

Wt.%
0.056 0.056 0.032 0.104 0.105 0.065 0.181 0.122 0.075 0.667 0.148

Wt.%
0.4 0.4 0.5 1.5 2.4 I.l 4.5 2.6 0.4 4.5 \.5

Wt.%
0.06-1.0 0.06-1.0 0.19-1.0 0.40-3.3 1.00-3.9 0.20-2.2 \.0-9.0 \.2-3.8 0.09-0.73 0.96-7.84 0.6-2.4

e.-

0.1522 0.1522 0.2911 0.2066 0.0846 0.2871 0.2893 0.3455 0.1973 0.6949 0.0437

Carbon on catalyst is treated using the coking relation, C =ot/' 4. The program also allows for different reactor types to where be called, (this is specified by the user in the input). C is wt. % carbon on catalyst The program is capable of treating data obtained a is a function of charge stock 25 from the following reactor types tc is the catalyst residence time (i) time-averaged fluidized dense bed data. n is an exponent which is a function of catalyst. (ii) time-averaged fixed bed data using a scalar to The equation below is a relation that is charge stock account for more efficient catalyst utilization. independent with a standard error SRof 0.24 (absolute (iii) instantaneous data - pilot plant fluidized dense wt. %) for wt. % coke produced on charge. Computed bed. coke yields are general1y within 6% or less of the ob- 30 With reference to the program of Appendix III, served values. PROGRAM MAIN reads in the input data and the initial guess for the rate constants associated with the kinetic scheme and proceeds to determine the best set of C = 1:'xJ 5.~ 35 rate constants that fits the experimental data. Beginning with SET ISEARCH, read in input data (1) yields from cracking operation, (2) charge stock where properties, and (3) reactor conditions. 0=0.631 P/o+0.ll0 NIo+ 1.475 Alo + 0.0727 CAlo Beginning with READ 3, read in initial guess for rate +0.631 Pllo+0.297 Nllo+0.773 Allo+2.225 CAho 40 constants. tc=catalyst residence time in minutes Beginning with 700BJSTR, the program determines P'o N,o Alo CAlo=Wt. % paraffins, naphthenes, arothe best set of rate constants to fit the experimental data. matic substituent groups and aromatic rings in LFO Beginning with C COMPUTE AVERAGE ERof charge RORS AND SE, the program computes standard erPho Nllo Aho CAho=Wt. % paraffins, naphthenes, aromatic substituent groups and aromatic rings in HFO 45 rors of the model fit for gasoline, conversion and light fuel oil. of charge. SUBROUTINE REACTR primarily sets up the fluThe coke yield in wt. % may then be calculated from idized dense bed FCC reactor model and proceeds with Coke Yield (wt. %)= 1.1 C (cat/oil) the integration of the differential equations through the SO reactor bed. Outlet concentrations are time-averaged to where the factor 1.1 accounts for the carbon hydrogen account for catalyst deactivation. The time-averaged ratio in the coke. computer values for yields of gasoline, conversion and light fuel oil are then compared to the experimental data COMPUTER PROGRAM to determine how closely the model predicts the bed The computer program of Appendix III facilitates the 55 behaviour. The reactor model may be of three forms, rapid treatment of experimental data. The program (1) time-averaged fluidized dense bed, (2) instantaneous performs the following functions: riser, (3) instantaneous fluidized dense bed. The reactor 1. Searches for the best fit to the data (G lump, Clump, model is specified by the user in the input. LFO) by means of a pattern search on the parameters Beginning with Y(I)=F(J,16), set up initial condiof the system. 60 tions for the kinetics scheme. 2. Goes into an output routine which prints the pertiBeginning with H = TIM(K), for the time-averaged nent process variables for each run and then calcufluidized dense bed, integrate the differential equations lates the light end and coke yields. through the reactor bed, and beginning with COM3. The program then proceeds to produce plots of PUTE AVERAGED YIELDS, YBAR (J,L) compute (i) observed vs, computed yields for G lump, Clump, 65 time-averaged yie1ds. and LFO. Beginning with RISER CALCULATION, the same (ii) observed and computed yields vs. space velocity. integration scheme may be applied to a riser reactor (iii) selectivity plots. model.

I )0.2

Beginning with LIGHT END AND COKE CORBeginning with INSTANTANEOUS FLUIDIZED BED REACTOR, the same integration scheme may be RELATION on page 16, light ends correlative prediction is generated. applied to an instantaneous fluidized bed reactor. Beginning with 101 CONTINUE, the program comBeginning with CARBON ON CA TAL YST, the putes the standard error for all the sets of experimental 5 coke prediction is generated. data provided. Beginning with 10 FORMAT, format statements for output are provided. SUBROUTINE GAUSS 6 allows the model yield spectrum to be time-averaged for the case where the The program of Appendix III is written in FORtime-averaged fluidized dense bed data is obtained with TRAN and is suitable for a Control Data Corporation 10 CDC 1604 computer. catalyst deactivation. SUBROUTINE CONVERT takes the input data The model and program are readily adaptable to any read in the main program and converts it to a more catalytic cracking operation such as a moving bed (e.g., thermofor catalytic cracking), and a fluid riser of a fluid suitable format for computation and printout. catalytic cracking process for either lab system or a SUBROUTINE FOXY represents the differential equations describing the main kinetic framework in the IS commercial unit. reactor model. These equations describe the rate of Appendix IV shows by way of example a comparison change of each of the ten lumped species in the kinetic between predicted and observed yields for two feed scheme shown in FIG. 2. It also computes the rate of stocks identified as WCMCGO and T-K520. Further formation of gasoline, conversion and light fuel oil. Appendix V shows by way of example under PARAMFurthermore, it computes the composition of paraffins, 20 ETERS a K- which gives a minimum error (SE). naphthenes, aromatic substituent groups and aromatic Appendix V shows by way of an example a printout rings in the light fuel oil heavy fuel oil fractions. of a best fit of yields for a WCMCGO charge stock in a SUBROUTINE OUTPUT uses correlations to prefluidized dense bed or fixed bed reactor under the conditions stated thereon. dict light hydrocarbon yields (CI-CS), and coke. These predictions together with the gasoline conversion (C lump-j-G lump) and LFO are printed-out in a suitable format and compared to the experimental yields. APPENDIX I
NOMENCLATURE Coking constant for Voorhies equation, C = ate" Composition vector consisting of j lumped species (aj = moles jlgm gas) Concentration of lump j (moles j/gm gas) WI. % aromatic substituent groups in HFO (650' F. +) WI. % aromatic substituent groups in HFO of charge WI. % aromatic substituent groups in LFO (430'-650' F.) Wt. % aromatic substituent groups in LFO of charge "C lump". WI. % H2. H2S. CI-C4 + coke Wt. % aromatic rings in HFO (650' F. +) Wt. % aromatic rings in HFO of charge WI. % aromatic rings in LFO (430 -6S0' F) WI. % aromatic rings in LFO of charge "0 lump". Wt. % gasoline (Cs + -430° F.) Rate constant matrix . Heavy aromatic ring adsorption coefficient (WI. % CAh)-i Basic nitrogen adsorption coefficient (gms Basic Nlgm catalyst)-I
0

15

4,187,548

16

aj
Ah Aho

AI
Alo C CAh CAho CAl CAIo G

K
KAh

MW

K.

Mean molecular weight of gas mixture = I~'

j

SWH Ie

T X Greek

WI. % naphthenic molecules in HFO (650' F. +) Wt. % naphthenic molecules in HFO of charge WI. % naphthenic molecules in LFO (430'-650' F) Wt. % naphthenic molecules in LFO of charge Absolute pressure (atmospheres) Wt. % paraffin molecules in HFO (65.0' F. +) Wt. % paraffin molecules in HFO of charge Wt. % paraffin molecules in LFO (430'-65.0' F) WI. % paraffin molecules in LFO of charge Gas constant (82.05 atm. cm3/g-mole OK.) True weight hourly space velocity (g feed/g catalyst-hr) Time from start of run. hr Absolute temperature CK.) Dimensionless reactor length Catalyst deactivation constant Catalyst deactivation constant Catalyst decay as a function of catalyst residence time, 1+ Sum Sum Sum
t

Y 4>(t,)

(TCl (Tel(TL2

Pt/Y

, (dimensionless)

of the square of the deviations for Clump of the square of the deviations for G lump of the square of the deviations for LFO

17
APPENDIX II Development of Reactor Model

4,187,548

18
aOj )

When gaseous chemical reactions occur which pro- ~ duce a change in the molecular weight of the reacting The rate constant need not be constant but can decay mixture (e.g., cracking reactions), the gas density with time. . changes accordingly. If these reactions take place in a tubular flow reactor, then this density variation proConversion to Laboratory Units duces a corresponding change in the linear velocity of 10 Experimental data are not usually reported in the the flowing gas. This needs to be modeled into the form used by the model equation. Mass fractions usually reactor description. If inert gases are present in the reaction mixture, they replace moles/g gas, space velocity replaces mass vetoo will influence this linear velocity and the reactant locity and so on. To make this model more readily concentrations. 1~ useful, therefore, we have changed it to accept usual To formulate a reactor model, several assumptions laboratory data. must be made concerning the flow in the reactor, both Let X=x/L=dimensiQnless distance into bed of gas and solids. SWH=g feed (oil+inerts)/(hr) (g catalyst) NOTE: SWH is not the same as the weight hourly Assumptions in Reactor Model 20 space velocity generally reported, i.e., g oil/hr g 1. Reactor cross section is uniform. catalyst, which neglects the effect of inerts. In this 2. Void fraction is uniform. discussion SWH will be used exclusively; it is the 3. Mass flow rate through reactor is steady and in True Weight Hourly Space Velocity. plug flow. From the definitions of G and S WH From I, 2, and 3 and the equation of continuity (i.e., 25 mass balance) G, the mass velocity, is constant throughSWHCeL out the bed. That is, . G = __;';";';"E_';"G=pu=constant

