Catalytic polyforming of gas oil with a hydrocarbon gas mixture
by Robert B Hamilton
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering
Montana State University
© Copyright by Robert B Hamilton (1950)
Abstract:
The purpose of this investigation was two fold: (1) to evaluate the polyforming process under catalytic
conditions as a method for producing motor fuel from a petroleum gas oil using a hydrocarbon gas
mixture as outside gas under 0, 900, 1500, and 2000 psig reaction pressure, and (2) to determine the
time of stream for mixed-gas catalytic polyforming at 900 psig and 455° C. .
Houdry fixed-bed aluminum silicate catalyst was used for all runs and the carbon was burned from it at
the conclusion of each run. The investigation was conducted at temperatures varying from 392° C, to
509° C.; and the liquid space velocities used were 0.6 to 0.8 and 4.0 to 6.0 volumes of charge per
volume of catalyst per hour. During a typical run, approximately 450 grams of feed were passed over
the 1000 ml. of catalyst.
Characteristics of mixed-gas catalytic polyforming are as follows: (1) yields of gasoline increase with
each additional increase of pressure up to 2000 psig at which point the yields decrease, (2) gasoline
yields surpass those obtained from conventional catalytic cracking using a space velocity of 0.6 -0.8
hr^-1 only at 1500 psig, and (3) carbon formation -exceeds that occurring in conventional catalytic
cracking at comparable oil conversions^, It was found that the time of stream best suited for mixed-gas
catalytic polyforming of gas oil at 900 psig was approximately 20 minutes.
CATALYTIC PQLI3F0HMING OF GAS OlL
VfITH A HYDROCARBON GAS •
MIXTURE
by
Robert Be Hamilton.'
A THESIS
Submitted to the Graduate Faculty
in.
■p a r t i a l fulT illm ent of th e requirem ents
fo r the degree of
Master of Science in Chemical Engineering
at
Montana S tate College
Approved;
Head, Mayor Department
C hair
Examining. Committee
!an, /Graduate D ivision
' N'ly.;,,.
Bozeman, Montana
May,, 1950
N 31%
HrIVSck -2—
- 2 TABLE OF CONTESTS
page
3
.ABSTRACT
I.
In tro d u ctio n ............................................................................ 4
II.
Equipment, Methods and M a terials..........
A. Equipm ent....................
B. Methods....................................
0. M a terials....................................
9
9
18
23
III.
Sample C alcu latio n s.......... ......................................24
IV.
R e su lts.................................. ..................................................29
V.
Sunmary............ ....................... ............................. ................. .34
V I.
V II.
L ite ra tu re C ite d ................................................... . . . . . . . . 3 6
V III.
Appendix.................................... .......................... ...............3 7
93813
■S
:
—3 *
JiBBTRAVT
The purpose- of t h i s in v e s tig a tio n was two fo ld : ' (I) to
evaluate the polyforming process under c a ta ly tic conditions
as a method fo r producing motor fu e l from a petroleum gas o il
using a hydrocarbon gas mixture as outside gas under O1 900.,
1500, and 3000 p sig re a c tio n p ressu re.,' and (3) to determine
the time of stream f o r mixed-gas c a ta ly tic polyforming a t 900
p sig and 455° 0 ,
, .
Houdry fixed-bed aluminum s i l ic a t e c a ta ly st was u se d 'fo r
a l l runs and th e carbon was burned from i t at the conclusion
Of each run. The in v e stig a tio n was Conducted a t tem peratures
varying from 592Q C6 to 509° Cl*; and the liq u id space veloc­
i t i e s used were 0*6 to 0 o,8 and 4 .0 to 6 ,0 volumes of charge
per volume of c a ta ly s t per hour* During a ty p ic a l run., approx­
im ately 430 grams of feed were passed over the 1000 ml. of
c ataly st*
C h a ra c te ris tic s of mixed-gas c a ta ly tic polyforming are as
follow s: (I) y ie ld s of gasoline increase with each ad d itio n al
■increase‘of pressure up to 2000 p sig a t which point, the. yield s
decrease, (3) gasoline y ie ld s surpass those obtained from con­
v en tio n al c a ta ly tic cracking using a space v e lo c ity of 0 ,6 0,8 h r»“l only a t 15.00 p sig , and (5) carbon form ation exceeds
th a t occurring in conventional c a t a l y t ic ' cracking a t compar­
able o i l conversions:^.
I t was found th a t the time of stream b e st su ite d f o r mixedgas C atalytic'polyform ing of gas o i l a t 900 p sig was approximate
Iy 30 minutes'*
o
«** 4; ***
BffiRODUCTKH
■During the la s t twelve years,, the need for economy in motor fuel
production has fostered the development of a number of new processes
in petroleum technology1-.- Two of these, the polyfarming process and
ca taly tic cracking* when applied to gas oil* are of in te re st to th is
investigation.
C a ta ly tic cracking i s a process fo r converting petroleum frac­
tio n s In the f u e l o i l range in to gasoline and other lower b o ilin g fra c ­
tions* . This p ro c e ss,produces a high octane gasoline in b e tte r y ield s
per pass th an can be produced by theim al Craekingt
I t a ls o ’gives
g re a te r y ie ld s of the lower molecular weight hydrocarbons which are
needed fo r the manufacture of 100 octane a v ia tio n gaso lin e,
As cracking proceeds.,, a carbonaceous deposit sometimes called
nCOketf or "carbon" is formed upon the Catalyst-*
t h i s deposit ranges from OHqoQ to
The composition of
Since the. carbon reduces
the a c tiv ity of th e c a ta ly s t, the time on stream between regenerations
i s a fa c to r v i t a l to the successful economic development of any fix e d bed c a ta ly tic cracking process*
TTost ( I ) - In v estig ated c a ta ly s t d e a c tiv a tio n as a. r e s u l t o f "cok­
ing” by passing gas o i l over a fixed-bed aluminum s i l ic a t e c a ta ly s t.
The op erating conditions used were, as follow s; .space v e lo c ity - 0,75
h r . " \ tem perature - 450° G. ,
and pressure, - 0 p sig .
With a time on
stream of SO minutes* the par cent conversion did hot change from th a t
observed a t sh o rte r tim es although the accumulation of "coke” upon'the
c a ta ly s t amounted to two per cent by w eight,
AftOr two hears on stream ,
the a c tiv ity of the c a ta ly s t gradually decreased to 75 per cent of
i t s o rig in a l a c tiv ity ,
In th is c ase s the deposit of "coken on the
c a ta ly s t was fiv e weight per cent,
According to Z co st, th is con­
tinued. a c tiv ity can be explained by the f a c t th a t the gaseous hy­
drocarbons are soluble in the deposit an d ■can contact the C atalyst
surface despite- the in te rfe rin g ' d e p o sit,
Present fixed-bed c a ta ly tic cracking processes lim it the Car­
bon accumulation on the C ataly st to about 1*1 weight per cent which
corresponds approxim ately to 10 minutes on stream.
The.polyfqrm process employs.the p rin c ip le of cracking naphtha
and heav ier o ils in admixture w ith varying amounts of norm ally gas­
eous cheap hydrocarbons^ w ith re s u ltin g increases in the octane
number, and a t the same time allows a higher degree of conversion
per pass than p o ssib le in the ordinary therm al cracking process w ith­
out an uneconomical increase in the production of permanent g ases,
6
O ffutt e t s i (S) in a study o f gas re a c tio n s of gas w ith products
from naphtha cracking found th a t gas (Cs and C4 hydrocarbons) suppressed
t a r and coke form ation by re a c tin g w ith some of the products from the
cracking re a c tio n which o rd in a rily in te ra c t to form t a r and coke.
It
V -
was noted th a t lower t a r y ie ld s were produced when the naphtha was r e ­
formed in a high gas d ilu tio n ,
Q ffu tt e t a l (5) showed th a t the same
type o f're a c tio n s fake place ,in gas o il pplyfonaingo
Gas o i ls which
, •
tend- to form coke at. moderate conversions w ith' ordinary therm al cracks
in g .g iv e in creasin g y ie ld s of gasoline when cracked in a one-pass op­
e ra tio n With increasing gas d ilu tio n s..
The increase in y ie ld is a t t r i -
,6
buted to the products formed by theims.1 alkylation# therm al polymeriza­
tio n , and o th e r a d d itio n type rea ctio n s between the gas and the re a c tiv e
cracked products of th e gas oil*
TM su p e rio rity of C atalytic' over therm al cracking led Dev (4) to
an in v e s tig a tio n to evaluate the process of gas o i l polyforming under
c a ta ly tic Conditions using propane as an outside gas.
c a lle d c a ta ly tic polyforming.
This process was
The y ie ld s of gasoline from the c a ta ly tic
cracking o f v irg in gas o i l w ith and w ithout propane a t d iffe re n t p ressures
were compared,
J t was noted th a t a t the higher p ressu re s using propane
as an outside gas an increased y ie ld of gasoline was obtained a t a tem­
perature which was t o o ,low f o r therm al polyforming*
Mayfield (5) in v estig ate d gas o il polyforming under C ataly tic con­
d itio n s using propane# iso-butylene.# and n-butane as the outside gases*
For a l l runs using an outside gas# the pressure# was held constant at
900 p sfg and the tem perature and space v e lo c ity were the variables*
At- ■
mospheric: c a ta ly tic cracking of gas o i l gave a d e fin ite increase in .gas­
o lin e y ie ld on o i l charge over th a t obtained from c a ta ly tic polyforming
w ith propane * A la rg e increase in gasoline y ie ld oyer th a t obtained from
S traig h t# c a ta ly tic cracking was noted f o r th e iso-butylene c a ta ly tic
poIy forming runs*
I t was further noted th a t the same runs made a t a space
v e lo c ity o f 4-6 h r , ^
gave an e s s e n tia lly constant y ie ld of gasoline over
the e n tir e tem perature range investigated*
n-Butane c a ta ly tic polyform-
Ing gave a definite- increase in gasoline y ie ld over th a t obtainable from
atm ospheric c a ta ly tic cracking*
Polich (.6 ) "evaluated"several c a ta ly s ts , both n a tu ra l and sy n th e tic,
fo r use in the c a ta ly tic polyforming process,
H orm l butane Was used
as outside' gas. and the. runs ware conducted' a t foO p sig u sin g a liq u id
space v e lo c ity o f 4-6
■
1 Houdry aluminum- s i lic a te c a ta ly s t was
found to be the c a ta ly s t b e s t su ite d fo r c a ta ly tic polyforming as a r e ­
s u lt o f the follow ing c o n sid era tio n s 5 ' (I)
HoudTy C atalyst was le s s
expensive th a n th e oth er sy n th e tic catalysts- which yielded a lik e amount
of gasoline,- and (#) th ere was no d e tectab le loss- in C atalyst a c tiv ity
■On reg e n era tio n a f t e r the passage o f 27 volumes of feed per volume of
c a ta ly s t,
Eimenga (7) in v e stig a te d the e ffe c t of 0, 300, 800 900 and 1200 ■
pound p ressu re s upon c a ta ly tic polyforming using iso-butane as the out­
side gas*
Space v e lo c ity was hold r e la tiv e ly constant a t 4-6 hr,"^* . ■
I t was noted th a t the gasoline y ie ld s s te a d ily increased through- 900
p sig aiid decreased when 1800 psig was applied.-,-;
The r e s u l t s o f ■these previoUs:'in w s t Igations in d ic ate that paraf­
f in ic gases in h ib it carbon depo sitio n and o le fin ic gases m a te ria lly In
crease the y ie ld s o f gasoline and the through?put of charge,,. Sheser r e ­
s u lts suggested th a t the use o f a gaseous mixture sim ila r in composition
to extraneous re fin e ry gases would combine the advantages o f each separ­
a te gas*
The sy n th e tic gas mixture employed in th is investigation, con­
s is te d of the follow ing c o n stitu e n ts expressed -in weight p e r c e n ts;
50'
M
»
>
3
Per cent n^butane, 10 per- cent is o - b u ta n e g o per pent iso-butylene^
BO per cent propane,, and 130 per pent propylene,
fPhe y ie ld s 'o f gasol^"
lin e from the c a ta ly tic cracking of gas o i l w ith the outside gas a t
Oj 900, 1500, and 8000 pounds pressure and varying tem peratures were
compared w ith th e r e s u lts of c a ta ly tic cracking without a g a s,
Boudry
fixedfbed sy n th e tic c a ta ly s t was used and th e space velocities 'were
held r e la tiv e ly cdnetant a t 0 ,6. ^ 0=8 h, jfr ,'^3.,fo
r c a ta ly tic cracking -and
■
a t 4-6 hr=""1 for cataly tic poly forming,
In addition,; the need fo r a determ ination of the time of stream
fo r c a ta ly tic polyforming led to the e v alu atio n of t h is process variable
a t 900 p sig using the gas m ixture as the outside gas.
The optimum, tem­
perature determined a t 900 p sig , 455° Ch., was used w ith a space veloc­
ity of 4-6 hr,***1,.
$1 EquiBffiltjT ? WJHODS AirompiRiiL'g
Ae EgulpfflaAt
' ■
" 1
The '8 quipiosnt used in t h is in v e s tlg atid h consisted -of a 0-1000
JpajLg re a s tio h system, shorn in Figure I , and. a O-2500 p sig re a c tio n
system, shorn in Figune 2* Each re a c tio n system was divided in to fom?
major p a rts according to t h e i r fu n ctio n ;
(I) feeding section^, (2 }
re a c to r section#, (3) condensing and' race ly in g section? and (4) gas
seetioue
'
'
low Ecessure Unit '
Feeding SeOt ion
'
.
The feeding, se c tio n included a nitrogen. Cylin­
d er, a feed c y lin d er and a Jerguson -gags*
The feed cylinder was con­
stru c te d from an e ig h t-in c h len g th of thre‘e>inch#. extra, strong s te e l •
pipe,.
The pipe 'was threaded a t both ends and f i t t e d w ith e x tra strong
s te e l caps which were welded on in the f i n a l assembly,
Eoth caps were
d r ille d and tapped f o r one-half inch pipe, and the inside o f .the Cap
machined to fa c ilita te draining=
These daps were f i t t e d w ith close
n ip p les and high pressure s ta in le s s s t e e l K erotest globe valves*
Each
valve was f i t t e d w ith one-half to one-quarter inch s te e l bushings and
b ra ss one-quarter inch pipe to one-quarter inch copper tubing, .adapters*
The bottom of the feed cylinder was connected to -the top of the
Jerguson gags with copper tubing and a te e .
The third, side o f the te e
was connected w ith tubing to another tee, and in' tu rn to the K erotest
valve a t th e -to p of the feed c y lin d er.
This lin e served to .e q u a lis e
the pressure across the feed cy lin d er in order to o b tain flow of feed
in to the Jerguson gage.
The other side of the second tee was connected
4 10 .^
by tubing to a pressure gage, and nitrogen cylinder,
nitrogen was Used
to furnish the pressure necessary to force the' feed into, the reactor0.
The glass at the bach of the Jargnsan was equipped with a semi.-stranb”'
parent rule' behind which was placed a lig h t to f a c ilita te the reading
of the scale.
_
The bottom of the Jerguson was connected with e x tra stro n g s te e l
pipe to a o ne-half inch) 600Q pound Yogt valve which was used to regu­
la t e th e feed r a t e .
The bottom o f the valve was connected to the top
o f th e re a c to r w ith o ne-half inch e x tra strong s te e l pipe through a te e
and a union, the male h a lf of which, was welded d ir e c tly to the top of
the r e a c to r .
The o ff-strea m side o f the te e was f i t t e d w ith a Black.,
SivaH s , and Brysgn fra n g ib le d isc s a fe ty valve which was equipped w ith
a 1255 p sig BJpnel diaphragm discharging to the outside o f the build in g
through a o ne-half inch pipe*
Reaetbr Section * The r e a c to r was made from a 15-inch length of
th re e inch' e x tra stro n g ’ s te e l pipe.
Welded in to the bottom of th e r e ­
a c to r was a on e-h alf inch s t e e l p l a t e , beveled on the. top side and d r ille d
a t th e c e n ter fo r o ne-half inch pipe*
A one -eig h th inch mesh s ta in le s s
s te e l screen, to a c t a s a c a ta ly s t support wap in serted on t op of the
beveled end of th e p la te ,
A six -in c h piece of e x tra -stro n g s te e l pipe
was in se rte d flu s h w ith the bevel of the p la te and welded on the bottom
side*
The threaded lower end o f th is pipe was screwed in to a tee,, the
branch being f i t t e d w ith a 0-2000 pound pressure gage, and the fun to a
o n e-h alf in ch , 6060 pound Yogt valve fo r re g u la tin g p re s s u re ,,
•* I l **
Ihe top of the re a c to r was threaded and fitte d - w ith gh e x tra strong
s te e l cap, to which the previously mentioned male h a lf o f the union had
been welded,
M ll/1 6 ~ in eh hole was d r i ll e d through the cap, thus giv­
ing a smooth, continuous surface-,
lHais design fe a tu re f a c i l i t a t e d the
■changing of th e Houdry c a ta ly s t and the 500 ml, of asso rted size s te e l
b a lls which served a s a p reh e a te r se ctio n on the top of the cataly st..
In the f i n a l assembly, the s te e l cap was arc welded to the re a c to r body
to prevent leakage.
Supports fo r the re a c to r were made by welding two 1 /3 -inch low car­
bon s t e e l rods to the re a c to r on the side opposite the therm owells,
Two-
p ieces of 1/ 3-7inch by one-inch f l a t bar stotik were welded -to the top of
the cap and th ey , in tu rn , were fastened by 1 /3 -inch pins to the back
o f the b arricad e to keep the re a c to r from tu rn in g when th e union was being
tig h ten ed or broken a p a rt,
Pour thermocouple w e lls, made from fo u r-in ch lengths of l / 8 -inch iro n
pipe sealed a t one. end by welding, -were in se rte d through h o les d r ille d
sy m etrically a t th re e -in c h in te rv a ls along th e length of the -reactor.
w ells were welded in place with the ends on the re a c to r a x i^ .
Into the
w ells were in se rte d iron-constantan' thermocouples connected- to a Leeds
and Horthrup in d ic a tin g potentiom eter, c a lib ra te d in degrees centigrade
and in d ic a tin g from 0 - l i o 0° Q,
The re a c to r was wrapped with asbestos tape,
TJie top one-half of
the re a c to r was wound w ith 50 fe e t of Hichrom wire w ith a re sista n c e
o f 1.71 ohms per f o o t, and threaded w ith perpelain f I i s h - spin© in su la­
to r s .
The lower one-half, was sim ila rly wound.
Each of th ese windings
The
t
IS
, 6®w
tnapsree
'
from- a 880-volt mtotvansfqwy* , Si&sse wl%4*
#g# ww.^wiw#a -with A &oy*» of eaWeto# wp$ g&d # 9 .
#ac&
%5*
g# RW**cm@ m&ifa w&#9 fl&oe& m***##. Kb# 3%)6uo$!Q%
Boa <A the to#
th ird s
..
-of th# eeStioa # 4 # » awoWA tba t&tbim <m#»
Saah o f %W^@ wiaAiaga m # ^ o # ra# e4 to a I lQ m a lt atstolrans-*
■ftyems and & # * fiv e
m xW %
tSXm -length # t the r o a s te r was v
the# AotefM 'with, <W&Wh asheetse bleaks and 'Otua eattBe
hp#rM
iR&lFh a#@#es aaia*,.