(.!..EL) + G(
ale x

ax

Ie

= -k/

por~:_

I+

LeAh

Assuming that the rate of concentration change with 30 where time, Gr=Mass velocity, g/(cm3 free cross section) (hr) u = Gas velocity in the bed, cm/hr p=Gas density, g/cm! A component material balance on a differential sec- 35 tion of the reactor gives is small relative to the rate of change with position in a fluidized dense bed this is tantamount to saying that the 40 oil molecules traverse the bed so fast that they see cataal + G ax - '} C x tc lyst of essentially the same age then our model becomes

(.!..EL)

(~)_

where aj=Concentration of component, j, moles jig gas rj=Rate of formation of component, j, moles j/(cm3 45 gas) (hr) te=Time from start of run, hr Now introduce catalyst decay as a function of catalyst x = Distance into reactor from inlet, cm residence time, te. Assume, too, that the decay is nonNo assumptions have been made to this point about the reaction kinetics so the model is still perfectly general. 50 selective: Rate of Reaction It is assumed that the rate of disappearance of a chemwhere kj are invariant rate constants With the ideal gas ical species, j, in a single reaction is proportional to the molar concentration of species j (i.e., paj), and the mass 55 assumption density of catalyst relative to the gas volume (i.e., Ce/ f). (NOTE: C, is defined as g catalyst/em- bed; f is bed void fraction). It is further assumed that the adsorption of heavy inert aromatic rings on the catalyst surface will then influence the availability of active sites and conse- 60 <I>(le)P'J1W kj aj dOj 1 quently the rate of reaction, thus dX = - I + Kh CAh
SWHRT

In matrix notation
da dX

65

= I+

«, CAh

P'J1W<I>(le) SWH RT ~!!_

The rate constant, k/, has units of (g catalyst/cm-)r I (hr)-I. Combining the rate and material balance equation,

This system is not linear because MW is not constant. It changes with distance into the bed. Note that

19
11W"=
'1.ajMj raj __ 1_ - '1.aj

4,187,548

20

since the units for ajis molesj/gm of gas. The computer program solves this system of ordinary differential 5 To see that this single result can be quite useful, deterequations numerically using an extrapolation to zero mine th. mixed a'.lerage concentration for a particular routine. run. From the initial conditions (the specific feedstock) Coordinate Transformation in Fixed and Fluidized integrate the model equation to give! as a function of Dense Beds Experimental runs using fluid and fixed beds often obtain products collected over the duration of a run. If catalyst decay is present, then this colJected material represents the mixed average reactor effluent. To account for time-averaging it is necessary to integrate the model equations from bed inlet to outlet (X =0 to X = I) and then integrate the reactor effluent over the duration of the run (/c=O to Ic=I'II")' To simplify greatly the calculational effort, the following coordinate transforniation is performed. Let
10

W.

Next evaluate W for X= I (reactor outlet)

15

where P, R, T, S WH are known from the run. Next choose six times from 0 to tc according to a 6-point Gaussian quadrature integration formula. Using 20 the equation above this specifies the six transformed coordinate v!!1uesat which !(W) is evaluated and sup41('(') P plied to the Gaussian formula. This together with the dW= SWHRT fiX appropriate weighting factors gives the time-averaged This transformation of the reaction coordinate, X, composition. yields a "crazy clock time" W which incorporates into 25 For any given feed composition, only one evaluation its definition the effect of SWH and tc and is given by: of 8j vs. W is required, thus computation time is substan41(,(') P tially reduced. W= SWHRT X It is important that the significance of this coordinate Note that this transformation holds only for fixed or 30 change' not be overlooked. With one set of solutions ! fluidized dense beds (for a riser cl>(lc)=J(X». The model vs. W, we know the reactor effluent (or all SWHand k becomes simply for both fixed and fluid beds. APPEiiDIX III _____ PI-(OGRAll~1:'1 ... CO~MON/fOXYI 8FTA1.9~TA2.UETA3,BET'4.~~EACT.PK8,HK9.R~10.HK11.~K'2 1.R~13,~K(~u).~WOllL(100)."WO[LHCI00'.Mwl~(lpn).Z(la).~ATYL(lCal • ._ 2RATHG(lJ~).RATlG(10CI.~(lDo.20),nH(lpa.?O),~~OIL(1~O) . CO"ON/GAUSS6/r~clnC.2D),r(lnO.2n),TI~E(12),TIHt121.GOGT~Cl~G) COMHO~UCO~jV~ il T ILH A~( 100) , GfJAln to 0.1_. t:;':' ~9.(1I.)lJ.) , PP_J1lh. 20 ) PC 1 0 n,2':) .• -- i-, VY (2 U .·t u-) • Vi' A r. (1 ,20 ) • S ('0 I •.C'" no 0 ) • CL (1 n I))
.. CO~HON/SEAHC~'~DATA.J,~,OUJ1.0"J~,oaJcn~,N~ATE.D9B.STEP.~1.N2.~? CALL 1 Hl::-ILE. I I f'Qo{MAT (411 ~l 1t-JpuT

Tv?E R~A~ HKOII.L.NWOll~.~WO[L.MWIN.LUAR

PRINT

---·-··---~EAD 1

1. r·; !).~T ~ • ~-R.\ Ti:: • N, I S EO R CI-1, I PL o.T , J. rO~MAT(613.1~X.2rl0.4,2~X,.\8) C SET ISE~~:H=l Ir SEA~CH IS REQUIRED C SF.T IPLUT=l IF PLOT IS REQUlriED _1:.._. __ ._. ._. .._. .._ ... __ REAU J. (RI\(J). P~INT 3, (RKeJ) J rO~MAT(i!FIJ).~) _ .. VO 5.1=1,~IlATA READ 6. (:lP(I,.I), J=l,Nt-lAJ!:) •• J=l,NRHE) _ . J=1.15)

._._. _ . P~ t N r

i-

,,~uA-"r"A.

~"R-iT·E~-N;S·i:ARCH-.-IPLOT. i

OA

TArULLO'~S

-'NP.

STEP.

.. . _

SSTOP.D'I8

....

1.

~:P.S T E? • SS TOP. 091:1

._

.. .

.. __

__ . .__ -_.

_ -.

._ .. __ .__ .. _.__ .

·-----piiTN-j-i::-;
6 _'O~)-1A

(P~·-(I-.-J)-;·

J=i:l-:>;
0 X, 7f1 G .4) . . . . .

-------."--. ._ .. _ .. _

T e JX,

A I. "IF 10) , 4/l

(n(I,J),J=2,l<l _._ ..... PRI\lT l. (ffCI.J),J=2,l,\1 READ 2~1. (~~( [.J),J=l,;

_____.. __ PRINT 211,-_.( ;'fU

READ 2,

.. )
. ..

_
o_. _

I. J, .J.=! ,Y_) __ _. __ ..
• -

___ .... 5

~Ol rO~MAT(Jx.Ab.f?4.6~lC.4/10x.7rl0.4)
2 .. CO'l T I NUt: 'O~MAT(lUX,7flG.'\)
-

.
• __ • 0', _. __

. _ ....

.. _. __ .

._._ .

j)~rA rH·S Tf1;:: ;:-QLL::J,.I'!G ,OR:·! _C ARI?~y PP(.J.'\) r-ifl·IT1:S0 P~JDlJCT_A~,~LYSI'5, r,(J.I{) 1 TO H:F.fl, A~!D C RReJ,r.) 10 ~~t,Clrlil cO··jilI1IO,>:S. TnF J RI'=P'H:SF'iiS THE RtI,\ ,',U:·l.'l::'(, C T H £: K R [" f? t: 5;: ~.:T ~, THE ;.> I· fl TIC l: L :. R _ IT F::1 0 F ij A TA •

••

IN?U1

21

4,187,548
rO_R_.A'I'C_RUN_J ,. ._. .

22
'_ _ ,__

c c
c
C _C
C C C

__THUS ,1.'l_Ahl-!'\_yf,_
HeJ,2l=',!T

PCT PCT PCT

peT

3 =wT .4_=~!1
_6 7

5 =wT
::CF
B

= I-IT

PC T hE A V Y. FUEL. H1::Allf, PCT ::CN _ Hr.Av"(. PCT

P-HEAVy 1~_Ht;:'VY fUEL OIL P-LIGHT IN LIGHT FUEL OIL i\_-,HEAV_Y_IN_J;EAVy_rUEL_.OIL __. ~-LIGHr IN LIGHT FuEL OIL
0 I L_.

. __ . z .._.,

.
." .

., _._
' __

.!:
C C C C

_C

9 =CP LIGHT, PCI 1 O_.=.CN_LI "He! ". f'Cl , ._________ _ 11 LI3fti FUEL OIL (;),N.A ASSUMED THE SAME) 12 :.1: \,1 Hc:.VY f'lJEl OIL (;>,N,A ASS-IJMFO THE SAME)._. 1 3 =~! T peT S IJ L P H Uil PI F J E L 0 [ L 14 _::~!T_ PCT. 1';1 .TROGE ~l_IN . fUEl. __OIl' .

=n,

_
. __ . __

_c.

.C
C

J C ___ . __ _ _ . ,__ _. C PP(J.2'=~T PCT ~~SOLIN~ IN P~OVUCT HYOROCAR30N' .C 3. ::~,T PC T_ C L lJrw I :\iPRO DUCL_H YD,~WC AR;J n \I _ ._ C 4 =WT PCT LIGHT fUEL OIL IN PRODUCT HYOROCARAON
!:1.5): C

IN ;:RRAy-;;,-·F"tiR"A'NY-RijN

'_' _._ .. _..