# 8 atitseirM eforaera ttere Buperior S ie o ir ie Oompany ^ /e r a t a t a *
The IlO m o lt pow eretats had a voltage f a n # tit 0*105 v o lts and laere
fused, a t 7,5 arsiperas;,
The SSOmolt pow erstpis ted a range- o f 0*860 •
vo&t* and wore fwea# at three mgeraat
Al/W&dh eteel, plot#
$0
lnptee by 98 $n#i#$ was %#nnte& hg&inat
the lahorattsfy'faO k snd th e re a h to r was fastened, to tM e p t e t e K Tteh
l / 8 -sinoh s t e a l p la te ro lle d in to a W i^ O ir p le -SiB in o te s in d im e te f '
and # W t e e long was hinged to the b a rric ad e m th a t i t WteM hieee
arenad # # reactor, sod eonld be faeWwA aoildiy with l/8*iB0h #&%#%.
Afeaa# W9#k'##8 boil* o# froiatte blngpd
.
0 *0 9 & gage
.
In^fr##8
.
"
.
and two thloktestee of W bty plate gl&te wore fastened in
the SpSNBBai'* Sdila p p o p lW % WEaty w W # " t h r # # wbleh th e & e# to h ld
ho cteerv ed dmiimg'fee d te g u id tie p l
. < w w »iag ea&
Sogtl# ^ $te b(#<m pf IKhe
nlatlhg W # ww ##*wdW # the top # » 80p
peg*
'##&' W hig
Oondoteer by womb o f a # w t p#O e of ooppsr tu b in g W e y te d th r o n g
a naoptete stopper^ &pieoo of glass tubing w# seated onto tte bottom,
o f the 1000 mlo fla s k which was used as a receiver=
The f la s k was
BBrsed m ah, isopropanol-dry ice b ath contained In a one-galIon thermo*
flasks,
fhe o u tle t o f the receiv er was connected by rubber tubing to
the gas condensing' system shown .in Figure I 0,
,Immediately follow ing the Cold tra p s was a tee,, the o f f side of
>
which was Connected to a '800 ml., evacuated g lass b o ttle so th a t a sample
of the uncondensable gases could be taken during th e ru n ,
The gas meter
follow ing th e gas<sample b o ttle , was a t h r e e - l i t e r P recisio n Wet Test
Meter*
I t , in tu rn , Was connected to a blow-down lin e to. the outside
o f the building*
The d i s t i l l a t i o n equipment co n sisted of a 16-plate oidershaw column,
a head s u ita b le fo r e ith e r high or low tem perature fra c tio n a tio n , and
two vapor traps*
The head was f i l l e d w ith dry ice-.isopropanol fo r low'
b o ilin g c o n stitu e n ts and w ith wet ice fo r those b o ilin g above 80° G0 The
d i s t i l l a t i o n .fla s k was heated by a 1 1 0 -volt, 550 watt h e a te r controlled
by another autotransform sr»
-M High .Pressure Unit
Stegtiing Section ■*>The Teetiing se c tio n consisted of % pump^ a- feed .
cylinder,, anti a. Jerguson gage,
The feed cylinder used was Constructed,
in a sim ilar manner as the one fo r low pressure runs w ith the exception
th a t i t was 16 inches in length r a th e r than 13,,
This added capacity
was a means o f allowing fo r the hold-up•in the pump and th e 30 fe e t of
tubing leading to the re a c to r,
A sh o rt len g th of 1 /2 -in ch copper tub*
ing connected the cy lin d er to the Jerguson gage*
This larg e tubing,
to g eth er w ith the pressure e q u a lisa tio n lin e shown in Figure 8 , insured
the fre e flow of feed to the Jerguson.
The bottom of the Jergusoa was
connected by l/4 -in c h copper tubing to a s ta in le s s s t e e l E erotost globe
valvej i t s only purpose being to d id ,in the co n tro l of th e i n i t i a l r a te /
o f feed*
The valve was# in tu rn , connected by two len g th s of tubing to
each sid e of the double a c tin g pump*
Feed t o the re a c to r was accomplished by a Eills-McOanna, Type Eli--SF,
sin g le u n it, two feed,. 1 /4 horse-power pump*
The pump was. connected to
the to p o f th e re a c to r by 1 /8 -inch s ta in le s s s te e l tubing and Weatherhead
Srmsto p ressure couplings and fittin g s *
B eactor Section * The c a ta ly s t chamber was constructed from a th re e fo o tppiece of IS-S-C5, Type 047# 2 -l/2 -in c h e x tra strong W . # , pipe*
A
3 -1 /3 -inch welding cap, f i t t e d w ith a short len g th of 1/ 2 - inch e x tra
stro n g pipe.# was welded to th e lower end o f the s ta in le s s s te e l pipe*. An
e x tra heavy te e was f i t t e d to the l/3 -in c h pipe t o hold th e 4 -foot long#,
1 /4 -inch standard pipe thermowell which extended through the rea c to r along
the os n t r a l axis*.
The remaining opening of the te e was f i t t e d fo r the
escape of Cracked products,,
This was accomplished "by in s e rtin g a 1/8-
inCh pipe in to the o ff-s id e of the te e and allow ing i t to protrude h o ri- ■
z o n ta lly through the re a c to r case.
An e x tra strong e l l was screwed on­
to the sh o rt' length, of pipe and was f i t t e d w ith a six -in ch nipple lead­
ing to on e x tra strong te e .
The b ran ch 'o f the te e was connected to a
0-5000 pound pressure gage and the run to a l / 4 -in c h , 85,000 pound s ta in ­
le s s s te e l Aminoo superpressure valve.*' This type valve n e c e ssita te d the
use Of superpressure couplings, bushings, and-tubing, made by the American
instrum ent Gompanyi
A 2 - 1 /3 inch ex%ra strong welding neck flange was welded to the to®of the re a c to r and a 2- l /2 inch e x tra stro n g blind flange b o lted to the
welding neck f l a n g e . Prevention of lea k s was .made possible, by in se rtin g
a s ta in le s s s t e e l gasket between the flan g es in the f i n a l assembly*
A
sh o rt nipple was welded to the flange and was, in tu rn , f i t t e d with ah
e x tra stro n g cross*
The top opening .of t h is cross was connected to a
high pressure-Hoke needle valve by means of a one-half to one-quarter mnch
'
bushing.
An S fneto te a was screwed into the valve and th e fun openings
were connected to the feed lin e s from the pump,
Another opening Cf the
cross was s im ila rly f i t t e d with a Hoke valve to a ffo rd a means o f purging
the chamber w ith nitrogen*
The remaining opening was connected by a short
nipple to an e x tra strong tee*
The o ff-stream sid e of th e-'tee was f i t t e d
w ith a Black, B iV alls, and Bryson fran g ib le sa fe ty disc which was-equipped
w ith a 3100 p sig Monel diaphragm discharging to the. e x te r io r of the, b u ild ­
ing by a blow-down pipe.
The run of the te e was connected to another Hoke
valve to perm it passage of a i r in to the re a c to r fo r the. catp.l^St'.'bi^til-of^f
-
16
-
Tha re a c to r was o rig in a lly designed to hold 0000 ml* of cataly st*
At the time the design was made^ i t was believed, that, liq u id space v e l ­
o c itie s of OtiS - 1*0 hour- -1- would be optimum.
Subsequent research w ith
the 900 pound U nit showed th a t the process operated e f f i c ie n tl y a t liq u id
space v e lo c itie s of 4«6 hour"-*-*
I t Was necessary, th e re fo re , to. reduce
the c a ta ly s t volume from 3000 ml. to 1000 ml.
This was done by fa b ric a te
Ing a number of c y lin d ric a l mild s te e l in s e r ts which would, f i t snugly
i
in sid e the re a c to r but allow s u ffic ie n t space fo r th e flow o f feed be*
tween the in s e rts and the thermowell*
These blocks a lso e ffe c tiv e ly
served as a preheat section*
The outside .pf the r e a c to r Was completely wrapped with, asbestos tape
and then wound with fiv e 48-foot lengths of IJichrome wire w ith a resis*-'
tance of I ,T l ohms per fo o t, and threaded w ith''porcelain fish -sp in e in s u l­
a to r s ,
Three of the c o ils furnished the heat ,for the preheat section and
the remaining two covered the c a ta ly st se c tio n .
Each o f the windings drew
s ix amperes from a 110 -v o lt autotransform er.
EouT iron*constantan thermocouples were in serted in to the- thermowell;
one ju nction was placed In the preheat se ctio n and the oth er three were
eq u ally spaced -along the 15-inch C atalyst bed,
Eour*kole p o rcelain in su l­
a to rs were obtained from the Stupakoff Company which were o f small enough
diam eter so th a t two separate lengths of th e in su la to rs Could be simul­
taneously in se rte d into th e l/4r-inch therm ow ell,' This- arrangement made
p o ssib le a. permanent thermocouple r a th e r th an n ecessitatin g , a p r o b e T h e
thermocouples w ere^pnnected to the potentiometer*
g&a
boused in a ate&l earn?, tW ehaps otabigb #&& a&
latorted AmiaWum o f a ^ymt4di , 13» dtoenSiOUS <?f the •aiftaa- isegm l/4«»
.
fnbb hy I? iaehee % sight 4uebes hy 60 iaeMs* W ee aidea # # fM*
t@wd together by f i l l e t ^siaimg i/S^iheh by 1^1/8' in<?h m 0 & irbas
in the
of the #9#e* lbs foo&t #&ot# «&G belted to the'&em&ia*
lag edg^a o f the aagle
#ba ease wag. atGbllilaal by threa-pmM&Gb.
pl#e& TWbidb mere welded to the tops of the #ia@# @u& were axtsMei to
the flow ' to forme, tripod* la additloa* two abort le&gtbs' of eagle iron
were weldga to the to# of the Oaee a&d to the laboratory r%6k* A obe*'
Iadb bole m e d r ilio l lb # &Q?ibdh pleoe o f l/4*i&dh fla t bar etodk @a&
maa tbaa gilpped otwthe ono»lbOh pipe e#e#&8@ from the blind aeok
flaago of the. remoter*-' Oble pie do me the# pibnel to the Aldde of the
osee ee that the yaadtor wgwil be- rigidly held la
After the fo&eter
had Wea lowered lata plate* the apace W%#@b the reactor and o a # was
eompletely f ille d with dWom&oaoqa earth to mlaimlze the hast loeeea*
!Bba asmaloibg parte of the ayatem wepe'ldontidsl to the## u@@d for
the l#0O*pa9a& W %
*• 19 ~
Bc Methoda
900 p sig rims
The feed cylinder was evaluated w ith a Oeaco Jfegavae pump, charged
w ith the d esired amount o f gas o i l , weighed on a BO-Icgc capacity tr ip le
beam balance, and then placed in a r e f r ig e r a to r m aintained a t "40° Cc
to c h i l l the oil*
A fter the o il had been thoroughly c h ille d , the cyl­
inder was placed on a balance and connected to the tan k Of mixed gas
by means o f Saran tubing»
A fter the scale had been ta r e d , the desired
amount o f mixed gas was. adm itted to the feed cylinder hy opening both
Connecting valvesv
The a c tu a l amount pf outside gas was determined hy
reweighing the cylinder on the balance w ithout the a ttach ed tubing,
The
contents were then allowed to warm to room tem perature»
The re a c to r was heated u n t i l the thermocouples in d icated th a t the
tem perature was s u f f ic ie n tly high fo r the re a c to r to average the desired
tem perature fo r the run.
A fter opening the feed ra te and pressure regu­
la tin g v a lv e s, the system was flushed w ith a short n itro g e n purge and ■
the v alv es then reclosed,c To the Dewar fla s k s containing isopropanol,
dry ice was added u n t i l carbon dioxide was no longer evolved;.
The gas
sample b o ttle -was evacuated, weighed, and connected to the system.
The
feed cy lin d er was then connected in to the system as shown in fig u re I
QTiri 300 pounds of n itro g en pressure was applied to the balanced pressure
feed system.
The Jerguson gage was f i l l e d w ith a portion o f the charge
by opening th e valve a t the bottom of the feed cylinder,.
The thermocouple readings were noted a t the s t a r t of the run and
continued a t one-minute in te rv a ls throughout the d uration of the wun.;
m 19
Timing o f the rati began when the' feed' re g u la tin g valve was opened.
Eteed
ra te was determined by noting the time fo r any gmyen drop in liq u id
le v e l in the gage which had been previously c a lib ra te d .
o c ity o f 4-6 hr*
For a space vel~
? the feed ra te was m aintained a t 17 lin e a r centim eters
or 85 mi. per. m inute.
-
. •
As a r e s u lt of the closed pressure re g u la tin g valve*, the hot expand­
ing gases w ith in the re a c to r caused the pressure g radually to ris e s
A
d if f e r e n t i a l back-pressure of 100 pounds was maintained during th is 'p re s s u r e
r i s e through the use of th e n itro g en c y l i n d e r W h e n the pressure'reached
900 p sig , the pressure re g u la tin g valve was opened ju s t enough to m aintain
t h i s pressure*
The system remained s t a t i c u n t il the end of the feeding
period which was ind icated by a sharp pressure r i s e ' in the re a c to r se e tie n
'
as a r e s u lt of the 100 pound back-pressure. The feed valve was: immediately
closed and the re a c to r reduced to atmospheric pressure a t approximately
the same ra te i t had bean pressurised*
gas sample was taken*
Dufing th is depressurization*: a
The gas was allowed to come, to room temperature,*
balance ag ain st atmospheric pressure, and weighed.
F rom these data* th e ,
,density of the noncondensable gases was determined*
IJpon completion of the run, the feed cylinder was removed from the
system and weighed* the amount of o i l charged thus being determined by
the difference..
The re c e iv in g fla s k and vapor tra p s were removed from
the system, wiped dry of isopropanol and immediately weighed to determine
th e 'weight of the condensable product*
The liq u id s were poured into the
rec eiv in g fla s k and the t o t a l weight recorded*
The fla s k was then attach ed
to the Oldershaw column and d i s t i l l e d fo r gasoline to 204° C. end p o in t.
So th a t any tra c e s of o i l in the f a c t o r might be recovered,' the re ­
a c to r was Connected through a s e rie s of cold tra p s to the vacuum pump
and evacuated.
The reactor was sim ultaneously purged w ith nitrogen which
aided m a te ria lly in recovering t h e ,Ia d t tra c e s of o i l .
The recovered
m aterial was weighed and added in to the weight balance as resid u e since
under these conditions the p o te n tia l gasoline in. i f would be n e g lig ib le .
D is tilla tio n Procedure
*
1
T heieceiving fla s h which contained the condensable gases in ad d itio n
to cracked stock was attach ed to the Oldershaw column by means o f a ground
g lass ta p e r jo in t,,
The d i s t i l l i n g head and “10^250° G= thermometer were
a lso attach ed by means of ground g la ss jo in t s Using silic o n e grease as
the se alin g compound.
The head was f i l l e d w ith isopropanol-dry ice ,
The •
product ta k e -o ff was connected to two vapor tra p s placed in Dewar fla s k s
which also contained isopropanol*-dry ic e ,
The vapors in the pot were a l ­
lowed to re flu x u n t i l a tem perature of “15° G, was reached,;
The a u to tra n s-
former was s e t a t 34 v o lts and the d i s t i l l a t i o n allowed to proceed to 7° 0,
At t h is points a f t e r a period of t o t a l reflu x * the vapor tra p s Containing
the lig h ts were weighed and rep laced by a weighed gasoline tra p was placed
in to a thermoflasko
When th e tem perature approached 20° 0», the isopro-
panol was ,removed and wet ice in se rte d in i t s p lace.
then allowed to proceed to 204Q G= fo r a f i n a l re flu x .
The d i s t i l l a t i o n was
The gasoline so ob­
ta in e d was weighed and the residue was weighed when the column reached room
tem perature,
G atelyst B urnrpff
During th e run, a deposit of carbonaceous m ateria l was laid.down upon,
31
#
the c a ta ly s t reducing i t s a c tiv ity and n e c e s s ita tin g a b u rn -o ff a fte r each
run.
In o rder th a t a weight balance might be e sta b lish e d f o r the system,
the weight of t h i s carbon laydown had to be determined*
This was accomp­
lish e d by.passing a i r a t a constant r a te through the gas m eter and. into
the re a c to r while m aintaining the rea c to r tem perature a t about 400° O6- ,by
means of the h eating elem ents. ■The e fflu e n t gas was analyzed a t reg u lar
in te rv a ls by means of an Orsat apparatus to determine the per cent of c ar­
bon d io x id e,,carb o n monoxide, and oxygen*
These per cents were p lo tte d
and the carbon lay-down wax Calculated as shown in the sample calculations?
The tem perature of’ the b u m -o ff was m aintained below the s in te rin g tempera^
ture o f the c a ta ly s t -, about 600° 0.
by c o n tro llin g th e ra te a t which the
a i r was adm itted to the reactor*
Determ ination of per Cent Outside Gas in Jeed Cylinder a t End of Bun
Samples of the gases remaining in the feed cylinder were -taken, a t 1000
p sig and a ls o a f t e r th e cy lin d er pressure had been reduced to 000 p sig,
These samples were analyzed with- the low-temperature g a s-fra c tio n a tio n u n it
to determine the per cent mixed gas rem aining in the feed cylinder and not
charged*
The data obtained were in co n clu siv e; so the method used by Mayfield
(3) was adopted*
By th is method, the valves of the feed cy lin d er were closed
a t the end o f the run. before the feed .system was depressurized.
The feed
was then removed from the system and th e re s id u a l gases,- containing n itro g en
and mixed gas, were bled into a 0 4 - l i t e r tank* ; This- allowed a l l the mixed
gas in the cy lin d er to vaporize and be accounted for- in the analysis ,of the
low -pressure gases in the tank.
A nalysis showed the re s id u a l mixed gas t o
be 10 gramS9 This value of 10 grams was used in the. c a lc u la t ions of a l l runs
involving an outside gas*
Sincd th e 10 grams was outside gas uncharged, i t
was su b tracted frqm the weight of gas charged to the feed cylinder p rio r
to each run'; end c a lc u la tio n s were based on the corrected gas weight*
1500 and $000 p sig KunS
The p ro ced u re' in the se runs was e s s e n tia lly the same a s described
fo r the 900 p sig runs w ith the exception of the d ifferen c e in feed ra te
re g u la tio n .
The feed cy lin d er was f i l l e d w ith an a d d itio n a l 70 gm,. of charge to
compensate for th e hold-up in the pump and feed lin e s .
I t was then con­
nected to th e top of the ,Terguson gage in the usual manner.
was f i l l e d by g ra v ity flow and the feed pump waa s ta rte d .
The gage
The proper
feed ra te was obtained by a t r i a l and e rro r adjustment of th e p iston
stroke so th a t a space v e lo c ity of 4-6 h r , w o u l d r e s u l t .
Timingiof the
run began when the f i r s t pressure r i s e in the re a c to r was noted*
The r e s t
of th e procedure was id e n tic a l.to th a t described f p r 900 p s ig ru n s.
*r S3 «
. ,0 «’
' ■ ■, .
Wii© gas oil, Used in t h i s in v e s tig a tio n was ;a Borger, Texas V irgin
Gas o i l obtained from H x lllip s Petroleum Company,
Laboratory inspection-
d ata fo r the' v irg in gas o i l are given in Table 1«,
The o u tsid e gas used was a m ixture o f 30% n-bUtanes 10% iso-butane
30% Iso-OUtylerie f 20% propane, and 30% propylene prepared' b y the Matherson Company,
.
'>*>
24
**
II I SififfIS GjILCDTATIGNS
'
'
OaToulal;ions o f space DaLoeityi weight o f permanent g a se s, carton
lay-down on the c a ta ly s t from burn-off a n a ly s is , o y e r-a ll weight balance
■y ie ld of g a so lin e , per cent conversion, and p e r cent u ltim ate y ie ld are
presented' f o r run Nwiber 15 as ty p ic a l of a l l the runs made*
Ajt
C alculation of Liquid Space V elocity;
Data;
Volume of c a ta ly s t in the re a c to r
'
Seeding time •"
Weight o f charge.