_ _

.c
C

c ---- C
C

_7

J~p_c 1 __Cl_
GJ

12 ~3

8 -::- ---CS-P-R i Mr. 9 __ = \1 ~C4 10 = 1-(;4 11 = C4 PRIHf'

~--

C2 PRIM=

._.

..~_

._" _

---~~-:..-6-----

.
----.

c C---_ _c:_

= 14--;;-----·-·.

I-C5 C:> -PRIMe------------------------·------·------------_

C 15 :: COKE -C"-----'-.-------,,---.. ----------.

.. __

_c

._ .

IN

ARRAY

:(

_ __
..

_
TypE

._.

.
BfD)

.
,,_~~

.
.__ _

.
_ .__ .. __ DAT~)

_C C

C RR(J,2'::

REACTO~

Cl.0=DENSE FLUID __( 2_.0 = ~ I S E R_ ___ __ .

_G_ __

C
C,
C ,C C

R_R_< _3)=_,'I~I(; J_.

RESIO~~CE TI~E,~l~ 5,=_NlTRJC!::N, HOL~PCTdCtl_OLES ~J2_J<'WLl:SOJ2 6 :: H ~ U, I,; 1 =c t C C:; RA '1 5 H 2 o / Cr. R A ~'S( H 2 G .. 0 Ill)
7 ::_ TE'1P ~H:'1 ur;E,_ D:oti;{<= 6 = PR!:SSIJ;~C:, pS 1 c 9 :: CAR~J~ 0N CATA~YST _. R~(1)=KAL3 ..

CATA~Ysr

4IHOliR

(3.o::PILor PLA~T- INSTANTA~EOUS L Y S;>~C =_VELQC I_U_,.f.R_A'1 S __ .JL 1!!:i_G O

i-iA_~:_G_AJ.:'I_;

s-

:S_.L.

.. 0IU).100.) H 1u 0 • 1

._

C --C- ---.-- -- -----.- ---------.------------------------------C C . _. RK(3)=K~LG _ RK(2J=KALC

.-

C
C C

RK(4)=K~L:
R ,; ( 7 )

C
C'

R:{(10):r.:,-';'L _ PK(lt)=":·~\-l\l. i-iK(~3):"::'~G RK(l~)=KAHC

;:K(16)=<{i\:1t:

= '" I;(;

RK(~)=KPLG " K ( n I = 8 i.: T ~

RK(A)=~PLC
P. K (
<)

R~(12'):I<i'cn)L
RK

= GA';

',! .\

. __ .__ =K·\HCAL
RK (22)

R~(15'=KNHn

-C-----R~-fl9T;,q;AHt; C RK(23)=SCALE C RKC24,=SCALE C RK(25)=SCAL~ C RK(26,=SCALt

.~ C

_RK_(1_7_)_=_~p!!G RK (2U) ="CAHCAL

H"ClO)=KPrlG_

(n,

=,,:~_:

C C _C
C

AND HEAv~TO GASOLINE _ FD~ P,N,A LIGHT AND HEAVY TO CLUMP FOR GASOLINE TO_GLUXP. ._ FACTOR FOR P,N,A HEAVY FUEL OIL ,0 LIGHT FUEL OIL ..__RK(27)=.'lITRJI;F\ POlSO:-.J TtR:1 . _ RK(301 t:Ffl:-CTo-r CA~BON--ON-·REGf:N CAr:-G:;:SO-L-i-~~s-f'OR~lA1IOi~ ReACT!.' RK(31) EU-t:(;l nF C:\=l80\1 U-N REilt:'~ CATCLlJ'lP FORMAT [DI'; R=~CT UJ'-.S RK(32' ~F~~GT QF CARBON ON REGFN C_T- G'SOLI~~ CRACKING ~E!CT;-' RK(33) SCAL~ FAGTO~ FO~ :'LLREACTIO~S** •• U~IT FAC10R*+ •• •••••• RK(34'=A05U~~TIO~ T~RM FOR CATALYST POISQ~l~GDUE TO CA HEAVY
FftCTO~ F.CTO~ FACTO~
RK(35)_:.CT_lv_.q!O,:~_f\E;1C;y_r_r<~_')-I_',ND __ n_JO

FOR

P,N,A_ LIGHT

GASOLlrlE:_
CLUMp

..

C_ C

C C

ACTlv~Tl0N RK(38) ACTIV~Tl0N _~K(39' ACTIVATION RKC401 ACTIV'TION CALL r:O\lv'::f?i

RK(361 RK(37)

ACTIV~T!ON

E\EijGy E\~AGy
E\ER~Y

fO~

AH,AL,~H.CL

FOR
FOR

E\ERGY E\ERGy

FOR FOR GASOLINE

PH,Pl,~H,~L TO GASOLI~E _ PH,PL.MH,NL TO CLUMP ALL LFQ-FORMATIO~ REACllONS TO CLUMP

TO

N1:1 --N2:NDATA

OBJCO:1=

r, u E-';~ 0·'--- --105,120

• --

23

4,187,548

----------------_

24
_

10-5 - CO'lT PJlJt=

If (I SEId~C~,c(J,l)

CALL Rt=AC1H ----fO-Of.lJS-TR=OdJC-O-i1

-- ---_ _, . .. . . _. .. _. _ _

no
8~-

,100

L=~3.~~;i

___ 100 ____

~~iL):HK(~).(1.0.STEP) CALL R E: ~ G r R __ ------- J 2 ,L::•UH J 1) 1 [I 0 ,90 ir (OR _9_0 R K_! LJ = fl K ( L)_~_ (1_._0 _-:-_S_!j::.£'J_~_( !...!. 0 +_~.H_P_!_ CALL IH:AC rf; IF" (ORJ? .l::, OoJj) 100.91 91. RKCL)=RK(L)/(1.0-STEP)
CO'H I NUt::

..

.
_

CQMP=08JSTh.U,999

IF'COliJeU;1,LL,CCMP)_]_()._7L. : _

CO'lT !'wt: IF' (STEP. L::. SSTQPl_ ll:_u, 121. --i2i---s TEP = S r e > 12 ____GO TO 70
120 COHlr'IUt: C CO .... UTt: P -·------SU:11=u. ____ . SU:12:0,U. SU~3=().U SUM4:0.0 A"I:~AGE: u-- -

71

ER'WRS

A.\;9 5i: ---------------.

ON

EACH Or _r.._C!L. --------". __ '.-

.
----_----_-_-

---,--------

--",-_--_._---_-------_.---------

____
-. -.--

-su·":;:o.o s !J2I 6 =:0 ,ll.

- Su.'ll

CALL R~"'C Ttl DO 100D J~l.NnATA SU~12 = S U··I<!

~ S U :11 .. ~:J::;
(I'

P ( .1. ~ l - G:J/. R ( J l )

S U '13 ~ S U ,\ S .. ft_ d S ( P r ( J • .: l - L 31· :l ( J ) L SUM 4 = SU,~t4 + {r ~ ( J. ( ) - G 3 .',~ ( J) , ...... ~ SU~s=SU~j.. (PP(J.j)-C~AR(J)I •• 2 S U '16 :: SU'·1 .. {) P' P ( J • .; l - L J .\ H ( J ) ) ... ?

.. ~ ,1 S ("?

(J.

s ) - c 9",K

(J)

...

. _,

._._..~

1000

CONTINU~ SU~12

----

-_ _--------------_...

-.---.--------~--.---,-- ~ -- ---

SUH1~SUM1/NUIlTA

= SU.'1~ INU/I TA S U ~.5 = S 1.1 .'1 SIN iJ II T A

pr~INT PHINT lLFO

SU~6=so~r(SUM6/(NDATA»
',I1j

SU'1~=SQH'(SUk4/(NOATA» SlJl~j = SOH r ( SUI'.'; / (NOA

Til)

._._ .._~

<JY

98 FORMAT(I/.~lH 99 FORMAT( ouH

AVERAGE

ERRORS

STAN~ARn

ERRORS

G LUMP
__

CLUMP

lFO

G LUMP

CLUMP

PRINT 1Ul, SUM1,SUM2.SUMJ,SUM4,SUMS.SUM6 101 rO~MAT(lQE3U.?) CId..L OlHf>UT

109 111 If" <IPlOr,E::lJ.ll CQ.'HINUt:
CALL PLUff

'109,111
. . . . _

J lllli

CO'H! NUl:
STUP f;NIJ

60

65

25

4,187,548
~N U....
::t:

26
<x: wer
N_'!l..-10 Uc> 0 e-

'z

~ r

.-f

I
! ,

I
!

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....... :z:rO:I"o 0 ,C!I

t-t..)CO ~

'I

O-lC3

W:rl:

f')o:r::C!I%:VlLl'

....'~->-.,_
Wa:O<
!I)

<...-I_J~-

3: 0: 1:

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Co

i
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NO-..JC!lWa:.n
<C:lC..JIl:<

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I ! " iz l-

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en

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lUI

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I

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,(:)

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lC ~ I 0:< :1:.

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Z.-I

o
Z
W

rl

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Z

+ .1\ <N
3:1")

<l\

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<:.1'1

"" :l: ....

u:

OO~~%~~~C~zz~~~» ~~~X_~%~Z~--_~O~~ .... Cl LU UI U « :-~ n. 0 ~ (., 7' (!) c..'l I'- t~oJ>< ~~~~ZZ-ZZ~2 ,0 ..... ~ t Zw ::> ._ :.n - ui (_~ 'U; c..~ w ,0 C

i..-4 ...... ~

IO:O'..u:);:r U

COO:::!l::;!;2 __. :;I) .,()

.::;

.1)

Q.. 00 v

C'I ~

..... _OC! X'~ .x: co 0 ~ ~:3

..u
C

::c

....