Density of charge
Volumsi o f charge
.'Space v e lo c ity
Bo
555 ml* % 60 min./hfo
6','58'min. z IOOO ml^.
=? 1000 '
ml#"
6 o58 min.
~ 444^0 gm, .
“
OoS ,gDXr/ffilw
4 555.05 ml*
'
5*05 Iirow-
C alculation of Weight of. Permanent Gas:
' D ata;
Volume
Volume
Weiglit
Weight
Weight
of undondensable gases
of gas sample b o ttle
of h o ttle and gas
o f ■evacuated b o ttle
of gas sample, by d ifferen c e
. «
1
»
40*0
808^2
'S
124*115
S
1851985
=
0*188
:55
I*
ml'*
gnk
gm^.
gm*
LVeight of permanent gases ~
40 I:* x 0*182 gm*
6.2082
gm*
C.
C alculation of B um -off
Data:
Time
(tain.)
Air
(L iters)
3
13
9.0
2 .2
15
13
10.4
30
25
60
(Plotted on Figure 3)
Ave.
CO2
From
CO
Plot
°2
0 .6
4.5
1.1
9.3
85.1
12.1
5.6
.68
3.8
0
9.9
3.2
0.3
86.6
11.9
13.1
1.56
11.6
7.3
0
11.0
5.5
0
83.5
23.7
16.5
3.91
50
12.6
7.8
0
12.2
7.7
0
80.1
49.5
19.9
9.85
90
51
14.0
9.0
0
13.6
8.3
0
78.1
51.7
21.9
11.31
150
48
12.4
10.0 0
13.5
9.6
0
76.9
49.5
23.1
11.43
180
40
10.8
11.6 0
11.6
10.7
0
77.7
40.9
22.3
9.13
210
43
10.6
11.8 0
10.7
11.8
0
77.5
44.0
22.5
9.90
270
46
5.8
5 .9 9.0
8.5
9.5
4.2
77.7
46.9
18.0
8.44
330
47
1.0
0
18.0
3.3
3.0
13.4
80.5
46.4
6.3
2.92
By
C02
Analysis
CO O2
By D iff.
N2
Vol. Bff. Vol. #
Gas
CO2 ^CO
T otal
/eight of Carbon = 69.12 x 640 x 273 x 12
22.4 z 760 x 303
= 28.1 pja.
L ite rs
CO2 4 - 06
69.12
—
D.
26
—
C alculation o f an O vor-all height Balance:
I per cent of charge lo s t = 7 x 100
444
E.
10850
S
10396
10
444
Z
S
S
3
3
S
S
-
164.9
208.0
35.0
28.1
1.0
437.0
7.0
g g g g g g g
Recovered m a te ria l:
Hydroca bon liq u id product
Condensable gases
Permanent gases
Carbon from burn -o ff
Oil from c a ta ly s t bed
T otal weight recovered
Weight of charge lo s t by d ifferen ce
Z
1.58
*
.Veight of cy lin d er and charge
Weight of cy lin d er a f te r run
(Atmospheric pressure )
Weight of gas remaining in c y lin d er
Weight of m ateria l charged
ggg
Data:
C alculation of Per Cent Gasoline Y ield:
Data:
F*
per Cent gasoline on o i l charge =
81.8 x 100
263
-
81.8
263,0
Sg
=
=
30.75
^
Gasoline from d i s t i l l a t i o n
Gas o il charged
C alculation of Ber Cent Conversion:
Data:
Residue from d i s t i l l a t i o n
Oil from c a ta ly s t bed
T otal residue
=
115.0
=
1.0
"
116.0
Per Cent conversion on o i l charge =
100 - 116.0 x 100
263.0
55,9
#
*
27
Go '.G aloulatioa Of Bsr Ceat U ltim ate Y ie ld ;
Dafa $
P er cent gasoline on o il charge
per cent conversion on o i l chargePhr cent ultim ate y ie ld ~ 0Ofl?5 x 100
55,9 '
r
SOflYS %
55»9 $ "
»
55*0 %
,
C alculation o f Apportionment of Carhon Per Pass fo r the lime on Stream
D etem in at i bn; ""
.........
The procedure followed fo r t h i s determ ination was to pass about
;
’•
450 gnu o f charge over the c a ta ly s t during a six-m inute period*
hydrocarbon liq u id product was C ollected and d i s t i l l e d ,
»
.
The
'
Erom t h i s .d i s ­
t i l l a t i o n , the p er cent gasoline y ie ld and per cent conversion per pass
could be calculated*
Six such passes were made and the carbon was
burned o ff th e c a ta ly st a t the end of the cumulative 40-minute period*
Thus, a method by which th e carbon could be apportioned p er pass was
needed*
_.
According to Eroat ( I ) , gaseous hydrocarbons are soluble in the c a r­
bon re g a rd le ss of th e amount of d e p o sit. • In other words, a f t e r an ex­
tended time on stream., th e form ation of carbon is s t i l l due to c a ta ly tic
a c tio n r a th e r than to therm al cracking*
Yoorhies (8 ) in a study of c a r­
bon form ation in fixed-bed,-cracking found th a t th e re i s a good co rre la ­
tio n between feed stock conversion and carbon y ield based on feed fo r a .
given c a ta ly s tj fee d stock, and temperature*
I t may be mentioned th a t
there are numerous o th er d a ta ■.a v ailab le which show th a t conversion i s
linear- with the logarithm of carbon' yield*.
“ SS "=■
Siaee Figtoe 4 prepared from runs 15-18, p resen ts the above r e l a ­
tio n sh ip fo r mixed-gas polyforming a t 900 p sig , the carbon deposited
per pass during the 40-minute residence time could tie determined from
the per cent conversions c alcu lated from th e d i s t i l l a t i o n residues=
The follow ing d a ta i l l u s t r a t e ' th is Prbeedure 0
Total, carbon from "burn-off - IlG 0Q gin*,
Bun.
Ho0
V
25
86
27
28
28
50
Blapsed
Per, Oent
Time (Min»). Conversion
1 1
■" 1 " "
S955
5905
IS. 35
46,7 ''
18,91
45,5
2.5,25
. 54,0'
53,53
S le2
40008
28,4
Per Cent Car­
bon, on' TbOd
Weight
(Figure 4)
. Carbon
,
Bevised
, Carbon'
J '
7,55
4,?C
4,50
2;85
2,55
T otal
52 o0
20:5
19,8
13,5
12,5
10,18
' 33,3
21,7
20,8
14,6
15,6
. in ......
12,0
.. .
116,0
108,6
■Since the weight of carbon determined from Figure 4 did not q,uite
,»
■
to ta l 116 gm,» equal increments were added so that the revised Carbon
*.
would Beet th is quantIty 0
<
S9 ~
17 BESULTS
Huna 1*2*5 and 4 in Table IJ p resen t the c a ta ly tic cracking o f gas
o IJ w ith a Houdry sy n th e tic aluminum s i l i c a t e c a ta ly st a t low space v e l­
o c itie s ,
FpUr atmospheric runs were made a t tem peratures Varying from
4.136 to 509° GeI space V elo city was held between 0*65 and 0*75 volumes
o f feed per volume o f c a ta ly s t per, ,hour=,
'A p lo t o f per cent gasoline y ie ld as a function of p er cent conver­
sion is shown- i n Figure S* The highest y ie ld of gasoline obtained, fro # •
- -. '
'
the c a ta ly tic cracking of gas o i l was 5506 per cent a t 429° 0« This
'
p o in t, however* does not. occur a t the 'peak Of the curve* The trend pf
:•
the carte in d ic a te s th a t th e maximum y ie ld of gasoline is approximately.
34 per cent a t a tem perature near 460
Gp
The th e o r e tic a l fig u re , ultim ate y ie ld on o i l charge, i s c alcu lated
by assuming th a t a l l o f the m aterial b o ilin g above the gasoline range
would, upon re c y c lin g , e ffe c t the same conversion.
This th e o re tic a l
fig u re i s p lo tte d as a function of per cent conversion on o i l charge
in Figure 6 .
I t is seen th a t a. maximum ultim ate y ie ld of gasoline was
not obtained*
Runs S'* 6 , and 7 in Table I I p resen t the c a ta ly tic cracking o f gas
o i l a t high space v e lo c itie s .
Three atmospheric runs were made a t tem­
p e ra tu re s varying from 380° .0 * to 444° G=» space v e lo c ity was held be­
tween 4b35 and 4=4 volumes of feed per volume o f c a ta ly s t per hour*
At comparable conversion, approxim ately 2S per cent (re la tiv e ) more
gasoline was obtained a t low than a t high space v e lo c itie s *
\ c
» 30 ^
The sole purpose of in v e s tig a tin g c a taly b ie Ofaeking was to estafeV
• :
I is h a b a sis by which mixed-gas c a ta ly tic polyforming could be evaluated„
I t i s w e ll agreed th a t space v e lo c itie s held between OoS and IoiO volumes
I
r
of feed per Volume of c a ta ly s t per hour are b e st su ited to c a ta ly tic
■
crap king 0.
,
'
■
Efeyfield (S) found th a t gasoline y ie ld s from iso-butylene polyform-
' '"
tag were, approxim ately the sane, whether obtained a t space v e lo c itie s of
4»0 to SoO hr#”"^ or 0»5 to IoO h r,
On the b a sis o f 't h i s observation,
the higher Space v e lo c ity was chosen fo r the in v e s tig a tio n .
Thus p gasoline y i e l d s :from mixed-gas .polyforming a t high space v e l­
o c itie s w i l l be compared w ith those obtained from c a ta ly tic Crahking a t
low space v e lo c itie s ?