L .... .1'\

x:

<I[

.'"
"')

"')

:-..:

e, 00

:rl C'\!"'"

C=cC==O~~~_~~_~~N~~C ooooc=oooo=o~o=coZ>~

!I\..o,.....

o .... -{N:"")

"'Cl' I,{\..c

e-, c.-!

!5
'.JJO
O'li

:.n

rx: :r

Ul

, =>

--~=~:~--=~==~=~-~%
~~~~J~~~~~~~~~~~

..J 0
(I)

Z 1: 0:
CI O 0:

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VI

" >J Z

Z'J >--::l -' ..... 'I.::.n m ui u: J

~QU;_J 07lf)'J

>-

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.1

0 0-

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a:

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c)

us
(';

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0:

....
Z

.- .~
>:Y-

0' 0 L.:2Z

-,

w
x

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60

65

Su~RnUil~~

CO"HO~/tOx" 1.R<13.RK(j~)."~OILL(10J).M~OILH(lDnl.~~'N(10n).Z(ln),~ATHL(100). 2 KAT t! G (1 'J u ) • K.q l G (1U (I ) • R (loa. 20 ), RiH tOr)•20 ) # :i'..l 0 IL< i o 0 ) CO~MON/GAJSSc'rF(100.20)#F(100.20).TIME(12).TIM(12).GOGT0(10C) ____ CO~H 0\1 'ClJ'~\'C:.q /Ul_:. '-I (1.00 ) • G~! AR (100 ,_# C9 A R (1 n a )• PP.(1 a 0 .20) ,p (10 a •.2 ill _ _ 1.YY(?~.lG).'dAR(I.2~).S(~U"CH(10UI.CL(100) __ . . GO'l~i(l'USt: f. k(;I'"I,t.U,\ If· J.'~, OBJ1, 03J~. O~~JCO'1. __ N:.{.\TE. 098. STEP .... N2. ~'P .. _. "1.
#

..._ ...._ .. ..._. __ . ~tACTR eETA1.~~TA2.8ET~J.8ETAC.~REACT.RKa.HK9.RKlci.RK11.RK12

27

4,187,548

-------._-_._------

__

..

_ ._.. _

..

._ 0 I '1E~; 5 liJi.i

Ty~E

REAL

K~urlL.H~OlLh.MWQIL.MWI~.LBAR
Y ('j 0
>

. __ . __ ..

...

. __

994 995 996 1

9

k~S(?~) If (N1 • HJ. -a ~9_._Cjl_'i.~_ PRI:-:T 'l'/'j PRINT 9% F: o~:",q(t! X. PRINT

AH
997

DI'1ENSIU~

-_-- ------_._------LF'O )
----:---

FQoiMAT(lHl)

112H_

G__ 1;> LU'

~M

PH

CH

G .. LUf'-!P__ . _C_ LUMP .._ C _LUMP __ ._ LfO __ AL NL pL CL OBS

_ ._. . PRED .

._. .__

--9-ij-7-F o~r{Af 111

ce x ;--:;VH---PRc-D 0i3J1::0'iJC:}N _.
. .

oas
.__ .

------_.

------PRED
.

OBS)
.__.

OnJ2=1J.1J NJI"iF=6 __ EP:;=l.<Ji::-iJo

.__

____
. 981 __

[U'lc=u.1l __

DO 981 1\1=1. RK.S(Kl) =>l< ( ....1) . 00 40 J=Nl.N~ _________ ._TTERf.I=l. 0 /R (J. 7) -1.

_ 0/7_55.2 .. __ ~ . .__ . . __ , . . . _

.E'I.=E_v_PC __h }_ nE~".'!...~!3Zl___ :-ko{ L .. E2=EXP(-R~(S6).TTE~~/1.987) ______ E3=EXPJ -i-l-< (Sf) .. TTE~~/l. 907 I.

ADJUST

ro~ ACTIVATION

E'lERGIES
. .__. "

A tu G ~.C~TU : .f!,N TO G . __-"LLLF'

E4=EXP(-R«j6).TTER~/1.9ti7) .E5=Exp ( -~< (.s'i). T TE~'1'1 • 90 ~L. ____ .~KH' :R<_tu *tL_
RK(14)=Rr{(14)·F2 E6=EXP(-R«40)*TTE:.{~'l.9b7)
RK(13)=r~«1.3)*E1 .__RK(2) =.Rr{ (2) ·C2 __ . ____
_____

P,N TO C
(;

G
. __ . _ .__ .

TO C ._

RK_(19)=rI<t19)·E?

_.

Hi«22)=t1"'(£~)"F7. R~ (.3): Rr<(_~, .!c,~ __ __ .

RI«~)=Rr«5)·1:3
(J.?)

______.RI((15) =:-!f.

.E3

___

RK(17)=rl".(1/Jo[=3 RK(~)=rt""(4)·E4

___

RI{(6):Rr«o).l:4 RI(J 1_61-=_R< (_1_0 )~F1_.

RK(18)=K«j ";'·).F4 __ ( 1 0 ) = I-{" ( 1.; ) • F ;;; RK RK(11)=KI\(lU*f:'5 RK(12)=K~(}~)·F5 RK (;'>1)

RK(2n)=K!\(;.· .. )~F5

=,i"

(~-l

i *F5

...

.__

'-'

. --------. _.__ _. _

. ....,-. _.

RK(7)=Hr\(I)·t:6

----BETA!

ADJUST

~R<·(~.» (33'-~~K

seALt:

f ACTO-~S IF ASKE[) - .-------~-

r on ..-----------------.;__ ....._.~

_ BEU?=RK (;'';) BET~3=KK:2~)

·RK (33) .. RK(33)

-i:

AETA<: =RK (')6)· Ri\(S3)

ADJUST KATE: (;O':5TA',;TSr:l::j CAR:30'J O'J REGE~E'RATED' ______ BE_TA 1 =F,,~T A1" ( 1 0 -.RO< (31) ) >II! (J. 9) , .. BETA2=fH::T:"2·(1.0-q.-;(31)."R-(J.9» . ._ BE T/,3 = hi:: T ;, ~" ( 1 ,Il - R >(( 32 ) .. f(rt ( J, 9 ) ) . BETA~=8~TA4·(1 .o-~{(30)*~R(J.9»

CATALYST
..

. .. . .

...__ ._

_350

IF(RH(J.l).E:Q.D93) __BE TAL =flt: T"1 ~ 1. ?O BETA3=tlt:T,\;S.l,£12:i 351 CO'lT I Nut. . .__ .

ADJUST

If CATALyST

IS U;3 .

350.351
. __ . . . . .

_ . ._. .__

C C C

fORM.

I NIT

AL CONDIT

10·\1 S

or

_P. N, A."IIl__~_ LII~PS

_._

._

-------y7i.'-:F'.(j:

YO ) = F' J, 16 ) (

29

4,187,548

30

)-)-.--- ... ----

.y(3'=F'(J,:5' Y(4,=O.U Y(5)=F'iJ.1:» Ye~)=riJ,4) _'-: __ Y_<U = F LJ, 2) .. Y(81=F(J,17) Y(91:FiJdb) -----.- e :) ) = G • U i _____ .?(6) =0.0_._ Z(6)=RiJ,5)+rleJ,6)

-------_._---.. . ._. . ._ __

.!'

c -----DO-i-oo-·-~;-G-·~----'----------------------__ 1_0O_.~( 0( ).=.O ..!.\J _.

. __ ._. ._._. .. ..

--,-----.----------.---

-- - -I F (NRE A L: _~O_1__.COj U IW.=

NR~ACT:~~(J,21+0.1

r •E Q

.3)

. .s 0 2;301--_· --------_ ._"

' .---.-----------------.--. _

-.-

..

c •••

cnxr

IFeNREACT.EU.l) 20~,201 I NUt TIMe: AVt:~:'Gt:D·FL_-UIOYS-EU-

D-Er;,;SE-6·EO-~·::::-·---··-·

CAL l ...GAUS So._. H:T I ~l( 1) ·-·-----·Do-·fo 8 -r<;-;-i;"JT·lr:<E·----·

105 106 T:TIM(K) CLL ·ill: X HA

X:O.O

--_._---------_
• .. -.---.-.-.---.-.-- --.-. - .. -

.._.-

-.-.---- .. -._.

..

i ,'I,lt', y;-~, E··PS. ::i)-----

-.. -----

-- -

ex. l T. TI 1;)6,110 .. ._.. . .__ . __.. ..__ .._ _ H:AMIN1(rl,l-X) GO TO Iv:; -'lTO-H:AM(I~l (~;.l~-f[~~ (~:-+-i)·'::x) -- .. --.----------. .C .. _STOR= OU,PuT COllr,s 1\ .yy._ .__ .__ :.. __ ... __ .. _. __ ..... __ ...
.IF'
YY(l,K)=Y(1) .Vy(2,r()=Y(;'-)

.. _ _. __ _ __._

--_ ..- -----_._- .__ ..

. ._.. ..... _

AL PL
G:'

......

_ .. _.'!Y_(

Yye3,K)=Vij)
4, K)

....
.._.

yye~,K)=l(::') .1Xi~._'r< ~:_Yl]._!+_!._i ?_l~Y_(_3_)_+_Y_(_9_;':_ Vy(7,K)=Y(~) ..r r r a , o{} =Y (6)

yyeil,KI:'f(/)

= l.i

~)

.. __ .__

..

. _

.. __.

.
:

._. .:_ .•

. __.__

-------_._;..:. --_._--_.' __
....-. ----. ----..... -----

~_

...

CL
LF

yye10,1<1:'I'(0)
.. _108 C YY(11,K,:n'" CO'!T I ~;u::......

- .. ---.--.-.-------

..

CA~ .. - .. - ... "CAL

. __ ._.
-e

r-'

_.

. FULL

C NO~ HAVE C COHPUT~

CO~P~I:I~D AV~RAG~O

._._~__ . ~UN ON fEED

..!
J

e- - •• -

00 155 L=l, 11 Y'1AR ( 1 , L ) = U • fJ B566 2 ~-;-... ,-y-y ( L ;-1")" YV (L.'J -6') ) + 0-.-1-30 :18 GB~' (yy (L, 2 " + Y Y CL, 5) ) __ .. .. _Y!:IAR(1 , L1.=- .. _D'8AR.l1,l,.L~9_._~.3.3~??_O.~_D·J_{L ,3_1 ~yY (L I.'!J)_L . ._ 155 covr 1 ~J:.J= .... VElAR( 1 ,1 ) = YtP" (1 , 1 ) • ~1:~o 1L L (J) IG or. J) +100 .0 TO( yaAR ( 1 • ~) ;,.y.p iH 1 ,2) * r. '10ILL ( J) Ir.OG To ( J) *1 (I 0 .0 .. YBAR ( 1 , .s ) = Y to Ml ( 1 , 3 I * '1 ~ (') I L U J ) I GOG TO ( J ) .. Ion • 0 .. .. ...,... ..