Table H I p resen ts the r e s u l ts o f mixed-gas c a ta ly tic polyforming
gas o i l a t atmospheric pressure# , Five runs were made a t tem peratures
varying from 405° to 475° G ,; 'space v e lo c ity was heId.between 4»5 and
4 ,8 volumes of feed per volume o f c a ta ly s t per hour®
i
-
1
■
■
A p l o t .pf per cent gasoline y ie ld as a fun ctio n of per Cent conver­
sio n is shown in Figure 7#
The curve shows, th e maximum yield, o f gasol™
lin e a s 86#6 p er cent a t 48,4 per cen t Conversion,
The gasoline- yl&ia,
Vhens was 27*8 per cent le s s re la tiv e than f o r atmospheric c a ta ly tic .
cracking*
.<
.
The curve showing per cent u ltim ate y ie ld g f gasoline versus
■•
.
■
--
per cent conversion in Figure 8 is also lower than f o r the c a ta ly tic
.
cracking curve®
The conversion p roducts» carbonand permanent gas, tend t o be more ■
pronounced when the gas o il is praeked in the presence of the mixed
gaso
Runs 13 to 18 in Table IT present th e c a ta ly tic cracking o f gas ■.
o i l at 900 p sig in the presence of. mixed gas.,
Six runs were made a t
tem peratures from 393° to 498° G, and a t apace v e lo c itie s held- between
4 093 and 5.15 volumes o f liquid, feed per volume o f c a ta ly s t per houro;
,figure, 9 shows the p lo t o f per cent gasoline y ie ld a s a function
of. per cent conversion.. The maximum y ie ld of 30.75 p e r Oonf odciirrod
a t 455° 0» and at & conversion of 85.9 per Oeat,
r
This y ie ld represents,
a r e la tiv e increase- o f 15*6 per coat ever the atmospheric polyfonning
yields*
The y ie ld s of gasoline, from conventional cracking*'however„
s t i l l surpass those obtained by mixed^gas polyforming a t 900 psig.
The relatio n sh ip - between ultim ate y ie ld on o i l charge and per .
cent conversion on o i l charge shown in Figure 10 in d id a te s .th a t the
ma-Hrm-nn y ie ld is obtained a t approxim ately 393° G='; t h i s y ie ld i s
le s s th an fo r t h e ,atmospheric cracking curve.
Carbon d ep o sitio n i s g rea ter and gas form ation i s le s s a t 900 p sig
than f o r atmospheric polyforming.
Runs 19, 30-, and 31 in Table T present the r e s u lts o f mixed-gasc a ta ly tic polyforming gas o il a t 150o pounds pressure.
Three runs were
1
-
made at.temperatures from-439° to 480° C. and at space v elo cities held
between 4.6 and 4.7 volumes of feed per volume of catalyst per hour. A plot of per cent gasoline yield as a function.of per cent convert
sion is shorn in Figure I I . The y ie ld of gasoline was 35.0. per cent f o f
'
' ' :.pach of the th ree runs made. The nonversion range was lim ited as a r e -
<?•
33
**
s u it of two o p e ra tio n a l d i f f i c u l t i e s $
(I) a tem perature lower than
430° Gt would..not develop the d esired pressure w ith a 500 gra, chargej
•and (3 ) a temperature- higher th an 480° C„ developed pressure so rap ­
id ly th a t v io le n t surging accompanied p ressu re re g u la tio n ,
fhe 55 per
cent y ie ld s rep resen t a re la tiv e in cre ase o f th ree per Gent over the
y ie ld s o f gasoline obtained by conventional c a ta ly tic oracking, • ThO
u ltim ate y ie ld of gasoline a t 1500 p s ig as shov®, in M gure 13 i s also
s lig h tly g re a te r than f o r atmospheric cracking*
Runs SSj 33 and 34 in Table T presen t the raised-gas c a ta ly tic polyforming o f gas o i l a t 2000 p s ig ,
Three runs were made a t tem peratures
varying from 440C) G, to 470° 0 .5 space V e lo c itie s were held between 403
and 4».9 volumes of feed p er volume o f c a ta ly s t per hour.
& phot of p e r cent gasoline y ield as a function Of p e r cent con­
v ersio n i s shown in Figure 13,
p sig curve,.
ThO curve is- very sim ila r to the 1500
The y ie ld s of gasoline are 30 per cent for. th e conversion
range studied*
The reason for the narrow conversion range has been pre­
v io u sly discussed*
I t w ill be n o ticed from the curve th a t in order to
o b tain comparable conversions* a lower tem perature is req u ired a t 1800
pounds than, a t 2000 psig*
The curve showing per cent u ltim ate y ie ld of
gasoline versus per cent conversion in Figure 14 follow s a trend sim ila r 1
to the .1500 pound curve, the exception being a IS, 2 p er cent re la tiv e
decrease. 'In y ie ld a t conversions of 56 p er cent.
Table Y I p resen ts th e r e s u lts of the time, of stream determ ination
w ith gas o i l and mixed gas a t 900 p sig .
Six runs were made a t tempera­
tu re s h eld r e l a ti v e ly constant near 455° 0* (the tem perature found to
~ SS ~
b© optimal?, in fig u re 9}; space v e lo c ity was held between 4*5 and S0IB
volumes of feed per volume of c a ta ly s t p e r hour,
A p lo t of eumulotive weight p er cent' of conversion products as a
fu n ctio n of of aching time o r time on stroam is shown in F igure'14,
fhe
y ie ld s of gasoline and permanent gas had decreased about th re e per Cent
a t the end o f 80 minutes^
products ra p id ly decreased,
Upon continued' cranking* the y ie ld s of these
i t w ill be noticed th a t the weight o f c a r­
bon on the c a ta ly s t is approxim ately.a. lin e a r logarithm ic function w ith
tim e.
The curves show th a t the C ataly st re ta in s most of i t s o rig in a l
a c tiv ity a f t e r 40 minutes d esp ite the considerablenamount o f carbon,
which was deposited,
. ,,
a*- 34
¥ SOMlARt
The r e s u l t s foutid in th is in v e s tig a tio n may be summarized as
follow s t
(I)
The. increase of re a c tio n pressure used fo r mixed-gas c a ta ly tic
• polyforming o f gas o i l r e s u lts in a d e fin ite increase in gaso­
lin e y ie ld u n t il SOOO p sig i s reached a t which p o in t the y ie ld s
decrease,
(S)
Oafbon deposition increases w ith each a d d itio n al pressure, in ­
crease ,
(3)
Oas form ation in mixed-gas c a ta ly tic polyforming i s a t a mini­
mum near 1500 pounds, pressure,
(4)
Oarbon form ation in mixed-gas c a ta ly tic polyforming i s notice­
ably g re a te r than in conventional c a ta ly tic cracking,
(5)
Mixed-gas c a ta ly tic polyforming a t 1500 pounds p ressu re gives
a d e fin ite increase in gasoline y ie ld over th a t obtainable
from atmospheric' c a ta ly tic pranking»
( 6 ) A. suitable- time, o f stream fo r mixed-gas c a ta ly tic polyforming
i s 80 m inutes,
.
(?) • The r e s u lts of the tim e of stream determ ination tend to in dicate
. th a t mixed-gas c a ta ly tic polyforming could be operated a t a cycle
through-put considerably g re a te r th an th a t used in normal p e tro l­
eum cracking,,-
' ;
■
Bbe
w ltb tho&kg tW ocm rw ayg# # e
j&Kttl&jpa 3&$*@3*q& Oaqpaay %W &B088#e*A IBwe
gb&a&tbj# #o#kwaa #meie'A ou#t
W b*
*** 36 •=?
VIZ LlTSRiVUBS <XM>
Th ZBmi^L Tiziamsmi mmii,- u f
(1)
'
F rost, Al
ib is -s
(2)
O fiM tt» Wi O i, O ste rg a a rd , P» , F o g le $ Mi 0», and B e u tiie rs.
(1 9 # I
s W phtM Polyfor-miBg* O il' Gas '31»,: 45> Ho* 87, ISO-iS
(1946) # (0*A^
(3) •O ffu tt, Wo C. s OsteZ1Saard9 P , - Fpgle 4'!Si0 . and BeUther,, •
S#, W Oil ibl#oW
&
g» O
il A
as
B
I,, 80^
9
(1947) i- (0*A^m.7?]#' ' ' ' '
'
(4)
Dev, Ram4 M4Si T h esis, Montana S ta te Oollege (1943)
(5)
M ayfield, L..GV, MeS, ThesiS5 Montana 'State College (1949.)
(6)
Polioh5 Wx T i i MvSi T h esisx Montana S tate College (1950),
(7) Ennenga9i S» Al, M,S«' T hesis, Montana S tate College (1950)
(S)
.
Voorhies5 Ae 5 Carhon Fomnation i n -C atalytic. Oraelcing,.
In
d
* Sng9C
beaw S
T
, 318*82 (19#.^
H I I APPENDIX
page
Table I
Das Oil luspeciiou Data#*6q**#s****g4**s*o***oeo 39
Table IX
- Catalytic QracMng of Das Oil at
Atmospheric Pressure*6**»**4**6*9**f@t**««»i*^*** 40
Table I I I
- Mixed-Das Catalytic Polyforming o f' Das
Oil a t Atmospheric Pressure
Table I ?
- Mixed-Das Catalytic Polyformihg of Das
Oil a t 900 psige o»16»^6-e'»ee be"»6 o#ae#e o• e-ee O'e9 *, 48.
Table T
Mixed-Gas Catalytic Polyfdrming of Das
Qil at 15OO and <3000 p s i g e »**9 »»»**&**« 48
Table TI
- Pigure I
« 41
~ Time of Stream Dsterminatibn6 Das Qil ■
With Mixed Das at 900 p s ig .. ...... .......................
44
«■ Schematic Diagram of .Low Pressure U nit.
45
Figure S
- Schematic Diagram of Higli- Pressure U n it.. . . . . . . . 46
Figure 0
- Composition of E fflu e n t Das During Cata­
ly s t Burn-off.b
47
Figure 4
- E ffe ct of Conversion on Carbon' TieId a t ............