YIELDS,YOA~(J,L)

Y8AR(1.11)=Y~AR(l,11).~~OILl(J)/r.Or.TO(J)·100.0 _. ._'t'.HAR( I.!} :YtPfU 1,J) ~M'..IOILH(.JUGr)(lTQ(J __ ) .. 100

'BAR(l,d)=Yd~H(l,A)*'1WOILH(J)/GOGTO(J)+lno.o
.. __ .. _.YElAR(

e.,

0 ____ . .
.. _. .

'

·_ .._··· ·
.__.. _

______ __

1, ~): YdAR (1,9) *'l.~n I LH (J) IGOGTO( J) *1 n Cl • n yRAR(1.10)=YriA~(l,IG}.M~orLH(J)/GOGTO(J)*100.0 .GBAR (J) =Y3Ak (1,4) *1 0000 ,/GOGTO (J ). __ ._ . ._ ..

C. _'* ** 201 C_ ..... ~

CHAR(J):y~A~(1.5).4UUO,/GO~TO(J) ..__ 19 AR (J) = yS "r<! 1.., 6) ._~,,,OJJ.!..(J)J_r,CGJ.O.UJ_~loa GO TO 202

.•-o
, ' _

111 It .. *_'* .._~ .,,_*_~_!_ ... ~!.!._~_~.*_.~~._ .. '!'_,~_~_1!~ _-:_ *. .. co'HINUt .Y (SE R . Ci'L :;_llLA_l1Ofi_~*!.!.!.*.!_· .• • ~~!.!~* ..~_._.

••• ",~ ..... T:1.0

____ ..x:o. n
_205_ _206

H=O.5
CAll
IF'eX.L
H:Hljri

D ,<T 'l~ (f" x , H, ~p_SJ. S) .T) 2116.210

(rl,L-lI.) ----'-

s.,

--------------------_ .. _- ._----.._-----_._---_ .... -_._ ..__ . __ - -_._ _.- .... ..

__________ R (J )= Z (~ I•4 r'l) (J CB"

GO TO ~u5 _UO CO'lTI NII!: -__ ...- GgAR(J)=y(<l)*10000./GOGTO(J)

.1 GOG

31

4,187,548
__

32
_
_

T:) (J)

_________ il ( J, .T: 305

CALL

"_*-_*.~ •• *'.* '* .............. -:.*_.. ~ .. * .. *.._*, ..~.!_~_._"~.*.'!'.*_* ~_"_~_.~*~~ " _' _ '_'_-::. * .• .• _ ._. GO TO 2112 _c __ ~*.! _ISS TA N TA:,=_O_U~ __£_LU_lDJ SE [) __ E [LREA C IO!L_~.! 0 .. ~_'t..* *_!_*___!__*!*_*_. 302 X:O.O _
Cl )

lR"R(J)=(Y(1)+V(2)+Y(3)+Y(9».M~OlLL(J)/GOGTO(J)*100.0

"
_

._. _

I (R ( J. ~~*_0• Ii tiZ- ~ ( J,}U )

*1 • 0/_(

1 ... RK (8).

(R (J, q ) I .. RK (9» _

0= X T~A (N.)(. Y, IF(X.LT.T) j~6.310 _ 3_0_l? = ~'ll ~H ( ,,_, T_-:_~J __ _tl GO TO ;);17

H=O.~*T

"I. EPS,
_

S)

_
_ _ _ _ _

310

CO"

PJ'Je:

GBAR(J)=r(~)·lnOnD./GOGTO(J)
CflAR(J)=Z(~l··l;\OU;/GOr,TC)(J)

LaAR(J)=(Y(1).Y(2)+Y(J).Y(9».MWOILl(Jl/r,OGTO(J)·1~O·0 C _ '* !.•_ lilt. * * .. *' '* '! ~ *~ .• ~ .. ~.."_". ~ '*..! ~ .. to"',., ~ '* ~, • ..__ ".__ .'
202
F"U'lC = - -PR I NT 9U-;P-P (J:i")·;--GfAR-(j)-;PP(J~-i)-,CBA-R(i)~p-p (J;iL 2Y8AHC1,J),YrlAR(1,11)

covr

"_ ,.

. __

Pot!': F IJ.'JC + ( ...r' ( ,I, ? ) - ~ tl A ~ C J) ) *.2 + C P P ( ,I. ,II - C tl A R ( .J) ) •• ?

i.-ij-"R (J ,-;.PPi j",-4'-;--- -- ----.

lY~AR(1.7),YH'~(1,8),YBAR(119).YBAH(1,10).V~AR(1.1),YYAR(l,~), 90 FO~~AT(lX,A/.3(5X,f,.2,2x,r5.2),R(2X,F5.2»

,no
40

HK(Kl)=~KS(~l)

no

911l!

Kl=l.~·~

co'n

I NUl:

Q'lJ~=Sf)IHO

UNC/(NDATA» 131,141

IHOIlJ<'.Lc.UHJCOM) 08JCO:~:UllJ~

Ir(N1.f"J.'li').1I1t,993 . ._. _ 993 PRINT YYb.OllJCOM.QHJ2,rUNC,STEP 99a FO~HAT(II.~II S~= ,E12.4,10X,16HSE FOR TRfAL STEP=,E12.4'1~X,5H l=,El?~.lnx, 1nHST~P SIZ~=, F6.4,11.12H PARAMeTERS PR:~T VVV,(NK(J), J=1,NRATE) 999 Fn~HAT(luEl~.4)
1!) 1 RF. T UilN t::"JU

CONTJ~U'=

PH, __

45

50

55

60

65

33

4,187,548

34

Nt:I,:ntl'l n...JUU'~ :.::tI?ri 0::< .0:

i
I
i

lI !

I
0,I
n:I:

...... ~_..:cC) o
0::

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i !
I

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;

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i I
!

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I

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....:rX .....::::J c --to.

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I

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i

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i
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ill
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1-U.05~1" u.3270.0.093a,u.1350,O.2o~7.n.n530,~.0743,0.1514 ) Cl0;:~ DATA «CU:'f(Z.J) •. J=1,8):: .. __ . .. __ ... ..... __._._ .._... . .-- '2 -0.02340, U. (:'0 £'0, n • 1<: 4 7, U ~7911 .0 .1961 .0 .05 Q8 , 0 .277 (" 0 • 2 6 3 6 ) C2:: DATA «CO~F(J.J), J=1.8)= . .' .... . ----j--O-;-16 '7 3lt ,i-:fJ 7BO', O. Q679 ,'0~2296:o. 0913,O:-1360~2-6-55_;_O. ii-53---'--)-C3--" _ ... _DA rA( C COEF (<;, J), J:l.!l):. _._. ._. __ ._.'__ . ._._ .. '._ . _ 4 0.2540u, l,.3564,O.~424.0.0846,0.15~J,O.1818.n.oB22.0.14~9 G3::.
DATA (CC(J"f ('5,J), J=I,8)=

---'5-0,0358!j, u . 36?0 ,0 .2909,'0. ____ QAJA __tLcy.;:L( o_,J).,._,!~.1._B)= . ._______ 6 0.003505, l,J950,O.1';i51.,U.304,3,Q.0901.0.239?,Q.3271.0.1438
____ .__ DI\.TA .( (CO"V (7
I

3020' ,-O~-O-935-:-O:25·75·;ij. 311 G4.0.

. .. ._.

__ .__._. _.

d1S
_

) NC4
.__ .

J),

.J:1

I.d )=:_._ ..

IC';
.__ .. __ C4:

_. __
___ ______ ___

7 0.1286u.-u.unf,2,o.797£,O.3455,O.57~3,O.5450,O.246Q,O.5333 .DAJA. «GO=~ t s , J) •. J:1, Il) = .... . ._ _. ..... _ .. 8 O.05661,-u.~0?8,0.1747,O.1515,0.15Qn.O.2940.0.06B7.0.?'832

OJ

{J~rL «CQ.=F ~~., J), _.J=_1_,fU=_. .. O.lBI.i~J,-(;.:;(j~4.u.~!!!O,!).7:!.70:!).4'1Q3:n.A396.n.55ilO.O.7205 D..A TA._( CCO::IJ10, J), .1=1,8 >.=_. ..._.

.. . _._ _ ..

.__ .....

._.__ .. __ '_.' ) NC5 . ..... ) IC5 .__ . .__ .__ .__ .

___

(CCO;::F <l1 • .1), .J=l,S'= . __. .._. . __ . 1-0,06019. u.Sh5Q.o.2612,U.4102.1.S260,O.63BO,Q.19Q6,O.9007 .QA1~__U_R:\:A~II:(.L),. L=.1 ,1(1 )=_4_HC2._ ...~HC2;__.dJ1C:L.-,~HC:_3.=-._14HNC.1._,. 14HIC4 ,~HC~: ,4HNC5 .cHICS ,4HC5= )
..DI.TA 00 lOU
~I :j

A O.0895V,-u.u6~8.1.154U,O.08n2,O.78~1.0.1975,o.o515,O.72~8

) C5.
...

_.
. _

) CO~:: _

_J= 1. NUAT A

..

.__ .__. _._. _. _

...

.__ ...__ . _ ..

AH::I00.U-FF(J,2)-FF(J,4) ___ . ALR= ("10 (1- ~ F (J, 6 ) 1/100.0._ .. __.. tJ. .. __. __ __ _._._ .. . .._ _._ AH~=FFCJ,6)/IOu.O . DO 9 L = 1.11 _. _ ...__ ._ .. . _ _.... _....._ ..... ci r Gil T (L ) : {COcf (L, 1 ) .GH AH ( J) + C GE F (L ,2 I • CR,\;I ( J 1 ) • C If F ( J, 2 I • C Of' F ( L , 3 ___ 1.)_ + FF{J.4 ) • COI-'.F:. r t .• 41~~!:!Y_CtlF.rIL,?»· ,\ fL~~(_C(l[F (L.~J·.U.( 13 )+COU< .1 L,7_}. 2·fr(.1,5)+CO~FCL,B)*AL).ALR)/ICC.O c.. .T E'~? C0 ~.: E: C I I O'~ f 0;1 l. I G"! 1 EN [] 5 . _.. _ _ _ _._._ CLIGHT(L):CLIGHT(L)·(I,O+TE~PG(L)·(RR(J,7)-900·0)*G,Ol)
9 CONTINUf: . __ .... .

_._5__ F_O'l~I.T(053rll • FCC-O"'ERATING .. CO~!OITIQNS C ••• LIGHT E~D ANU rOKE CORR;::lATION ••• . _:....n: 1.0U._ U_-:.f U J,~ I-FJ:. (.J 1.5 L__ .

PRINT

*_.

_.10 .._.

..

C •••

C~~aON U\ C~TALyST C::A.TC*.N ••• A._ =(O.~~0'·fF(J,?)+.3~4.FF(J,C).:.?9D.~H).~HR+CO.5?OO.rFJJ.3)· 10.166G·~F (J,').O.8U/6.&L}*~LR

_ --. -.-------.---....._ .._. '--'---'

CA~8=.!./IUJ.J·(P"(J,4)/5.01·.n.1964 ---'ECC-=3 ,-UV-:-V~ "_.. _ .-------.----------------------. ·Ct.~9=CAi-l:.l.t:)(P

... _._-",-- ..... ---~ ----'---

TTERM=1.U/R(J,j)-1.0/7~5.2
C

-ECC-

TTErl ", 11~967)

CA~Bl:PPCJ,1?).RH(J,3) .. ~:~(J,<)/(60.0·1.15) _ ._._._. ..... CO<E=CA~9.t0.0·1.15/(RR(J,3>.RR(J,4»). PRINT 10, Pf!(Jo1) . . -iO-Fci'l~:t.. T(l';rl ";H:'RGE ST·(ICi<-·:--;A7_;_ii"----------·--·-------------·-·--··

11

.. IF (fiR (J. 2) .GT.~ .• I!) P i~I N T li.

13,1.1._._.

__ ."

_. __ ... _.

._ . __

.12 FO'l'::'T(<;7-ltiC·ACTOR . .T_YPE_-XLliIDISEll GO TO 10

__I"!ENSE

8ED

OR FIXED.BED
..

__

,_I )

_1.3 ... C 0 \j T I NUt: ._ . .. _. __ I F ( R f~ CJ , 2 ) • G T • 2 • U) 1 6 , 1 4 14 PR P.;y 1:) ~15 rO~~~AT(j:;rl Kr:AC-TOFi-TVPE .. L-ARORATORY

_---------_-_----_
RISER-:----·"--~,-,)----------

_---

16 PR [t~T 11 17 FO~ ~l:.1 Cj_o ::.!"ii'_As:r.Q.~_..!_~!..:£'JJ._Q_1.:_e~!<NT_[lF,!l.S.~_.i3EQ_

GO To 18

.. __

,_U

._

4,187,548
49
18

50 3---------- ----.-3 )
.FB.3) ,F8.3_) _ .F8.3

-20
22

CO'~TINUt: 2u. ~k{J.J) -_FO~HA T (jj"i ,; i 01 L/liRiwT

PRINT

C-ATALYSr---TIME
-

---- ---------;F8-.
MINUTES
-

-_
_ _

flR I Wi 21. R eJ. 3) -2i- F'O~~i\T< J5, i hUE ~:HSV.:-WT-n:ED;HR/i-iT-CATACY-ST----~f8 ____ PR_l NT 22 ._f'k( J ._ijl

-23
24

FD~MAT(j5~ CATALYST RESIUENCE PRINT 23. RfleJ.5) FOiH1AT(J:H :-':ITflQGE:I:';'1-oLE--P-CT PRINT 24 .RR (J_. 6)_ _

f"O=lHAT(5?ri
PR-INT 2~. 0 rl~lA-T(-j:iH

PR II\JT t!6. fol (J. B) 26 FO~MAT{jjH kEACTO~-P~ESSURE-PSIG __ PRINT 2/. RrceJ.9) __ 27 FO~MAT(J5rl G~H8QN Q~ REGEN CkTALYST-WT __ PRI~T~D 3D rO~MAT(III.?lH * y1ELDS •
.PR I N_T31 _

-2-S-F

~rEf.N-WT kk(J.7)

PCT

-R G" ACT

oR--r E.'1P E i1A TlJR-e --ri-EG- F

• F 8.3

) _

.F8.3
PCT ,FB.3)

_ PREDICTED)
_

osSERVED
_

31 F'O~MAT( PRINT_ j?,

35 FQ=lHaf(JUrl
DO 36

PP(J,5J,C"-IGHn_1_L_____________________

4dH
Cl

WT per
__

WT peT

./)
---- ---

-36--PH f N" - 'j'/",T'

L=1.1!J '"j~ i'~ E AM'

.lX.f7.3.5X.F7.3)

(L-)~-"?~P-CJ---;-L:4-)_;·c-CiGHT(-L'-----'------

---,--------

__37_F_O;{~A Tel x , A I ,2~X. F7. 3. 5x. F7 ,3) PRINT lS, PP(J,~).C9AReJ) 38 FOil~:ArcJtirl I; LU:H-' (:;4-+ COKE) --PRINT 3''/. f-'peJ.2)-.GilAR(j) ---------------

_ _ . ,lX,F7.3.5x,F7.3) ---_

j9._F --

o~r\ AI__(SU_-lGLI!I',P __ (G5-. ~ J O D_f:_G__E_l __ PRINT 4U. PP(J.4).~gAR(J) ~O FO~H.r(ju-l LFO (~Jo-650 D~G F)
-HFDQ=lJ8.n-pp(J.3)-?P(j;2)-P?(JI4~
HFOP=100.0-C~AR(J)-GYA~eJ)-L8AHeJ) FQ~:-'AT(jLrl

,_L~_,L7_._3_'5_:<_!.F 1_._3L
___ ..I

F 7 • 3 • 5 X , F_7 • 3 ) _

__41

PRINT

41. hfUQ,HFQP
tirO __

(!,:>Q+_)

.lX.F7_,3.5X,F_7.31

PRINT

4~. C~~Hl.CA~3
__ t~~~J2_!___£'___r,X_:~OORHf'F-<:

_-45.!.(~-l·~~_!.!.~U_r!_CA~

PRINT ~b, PP(J.15),COKE 46 FORMAT e JUH CO'<F. WT peT-VOORIIEES __ pnINT 4/. PP(J,l~),CLIGHT(11) 47 FOQMATeJO~ CQKF WT peT-CORRELATION 1 0 0 0 C0 'J TIN lH:
1: I~U 45
R~ rVflN

_._1X!U~_3_.~~~_~L·~

50

55

60

65

51
..... NZ...J~.JUJ~ U"-<.:x:-.:o: 0 .LI::::E~ :l: ~ Z U'_2

52
:r..1 Z

<.-i-l-ll-UOZ
I-~-",,(!J :1::

... "rClOr::E:~
U !I:' 0

:UXO<O :II :J::rC!>

-,

r•

..,
41: I-

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Cl

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.-i_':r.::.:=- ......~
:l<X :I:

OJc!)Z{/)N'I"""'IC:::)

-, :z a:
C

= ::>
.-1

r,

NO-~_'WO::"':l.<> <~a::::::x:);:4.-' ..JJi"#') I- a:: I- -::c II:.... • W 4I:1->-OVl

CD

...
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I

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1°
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I

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r-IX::l~""'X _. W ~ t:!l

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~

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:n::::
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~C'\.'''''}q!.l'\.o~-~:t:::
O!:>c:="CCu....T-C

OO;:)OO-:::>Z>-~
=:J..J~:::;' ,=>?==-j..,:l ...

.lJ

(f)

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0 e,

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=>1J>t

.:l
Z

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2
W

>- -:r. ~_':"'.~::n

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mWWJ
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,_

a:
X . IJ.I

.-

60

65

53 --- --.---"-_._--------'---'SUtiRQU TT,~~-'~LOT TI~~--------·

_._-

54

__..__ CO·"\ e ," I r G x Y I b r; T .\ • :3 E T ~ 2 •El"T t; 3 •B;:T' .: N 1 ,\ ,~:;/;:; H (, •H K 9 , H K 1 Q , R 1\ 11 , :; 12 t, CT. 8 :~ 1.R~13.R~(?U).M~01LL[lGO).HWOILH(10al.~~I~(lQO),Z[lG).RAT~L(l~O). 2RATHG(lOO)'~'TlG(11G),~(100.20).~H(lao.?n).~~oIL(lrD) ·CO,,\MON/G~JSS6/rF(lGG,2n),F(\OO,2D).TI~E(12).TIM(12).GOGTO(ln~) CO~MON/~~~V~~T/LHt.~(10n),G~AH(lOQ).C~l~(lnO).p~C10~,20).P(lDC.?~)

----l;yy
.__

C 0 ~ M0 'U S f:: ! fi CHI ~.JD~ T ~ , J • '~, 0 ~ ,I 1 • C:; J;> • 0 o:l J C 0 '1 , '" RAT E • n 9 fl • ST E P , foJ 1 • N 2. lvP TyPE R~lL H~OIlL.~~Oll~.~wOIL,MW(N,LHAR __ __ .01 "IE N S (ON . 1J( <: ) • V (2) • cell-=! ( 100 ) ,C;Urt ( 1 0 n I .i. F! UR ( 1. 0 0 l • I I;WF (11) G U ) 1.RTEMP(lDG),HX(10n),RS(10Dl,QQQ(100),RZ(lOOl.QP2Cll,QP3(1).QP4(1),
lRR~ (1) -TYPE RE;\C--C;'JR-_ CALL_ PLUi5( bUr-, 10,H,. 28' __ . CALL L. Pl1 TS ( 11, ) PR 1 NT ,)U 6 ._. . '-.. ..
. .__ . .

(2U .l~),

Y·bA:::;(1.

2C?

,S(:,'O)

.eH

(1110)

.ci, (1 00

. .__
_.'.

---

_-

._.
..

.
. .

.
.__ . __ . ....

306 FO=l~"n(4(;"1 307 Nl=l - . - .-i-J 2 = iii 0;\ T "

00305 ·---GfiUR (

PLoni':G

-I~-PROGRESS

--'-_._--------._.__ -----_ ._

(J