•900 pSlg* .
*0*9*0. **b-. * * « * . • « . * * . * . . *'eo®**o0«o 48
Figure 5
- E ffe c t of Conversion on Dasdlihe Y ield a t ''
Atmospheric Pressure %.*..*$**....*****•*.* ** *.* * 49
Figure 6
- E ffe c t of Conversion on Ultimate Y ield of
o Gasoline a t Atmospheric: P r e s s u r e . * * 50
Figure 7
*■E ffe c t of Conversion on Gasoline Y ield a t
Atmospheric Pressure w ith Mixed Gas*
Figure 8
-•* E f f e c t o f C onversion on U ltim a te Y ield of
G asoline a t A tm ospheric p re s s u re w ith Mixed '
Gas,.*., . * . * * .,* «*-« *;» *.♦ * »-s * «;»»«.-* * . *.«'«.* s • » *« 58
Figure 9
- E ffe ct o f Conversion on Gasoline Y ield a t
900 psig w ith Mixed Das.
51
55
38 -
Page
Figure 10 - Effect of Conversion on Ultimate Yield of
G a so lin e at 900 psig with Mixed Gas. . . . . . . . . . . . . . „ 5 4
Figure 11 - Effect of Conversion on Gasoline Yield at
1500 psig with Mixed Gas............. ..........................„..55
Figure 13 - Effect of Conversion on Ultimate-Yield of
Gasoline at 1500 psig with Mxed Gas............. . . . . . . 5 6
Figure 13 - Effect of Conversion on Gasoline Yield at
2000 psig with Mxed Gas............................................. 57
Figure 14 - Effect of Conversion on Ultimate Yield of
Gasoline at 2000 psig with Mxed Gas................ ....5 3
Figure 15 - Effect of Stream Time on Yield of Conversion
Products at 900 psig with Mxed=Gas......................„.59
« 39 -■
TASDffl I
Qas O il Iiisp ectien fiata
(Borgen5■Texas Virgin G
as Oil)A
.S.T
.M
. D isto pB10
F i r s t dnop
-
.Sg?:
5^ CQnds 760 mms
555
• 565
IOgG
577
W
.591
Wo
(;
605
Wo
' 633
Wo
659
Wo
663
80%
693
90%
735
95%
740
End Point
748
Recovery
98%
Residue and loss
2,0%
Gravity 0AH
36«,0
V isc o sity , SSBf/lOO0 S6,
55.6
We ight per cent, sulphur
ObSl
TABLE II
C a t a ly t ic C racking o f Gas O il a t Atm ospheric B ressure
Run No.
No. Runs on Catalyst
Avg. Reactor Temp. °C.
Space Velocity hr . - 1
I
49
413
0.75
47
422
C. 65
3
48
432
0.70
4
50
509
0.67
Material Charged
Outisde Gas
Charge Stock, gra.
Total Charge
—
—
—
—
—
—
264
264
mmm
m————
250
250
267
267
Recovered lk iterial
H.C. Liqd. Prod.
Condensable Gases
Parmanent Gases
Oil from Cat. Bed
Carbon by Burn-off
Total Recovery
233.7
4.6
3.5
5.0
6.45
253.25
222.4
9.6
4.13
1.9
6.4
244.4
215.7
23.8
14.3
10.75
5.6
4.46
2.24
Losses by Difference, gm.
/o Losses on Charge
D istilla tio n Data
At. of (7-204) C. Gasolinegg. 3
Wt• of Itesidue
1 2 0 .6
At. of Condensable Gasesi 26.5
%
fo
■%
fo
Carbon on Total Chg.
Gasoline on Oil Chg.
Conversion On Oil Chg.
Ultimate Yield
2.44
32.7
52.4
62.4
2
84.0
104.8
31.7
2.56
33.6
57.3
58.6
5
6
6
398
4.35
7
380
4.4
444
4.4
—■■I■^ —
»».
261
261
254
254
269
269
263
263
192.4
31.9
17.7
216.8
13.2
5.5
206.1
26.6
5.8
1.6
0.8
12.4
267.3
1 2 .0
15.3
258.1
7.5
255.0
232.7
8.3
2.3
9.2
1 1 .0
263.5
7.2
256.7
-0.3
2 .0
—
1 .0
5.5
6.3
- 0 .1 1
1 .1
-0.4
2.04
2.9
84.7
48.6
83.0
73.2
52.1
58.6
132.0
8.4
4.64
33.2
67.7
49.0
5.86
31.8
71.6
44.4
8 8 .8
2.95
23.1
43.4
53.2
59.1
159.1
6.3
4.09
2 2 .0
37.5
58.7
7
8
1 1 .0
62.3
133.4
21.9
2 .8
23.7
45.0
52.7
TABLE I I I
Mixed-Gas C a t a ly t ic P olyform in g o f Gas O il a t Atm ospheric P ressu re
Run No.
No. Runs on Catalyst
Avg. Reactor Tenp.° C.
Space Velocity hr . ”1
44
405
4.6
9
45
412
4.7
Material Charged
Outside Gas
Outside Gas, gm.
Charge Stock, gm.
Total Charge
156.4
259
415.3
Synthetic Gas Mixture
149.4
165.4
264
259
413.4
424.4
Recovered Material
H. C. Liqd. Prod.
Condensab Io Gase s
Itermanent Gases
Oil from Cat. Bed
Carbon by Bum-off
Total Recovery
219.7
152.4
5.9
15.5
10.5
502.7
Losses by Difference, gm.
% Losses on Charge
8
Carbon on Total Chg.
Gasoline on Oil Chg.
■Jo Conversion on Oil Chg.
% Ultimate Yield
11
12
51
458
4.65
52
475
4.5
158.4
267
425.4
148.4
270
418.4
176.3
208.5
149.3
215.8
39.2
0.9
403.8
203.1
188.5
9.1
11.3
11.3
408.0
2.9
11.5
421.8
416.8
1 1 .6
5.4
1 .2
3.6
1 .6
2.7
1.3
0.3
0.85
0.38
53.4
164.4
137.7
56.0
146.7
153.1
71.0
140.1
134.0
2.7
2.7
25.4
39.0
65.1
2.7
26.6
46.4
57.4
D istilla tio n Data
Wt. of (7-204)° C. Gasoline 51.4
153.3
Wt. of Residue
Wt. of Condensable Gases 137.8
-%
ia
10
46
443
4.8
2.5
19.8
34.9
56.7
226.1
157.9
6 .8
6 .0
1 1 .2
2 0 .2
35.5
57.0
2 2 .6
1 1 .6
67.3
118.4
133.4
2.78
24.9
55.9
44.5
TABLE IV
Mixed-Oas C a t a ly t ic BolyTonaing o f Gas O il a t 900 p s ig
Run No.
No, Runs on Catalyst
Avg. Reactor Tempe0 C.
Space Velocity hr . ”1
13
42
392
4.95
Material Charged
Outside Gas
Outside Gas, gm.
Charge Stock, gm.
Total Charge
161
268
429
Recovered Material
H. C. Liqd. Prod.
Condensable Gases
Baroanent Gases
Oil from Cat. Bed
Carbon by Burn-off
Total Recovery
Losses by Difference, Gnu
Losses on Charge
D istilla tio n Data
Wt. of (7-204)0C. Gasoline
Wt. of Residue
Wt. of Condensable Gases
# Carbon on Total Chg.
dJ o Gasoline on Oil Chg.
$ Conversion on Oil Chg.
56 Ultimate Yield
224.7
153.0
18.9
14
31
430
4. 92
15
32
455
5003
16
34
470
5.15
Synthetic Gas Mixture
157
181
170
270
269
263
444
427
439
2 0 2 .6
15.1
424.3
170.0
25.2
0.5
20.5
418.8
4.7
164.9
208.0
35.0
168.2
17
33
492
5.09
18
41
498
5.0
166
262
428
164
271
435
125.6
186.5
60.0
178.4
192.4
64.6
1 .0
2 1 0 .6
2 1 .0
0 .6
28.1
437.0
29.4
429.8
44.5
417.2
45.4
422.4
8 .2
7.0
9.2
1 0 .8
1 2 .6
1 .1
1.9
1.58
2 .1
59.0
162.6
97.2
79.3
134.2
140.3
3.5
4.8
29.5
50.1
58.8
1 2 .6
2 2 .0
34.5
63.8
0 .6
2.52
1 .6
2.9
81.8
115.0
147.5
80.7
106.3
161.1
72.3
81.1
125.5
70.5
74.9
137.4
6 .2
6.7
30.0
60.2
49.9
10.4
27.6
10.4
26.0
71.8
36.2
30. 75
55.9
55.0
6 8 .8
40.1
TABLE V
LIixed-Gas C a t a ly t ic l b ly fo rm in g o f Gas O il a t 1800 and 2000 p s ig
Run No*
No. Runs cn Catalyst
Avg. Reactor Temp. °C.
Avg. Oper. Press, psig
Space Velocity h r.”
19
4
439
1500
4.6
20
6
449
1500
4.7
Material Charged
Outside Gas
Outside Gas, gm.
Charge Stock, gm.
TotalChargo
155.5
256.5
432.0
Recovered Material
R. C. Li rid. Prod.
Condensable Gases
Permanent Gases
Oil from Cat. Bed
Carbon by Burn-off
Total Recovery
249.7
137.5
12.9
3.9
28.8
432.8
216.0
127.4
25.5
3.5
36.7
412.1
Losses by Difference, gnu
- 0 .8
dJ0 Losses on Charge
D istilla tio n Data
Wt. of (7-204)°C. Gasoline
Wt. of Residue
Wt. of Condensable Gases
$ Carbon on Total Chg.
Gasoline on Oil Chg.
% Conversion on Oil Chg.
$ Ultimate Yield
$
21
22
23
5
480
1500
4.6
7
440
8
460
24
9
470
2000
2000
2000
Synthetic Gas Mixture
152
180.3
264
255.7
436.0
416
4.5
4.3
4.9
195
306
501
304
506
200.5
306.5
507
183.2
164.2
29.0
4.8
46.5
427.7
265.4
181.7
17.8
5.1
27.7
497.7
263.4
170.7
24.2
8.3
36.5
503.1
256.2
161.9
34.6
11.5
38.5
502.7
3.9
8.3
3.3
2.9
4.3
- 0 .2
0.9
1.9
0.7
0 .6
0.9
93.1
113.1
137.8
92.5
85.4
144.4
89.5
63.2
152.9
91.0
143.9
161.0
91.8
126.2
167.3
91.8
113.3
155.9
6.7
34.9
56.1
62.2
8 .8
35.0
64.4
54.4
10.7
55.0
73.4
47.7
5.5
29.7
51.4
57.9
7.2
30.2
55.9
54.0
7.6
30.0
59.3
50.8
202
TABIE VI
Time of Stream Determination • Gas Oil »ith Mixed Gas at 900 psig
29
38
456
26.23
5.12
39
458
33.53
4.50
30
40
454
40.08
4.85
165
272
423
162
261
234.8
154.1
14.6
425.0
220.3
166.9
27.6
0.3
13.6
428.6
422.4
5.0
8.4
0 .1
1.16
1.92
0 .0 0
Run No.
No. Runs on Catalyst
Avg. Reactor Temp. °C.
Cumulative Time on Stregm, min.
Space Velocity h
r
.
25
35
456
6.53
4. 74
26
36
463
13.33
4.30
27
37
460
19.91
4.96
Material Charged
Outside Gas
Outside Gas, gm.
Charge Stock, gm.
Total Charge
164
271
435
Synthetic
173
262
433
Gas Mixture
166
167
264
265
430
437
Recovered Material
H. C. Liqd. Rrod.
Condensable Gases
Permanent Gases
Oil from Cat. Bed
Carbon by Calculation
Total Recovery
163.5
201.0
31.5
0.4
33.3
432.7
196.1
188.1
27.3
0.5
21.7
433.8
208.0
155.9
33.2
0.3
225.8
156.7
26.8
2 0 .8
418.2
Losses by Difference, @n.
2.3
1 .2
14.8
dJa Losses on Charge
0.55
0.28
D istilla tio n Data
Wt. of (7-204)° C. Gasoline
Wt. of Residue
Wt. of Condensable Gases
'% Carbon on Total Chg.
% Gasoline on Oil Chg.
dJo Conversion on Oil Chg.
dJ9 Ultimate Yield
31.5
108.9
155.4
7.65
30,0
59.5
50.5
71.6
138.9
144.3
5.00
27.4
46.7
58.6
3.42
72.0
144.2
128.0
4.80
27.0
45.5
59.4
1 .1
80.0
173.1
113.3
3.39
22.7
34.0
66.7
20
59.8
187.0
1 2 1 .2
3.11
23.0
31.2
70.5
2 1 .0
1 .0
1 2 .0
50.5
186.0
134.6
2.84
19.35
28.4
6 8 .2
-
45
-
NITROGEN
CYLINDER
Figure I
Schematic Diagram of Low Preanure Unit
J
— 46 —
TO BLOW DOWN
SAFETY DISC
TO BLOW DOWN
OAS METER
PREHEATER
REACTOR
F E E D ___
CYLINDER
CATALYST
GAGE
JERGUSON
GAGE
[JTHERMOWELL
X CONTROL
. VALVE
WATER
CONDENSER
^DRY ICE-ISOPROPANOL
PUMP
RECEIVER
Figure 2
Schematic Diagram of High Pressure Unit
GAS
BOTTLE
18
time
, ^I n d i e s
Figure 3
Composition of Effluent Gas During Catalyst Burn-off
48 -
GAS
OIL W IT H
S Y N T H E T IC
SPACE VELOCITY 4 - 6 HR-1
GAS
M IX T U R E
CARBON
ON
OIL A N D
GAS
CHARGE
PRESS. 9 0 0 - PSJG
°/o C O N V E R S IO N
ON
O IL
CHARGE
Figure 4
Effect of Conversion on Carbon Yield at 900 psig
GAS
SPACE
%
VELOCITY
C O N V E R S IO N
ON
O IL
0 . 6 - 0 .8 HR
O IL
CHARGE
Figure 5
E f f e c t o f C onversion on G a s o lin e Y ie ld at Atm ospheric P ressure
SPACE
GAS O IL
VELOCITY 0 . 6 - 0 . 8 HR
i
8
I
%
C O N V E R S IO N
ON
O IL
CHARGE
Figure 6
E f f e c t o f C onversion on U ltim a te Y ield o f G a so lin e at Stmosipheric Pressure
60
GAS
O IL
SPACE
S Y N T H E T IC
W IT H
VE LOCITY
4 - 6 HR-'
S so
GAS
M IX T U R E
PRESS. 0 - PSIG
__________ i__________ I__________
cr
<
x
O
O
Z
° 30
458
4 4 ---------0 --------- 475
Cl
V0
LU
>
°\
Ol
H
«412
405^
20
I
UJ
Z
O
05 10
<
O
*5
0
0
10
20
%
30
40
C O N V E R S IO N
50
ON
O IL
60
70
CHARGE
80
Figure 7
E f f e c t o f C onversion on G asolin e Y ie ld a t Atm ospheric P ressu re I i t h Mixed Gas
90
C;a s
o il
S PACE
W IT H
VELOCITY
S,Y N T H E T I C
4 - 6 H R-'
GAS
M IX T U R E
PRESi3.
O - PSIG
443 0
O 60
U L T IM A T E
Y IE L
xX x
4 0 5 $ 4,2
L_
r
''
\4 5 8 0
50
0^475
—
20
%
30
40
C O N V E R S IO N
50
O N O IL
—
60
CHARGE
F ig u re 8
E f f e c t o f C onversion on U ltim a te Y ie ld o f G a so lin e a t Atm ospheric P ressu re With
Mixed Gas
60
GAS
VELOCITY
S Y N T H E T IC
4 - 6 HR"'
GAS
PRESS.
M IX T U R E
9 0 0 PSIG
G A S O L IN E
Y IE L D
ON
O IL
CHARGE
SPACE
OIL W IT H
O
10
20
30
40
% C O N V E R S IO N
ON
30
O IL
60
CHARGE
70
80
Figure 9
E f f e c t o f C onversion on O a s o lin e Y ield a t 900 ps ig Wfi th Mixed Oas
90
80
GAS
OIL
VELOCITY
S ) fN T H E T K :
% U L T IM A T E
GAS
PRESS
4 - 6 HR"'
Y IE L D
SPACE
W IT H
^
M IXTU R E
9 0 0 PSI G
4 30"
C
Xx4 5 5 "
O
N
50
$70"
D
----------
o
92"
\
4 98"
\
20
%
30
40
C O N V E R S IO N
50
ON
O IL
60
CHARGE
70
Figure 10
E f f e c t o f C onversion on U ltim a te Y ield o f G a so lin e a t 900 p s ig With Mixed Gas
60
<3AS
OIL W IT H
iSPACE VEL OCITY
S YNTHET C
4 - S HR-'
GAS
PRESS.
F IX T U R E
1500 - PSIG
LU 50
O
CE
<
X
°
40
439
449
480
---- O ------ ----- O ------- ----- 0 ------
Z
O 30
I
LU
Ul
>
Ol
—
8
S '0
C O N V E R S IO N
ON
O IL
CHARGE
Figure 11
E f f e c t o f C onversion on G a so lin e Y ie ld at 1600 p s ig With Mixed Gas
I
80
GAS
OIL W IT H
S Y N T H E T IC
SFttCE VELOCITY 4 - 6 HR-1
GAS
M IX T U R E
PRES$, 1500 - PSIG
70
U L T IM A T E
Y IE L D
\4 3 9
50
30
20 L-
10
20
%
30
40
C O N V E R S IO N
50
60
ON O IL C H A R G E
F i g u r e 12
70
80
90
E ffe c t o f C onversion on U ltim a te Y ie ld o f G a so lin e at 1500 p s ig w tth Mixed Gas
100
60
GAS O IL W IT H
SPACE VELOCITY
S Y N T H E T IC
A -G H R -1
GAS
M IX T U R E
PRESS. 2 0 0 0
- PSIO
S 50
cr
<
I
o
_J
40
O
Z
O
140 460 4
"0
O
C)7 0
O 3
-I
UJ
>Ol
-a
LU 20
O
CO
<
O IO
20
%
30
40
C O N V E R S IO N
50
ON OIL
60
CHARGE
70
80
Figure 13
Effect of Conversion on Gasoline Yield at 2000 psig with Mixed Gas
IOO
GAS
OIL W IT H
VELOCITY
4 - 6 HR-1
GAS
M IX T U R E
PRESS. 2 0 0 0 - PSIG
U LTIM A TE Y IE L D
SPACE
S Y N T H E T IC
%
C O N V E R S IO N
ON
O IL C H A R G E
Figure 14
E ffe c t
o f C onversion on U ltim a te Y leM o f G a so lin e at 2000 p sig w ith Mixed Gas
— 59 —
GAS O IL W IT H
S Y N T H E T IC
SPACE VELOCITY
GAS M IX T U R E
4 - 6 HR-1
A
RESIDUE ON GAS OIL CHARGED
IOO
O
GASOLINE ON GAS OIL CHARGED
90
Q
CARBON ON CATALYST
#
PERMANENT GAS ON TOTAL CHARGE
CUMULATIVE
WEIGHT PERCENT
60
4
3
6 7 8 8 IO
20
30
40
50 60 70
CRACKING TIME, MINUTES
F i g u r e 15
Effect of Stream Time on Yield of Conversion Products at 900
psig With Mixed Gas
MONTANA STATE UNIVERSITY LIBRARIES
III
3 3 8 /3
762 10014180 1