l=l.'lnATA =Pi' ( j. ,2)

------.------------.-.--.---.

. CBUR ( [ ) = P;>( I .3) lflLlR (I) =;>;> ( I. r,) .311_3_ . GO N T [ '~U.t: .

. ._. __
_

.. __

. _.

.__ .__

____
.

OXN=10. OYN=lll ._.

Sy=5 • 5X=5.

..
.__ . .

.
. .

.
.

.
.

..... ._ __
.._.. __ ._

____
__

.__CALL .A X I S etl , .0 •• 11 U (l ) = Ill. ___ . V(ll =10. _. __ ._. .

XO=10. yO~1_0 •.. . CA~L ~X!S:D.,D

. .• l1H
H

_
_Y _ 03SEHvED . _ .._._. )

Y CQMPUTEO.-ll.SX.O

.11 •.5Y,

0 •• YO ,1l.yNJ._ .. . ,.

•• XO,OXNl

.__ ..

._.

. __ .

____

U(2)=6G.

Vt~L=6!) •.

CALL ______ C ALL ____

__

LI~~(U,V.2.l.q,1. xO.IlX~,YO.DY~) l [ -'I t= ( L b UK. L BAR._ , \I D A Til. 1 • - 1 • 4 • X 0 • 0 X N • YO, I) Y N ) . CAL L S y ~1 J L (. 75 • 5 • '5 •• 14 • 29 H F L ut n i 7. EnD E 'I S E 8 E 0 CRAe 1\ I NG , 0 • , 29 n CALL SY'1H:)L( .7??f1 •• 1t.,291l LF"O _(43Q _- 6~O r) .O,,?91

CALL

Xo=?

NXIP:.T(SXl
_.

.._

.5y::5,

YO::; •

____

5x=5. OX\j=5. DYN=? ~ ALL _AX IS ( _ U(1)=:i.

I) ••

CALL

AX[S(~

u .•. H Y_C::l:~~lJTJ.O,~ 11. SX, 0.• .1 xn. OXN) _ . 11 .• o, .1tH Y 03~EHV~O.11.Sy,QO .• yO.OvN)

VOl:? V(2J=3L UUl:Scl, CALL Ll"HL'.~·,('.l.n,l. XO,()X\l.YO,llY~) _._ .. ._. __ '" CALL LIN~(L~0~. C~~q ,\UATA.l,-1.4.XO.DX~.yo.nYN) r: A I I " V ;1 t, 11 ( ,7 r, • 5 - 'i •. 1 4 • ! 911 _rt II r f) [ 7 F n n;:" <:; r B Foe il A CK r N G • n •• ? 9) CA L L S)' ';0 JL-(• '0-,-. f4- ;'29 ii- C'L"Uilp· ('Ci---:-C4 --.~. CG~·E, .. -- ..-. - ,0 ', ~29 .) r.t..LL N)(rp~T(SX)

is ;:;, .

YO=20.
5x=5 OX\j=10.

XO=20.

. sy = 5, ..

._ . .__

._.~

._._..

~_ ..

DY'l=10.
CALL

AX IS (~.;

o·.:-ii~-Y -CDHP-u'TEo;:li:
.

SX:O.~· xo·.-OXt.I)·----·- - .. ---- - - .

.__._ .. ._. 0 •• y n , 0 y N , .__ ..'__ '_

__

...u (2) = 7 0.,_._.

V(Z)=70.
CAl. LA":

.U( 1) =2.i1. V(1)=2G.

I S ( u •• 0 • , 11 >-l

Y. .09 S E ,{ V r. D • 11. S y •
I, • )(

CALL LINE(~,V.?1.0.1,XO,OXNIVO.DyN\ CAL L L [ N l: ( ld l' R. G ;,j 1\ q .' 'J!.l A T A • 1 • - 1 , C r, L L S Y:-,~ J L t • "5 • ~ • ') •• 1~, 29;·1 F L III n I

z:: D

0 • 0 X 'J , Y lJ. D Y N 1 . .__ _ DfO~; S~ n r: D CRile K I ~iG , 0 • , ? 9 )

55
____

56
_!..!l...!...L?9) __

--

... -DO

CALL NXTi>LT(SX) HAM=N

117

~.A '-:L__S _~~ _oJL ( •

Zr,_,_.?_!g~J~!_~_H_~._L,JL'"lY_ 5_~.L::._~_.3.0 J.> ..

. _
.. .

J;l;r\.Liiu--.--------.-------.-.-----__C"!r..

.-.-.--.---------.---•. __ . • __

_____ C
~

R.TEMP (J) =:n J, =S) . "x 08Sc~VcU C+G

RS_.C_A.LCPL".JEn

RX(J)=PP(J,~)+PP(J,3) __ .11 Z .C TIN UE .... 0" ... DELSV=l

---'NPOINT=J9 -' ;.1=39' --N=~.A,~ NPART=3 N?=K

.--_-----------.--._. --_-..-----. ..__ --.----.------.-.--.----------

- ... ------.--------.---

_____

I?_o__ l_1J __~=-l_!_~._.

-'. ----

---Nl
'-- __

=K' -----------.-- .. ---._

---------- ---._--.- --- ----.

_ _

------si NNN·~-.-oi--·----'_S_IN2'l N =_ • .!J 9

--->-----------------.--- ... ---.---------

DO 159 Jl=l,NPOINT IF(Jl . --50CDEL..SV~. LE.IU) ~ -501,503 ..---.----;-------.--.-------.--. -------.-------.-------.--______ GO TO 5U~ ..__ . . .. ._._.. .. _._

--505- CO'''T INlJt:"R (,( ,3)

503 OELSV=l •.s OELSV=I.1

CA!..L Ri:ACTR

= S !r. '" '._.

----------------------. _. . __ __
_.__ .. ----

..---------._. .
-'_-_-" -------

.__.'_
__ - _..

_.

._.

._ .. _..

OQQ(Jl)=R(K.J).GOGTO(K) CBuR (Jl) =C~.\.~ (K)

_.._,._-,,-,--- -,------.

--_

)=~i.i.:.fi(K) ..- UIJ~(Jl Jl-"=Gb~k-iK )'_ --- ..----.---.--------.-.--------------------------.GBlJ~( S I ~NN = S II~ ~J,~ ·t:'EL . ... SV ._. ._..._... __ _. _._. .. _
159

covr
00

. _ _ __ ..._ ._. __.. _ __

PJUt: 131 1=1, N

I ) .·Ci-!U ,I ( l )_. ._. ...__..... . _._ ..

1-1=,59

______

OP2(1 )::"r'(1'..2) . -------0"3-( i')~PP (-~·:_,j"i.. ---------------.-----------------.. _.. _OP4 (1) ="'P (K. 4)
)::~H(K,~q

131

HS ( J ) =G,J,H: CO'H I ~IU=

--.__.. _._. __ ._.

- -- ..

.__ ._.

.__ ..._ ..__ .. _

~=39 __ . XO=O,
YO=O. Onl=10.

RRiHI

... _
--•

---jj X;~ = 4 ~-----.--

-----_

..

_---

SX=12.5
SY=10.

SX=8, _,_~_'(=.5•. DX'l:5 • .... D.y\l-=20. _...

CALL

. _ _

_ .. ._. ._ .. .. __ ... ... WT. PERCl::NT .20.SY.98 .. YO,OY'J) VELOC 1 TYC',JLOIL/WT .CATl>.LYST HR). -39, ..._.. _ 5X
I

AXI~(U.,O.,20ICYIELO
~ (U.,

"

.10 •• XO,!J)(\') ___ CA LL __L I_NI2( _£H~Q

CAL.L AX I CALL CALL

O .•. 9HS~"CE J

LIN~(
LI'JEe

CALL CALL

LIN~(NHR

UOa OCD_

LI oIIE(R Hi<

• l. HUR, M._ ~ • 0 •5,_XQ •. DX1L YO, D YN )._._ _ ,G9UR,~,1,0.4,XO,DXN,YO,DYN) .C3UR,~,I~O.11,XO,DX~_YO.OYN) .QP2 , 1,1.-1,4.X~.DX~.YO.OYN)
__ f.QF:~
.__

._---_._-------.._

~_._t'-l, ..:_1 tJ 1 .X 0, D XN. '!' 0, II nJ)._. __.__ ..

. _ _CRA-CK 1 NG, (;.0,23) _.__ CALL _SY~I('JL (t, .5.• .14. 2:SHREs\CJO~ __ 5, TYPt:... . .... __ _._.:_0.0,23) -----.CALL SYM~)L(~ ••6.,.14,P?(J,1),O.O,7) ____If'. (PReJ,2).-2. )171,_17.3,115._ . ._._. .__ ._ 171 CALL Sy~ltJJLC3.0.5.~ •• 14,32HFLUIDJZE~ OENSE BED .0,,32)

~---CA·CLSYi-ldJW-:-:-6:-:-:-i4~·23rlhUDCAT"A-LYS;: I

CALL LIN~("Rk J=i{'

,CP4

• 1,1,-1,5.XO,DXN,YO,OYNI

i73C;'LL.-'·SY;'l~j(JL (;j·:0;5~5:-:Tii-~j1HLABOR/,TO'R'y--"Ri"SER

r.n

Tn

/0

1"Ts-

1?9 CON T INUt

GO TO _17'.1 C A'~ L ~f;., J J L(:-f.o y

-------·--,o-:-o:-Ji'----- ... ----

.. _._. __..

-; 5 • 5 ~-:i'L jif:tPTL-OT -PLAtH

.__ ..

..

.__ .__ . .

._

• 0 • 0 , 31)

..-._ .. -.-

57
CALL SyMdJL(.5.5.0,.14,5.0.0,-1) ____ !!ALL_S_y JLi.L_1I .5., O_!_.l_~,) ~Id CALL sn1ci:;l(4.'5.:>.O,.14,J9f1TC _. 1,0 ••39) __ . . TC=RR(J,4)

4,187,548
8t!L ,L._O....L__L1)_8_~_6_'5 _[_)_, O._!.1A_L Q

58
_

MIN

._._._. _

._

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1, 0 • , 39) . _ _._.. .... .... _ -.- . . CAL L N U ~lrl :: il ( 0 • iJ , :; • 5 •• 1 ~ , R R ( J , 6 ) , ~), 0 • 3 ) __ q LL _ 51'''1,., JL(.-f. ':i,3 , n, .1 ~ , 3.9H'J" t: S5 ... . .
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I • I

1.0.,39)

C 4 LLSI' :-1l' J L ( • '::> • 4 • n , • 1 4 I CAL L 5 y ::;:: oj Le. 4,:, • .4.• 0 !.,1~

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AX I S ( u -,_,0 .•.•. 1.4 .IC.Ofl{V;!'IS I o~~ __ ,_-..14.,_5 X. 0 I, XO, DXN l __ . _. . CALL AXIS(0"o.,~OYYIELD WT, PERC~NT .'a,SY. 9~.,YO.OY~) CAL L L I \1 t ( H S , L 9 U R , '" , L 0 , 5 , X 0 , n x N , YO, D Y N ) . __ .__ ... CALL LI~~( ~S ,G3UR."I,1,O,4.XO,OXN,YO,DYN> .CALl Lf,~E( tiS .C5UR .• '1.1_,Q,.11 •. lCO,DX'J,YO,DYN1 .. _
RZ(1)=ilX(.(J

. CAL l SY~" I.( i " 5 ,'; .14 •23 HREA C TOR TYPE 80 , CALL SYMaJL(~ .• 6 ••• 14,PP(J/l),O,O.7) __ ._._1 E_. $.Rf?eJ .?)-:-;:_.)_1_9~ ,1.93_, 19>191 CAll 5Y~dJL(j.n,~.~,.14,32HrLUIDIZEn DENSE
GO.TO 199 . ._.

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__ . _ , O. 0 ,23 ) ..... _. .• 0.,32)

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.

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193 CALL
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SYMJJL(~.D.5.5,,14,JIHLA90RATORY
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NXH'LT(SX)
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We claim: 1. In a catalytic cracking process comprising contacting hydrocarbon feed with hot cracking catalyst under operating conditions sufficient to crack said feed into a 5 desirable product distribution, including hydrocarbon products of lower molecular weight, while depositing
MATRIX

G=G lump (Cs+ -430· F.) C=C lump (Cj-Ca-l-coke). 3. The method of claim 1 wherein said operating conditions include the following reaction rate constants:

OF RATE CONSTANTS

~ G C

-(Kphpl+

Kphg+ Kphe) - (Knhnl+ Knhg + Knhe) - (Kahal+ Kahg + Kahe + Kahea/) - (Keaheal+ Keahe) VhI Kphpl -(Kplg+Kple) Vhl Knhnl -(Knlg+Knlc) VhI Kahal V hi Kaheal V hi Kcaheal Vhg Kphg V hg Knhg V hg Kohg 0 Vhc Kphe V he Knhc V he Kahe V he Kcahe (Mol. WI. of heavy fuel oil/Mol. Wt. of light fuel oil) coefficient (Mol. Wt. of heavy fuel oil/Mol. WI. of gasoline) coefficient (Mol. Wt. of heavy fuel oil/Mol. WI. of Clump) coefficient (Mol. Wt. of light fuel oH/Ma!' WI. of gasoline) coefficient (Mol. Wt. of light fuel oil/Mol. WI. of Clump) coefficient (Mol. WI. of gasoline/Mol. Wt. of Clump)
coefflcem

-(Kalg+Kalcl -Kcalc VlgKalg Vic Kale

0

Vic Keala

-Kge Vge Kge

where,

V", ~ V h,r( = V he ~ V If#: =

Vic

V R"

Stoichiometric Stotchiometric Stoichiometric Stoichiometric Stoichiometric Stoichiometric

coke on said catalyst, separating said products from said coked catalyst, recovering said products, regenerating and heating said catalyst by burning coke therefrom, and contacting said regenerated. hot catalyst with hydrocarbon feed; the improvement which comprises: A. Lumping said hydrocarbon feed both kinetically and according to boiling range into at least two lumps including (1) compounds with carbon atoms in aromatic rings and (2) compounds with carbon atoms in aromatic side chains associated with the aromatic rings; B. simulating said cataytic cracking process based on invariant simultaneous and consecutive reactions of said lumped hydrocarbons under a selected set of operating conditions to determine a yield product distribution; C. repeating step (B) at different simulated operating conditions until a predetermined desired yield product distribution and coke deposition on cataIyst is determined; and D. operating said catalytic cracking process at the operating conditions selected to result in said desired yield. 2. The method of claim 1 wherein said reactants are lumped as: P/=Wt. % paraffinic molecules. (mass spec analysis), 430· -650· F. N/= Wt. % naphthenic molecules. (mass spec analysis), 430· -650· F. CAI= Wt. % carbon atoms among aromatic rings, (n-d-M method). 430·-650· F. A,= Wt. % aromatic substituent groups (430· -650· F.) P/r=Wt. % paraffinic molecules, (mass spec analysis), 650· F. + NIr= Wt. % naphthenic molecules, (mass spec analysis). 650· F.+ CAh = Wt. % carbon atoms among aromatic rings. n-d-M method. 650· F. + AIr= Wt. % aromatic substituent groups (650· F. +] and wherein said product yields are lumped as:

4. Apparatus for predicting the reaction product yields of a catalytic cracking process for the conversion of a stream of hydrocarbons wherein said stream is 30 contacted with an active catalyst in a reactor maintained under catalytic cracking conditions to provide reaction products which are removed from said reactor, the catalyst in said reactor becoming contaminated by the deposition of coke thereon, said apparatus compris35 ing: means for lumping said hydrocarbons both kinetically and according to boiling range, two of the lumps of said hydrocarbons including: (1) the carbon atoms in aromatic rings and (2) aromatic side chains associated with the aromatic rings, 40 means for simulating said catalytic cracking process based on invariant simultaneous and consecutive reactions of the lumped hydrocarbons, and means for 'producing an output representing the yield of said reactions based upon said model. 45 S. The combination of a cataytic cracker which converts a stream of hydrocarbons wherein said stream is contacted with an active catalyst in a reactor maintained under catalytic cracking conditions to provide reaction products which are removed from said reactor, 50 the catalyst in said reactor being contaminated by the deposition of coke thereon, and automatic computing apparatus for predicting the reaction products of said catalytic cracker comprising: 55 means for lumping said hydrocarbons both kinetically and according to boiling range. two of the lumps of said hydrocarbons including: (1) the carbon atoms in aromatic rings and (2) aromatic side chains associated with the aromatic rings, 60 means for simulating said catalytic cracking process based on invariant simultaneous and consecutive reactions of the lumped hydrocarbons. and means for producing from said model an output representing the yield of said reactions based upon said model. 65

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