Nov. 13, 1962 , w. R.

EPPERLY ET AL - 3,063,934
REMOVAL OF AROMATICS, OLEFINS AND SULFUR FROM NAPHTHA FEED
Filed April 10, 1959

4
05/06 FEED>

ISOMERATE William R.FE|%%erIy J

George F. e ouer r.
BENZENE John R Tume Inventors
Charles W Tyson
By W UU. 277*? Attorney
 United States Patent 0 3,063,934
Patented Nov. 13, 1962

1 2
of ole?ns is highly undesirable in feeds for an isomeriza
3,063,934 tion process using aluminum bromide catalyst, since the
REMOVAL OF AROMATICS, OLEFINS AND SUL ole?ns react with the aluminum bromide to form sludge
- FUR FROM NAPHTHA FEED
William R. Epperiy, Roselle, John R. Tuttle, Summit, compounds. This reaction consumes costly aluminum
George F. Feldbauer, Jr., Cranford, and Charles W. bromide. The sludge and any sulfur present also fouls
Tyson, Summit, N.J., assignors to Esso Research and and deactivatesthe catalyst support and is highly cor
Engineering Company, a corporation of Delaware rosive.
Filed Apr. 10, 1959, Ser. No. 805,531 Known natural adsorbents such as silica gel have proven
14 Claims. (Cl. 208-91) ineffective in preparing feed for aluminum bromide isom
10 erization. This is because their selectivity for aromatics,
The present invention relates to the preparation of feed ole?ns, and sulfur is not as great as the synthetic sieves.
for isomerization and para?in alkylation. More par Broadly, it is the principal object of the present inven
ticularly, it relates to a new and useful process for re tion to provide a more e?icient method for removing
moving from the feed certain hydrocarbons which are benzene, related aromatic hydrocarbons, ole?ns and sulfur
detrimental to the catalysts used in isomerization and 15 from the feed to a naptha isomerization reactor as well as
para?in alkylation. Even more particularly, the inven to upgrade low octane normal and isoparaf?ns to high
tion relates to the removal of benzene, ole?ns, and sulfur octane branched chain para?ins. '
compounds from the feed streams by adsorption with a Aromatics, ole?ns and sulfur are removed from the
molecular sieve, and utilizing the isomerate to desorb or _ isomerization feed by contacting the feed with an ad
purge the sieve. 20 sorbent material selective to aromatic and ole?nic hydro;
With the modern trend to the use of higher compres carbons and sulfur, eg a 13X molecular sieve. The
sion ratios in automotive engines there has been an in e?ectiveness of the molecular sieves is directly dependent
creasing demand for motor fuels of higher octane rating. on the excellence of the desorption. The development of
One of the processes employed for improving the octane aluminum bromide isomerization and paraf?n alkylation
quality of naphthas that are blended into gasoline involves 25 has necessitated the removal of essentially all of the hen-1
subjection of a fraction comprising normal paraf?n hydro zene from feed stocks. In the case of aluminum chloride
carbons to a catalytic isomerization reaction wherein con isomerization, it is su?icient to reduce the benzene in the
version to branched chain hydrocarbons takes place. The feed to less than 1%; while in the case of aluminum
isomerization of normal para?ins to isopara?ins in the bromide isomerization it is necessary to reduce the benzene
presence of a Friedel-Crafts type catalyst, of which alumi~ 30 in the feed to less than .02%. To obtainless than 1% of
num bromide is an example, and in the presence of pro benzene the saturated molecular sieve may be desorbed
motional amounts of halogen-containing promoters, of by heating, vacuum desorption and cooling. However,
which hydrogen chloride is a typical example, is old. this desorption cycle is not adequate to reduce the benzene
Numerous processes have been devised, both vapor phase to the target level needed for aluminum bromide isomeri
and liquid phase, 'for the isomerization of normal paraf 35 zation.
?ns to the corresponding isoparal?ns. In accordance with the present invention, it has been
When the light naptha being isomerized contains appre found that the saturated molecular sieves can be effectively
ciable amounts of benzene, ole?ns and/or sulfur, the desorbed by utilizing part or all of the effluent from the
ef?ciency of the isomerization reaction is seriously im isomerization reaction. This isomerate is used to heat,
paired. The presence of benzene in the feed to the purge and cool the sieve in an economical and highly
isomerization reaction in quantities greater than about efficient manner.
.02 volume percent is injurious when the highly active The nature of this invention will be more fully under
aluminum bromide catalyst is employed. To ensure that stood when reference is made to the accompanying draw
the'isomer'i'zation reaction will not be retarded, it is neces ' ing.
sary to remove these aromatic and ol?nic hydrocarbons 45 Zone 1 illustrates the adsorption stage of the process.
and sulfur or substantially reduce their concentration in ZonesZ and 3 show the heating and purging and the
the feed stream. In addition the presence of benzene cooling stages of the process. Three contacting zones
interferes with the separation of heavy naphthenic bot 1, 2 and 3 are shown in the adsorption, heat-purge, and
toms by fractionation. This may be a desirable step in cooling stages of the cycle respectively. In the operation
preparing the light naptha as an isomerization feed. The 50 of the invention, each of the three contacting zones passes
benzene, which has a normal boiling point of 176 F., successively, starting at stage 1, through the three stages.
forms low boiling azeotropes with normal hexane and After the sieve is cooled in stage 3 it may be used to
naphthenes such as methyl cyclopentane and cyclohexane. repeat the cycle. In the actual operation of the apparatus
Efficient separation of the naphthenes and benzene from andprocess the contacting zones remain in ?xed posi
the para?inic compounds is impossible because of the 55 tions and a manifold is utilized to control the input and
azeotropes which tend to come overhead with the desirable exit gases to and from each zone. For simplicity, how
para?inic compounds. These azeotropes boil in the same ever, the apparatus and process will be described as though
range as does normal hexane in a light naphtha cut, i.e. each sieve case is physically transported from one stage
150 to 160 F. Once the benzene is removed, this to the next.
separation becomes simple. The separation of aromatics 60 Turning to Zone 1, hydrocarbon feed, containing aro
can be done by such methods as solvent extraction, ex matics, ole?ns and/or sulfur, is introduced through line 4
tractive distillation, and low pressure hydrogenation using into furnace 5 wherein it is vaporized and preheated to
a catalyst such as palladium. Operations of this type are about 250 F. It should be noted that though the feed
costly, however, and the need for better methods for re to the sieve case or adsorption is generally in the vapor
moving aromatics has continued to exist. The presence 65 state, in some situations it may be advantageous to carry
 3,063,934
3 4
out the adsorption step under mixed phase or liquid phase available is not of a high quality, it is desirable to use
conditions. This preheated feed enters contacting zone this modi?cation.
1 thru line 6 and is stripped of aromatics by a fresh 13X In another modi?cation, the hot sieve case which has
molecular sieve. The aromatic-free hydrocarbon sievate just been purged may be cooled by circulating sievate
leaves through line 7, is cooled in condenser 8, and passes through it in a cooling loop. This procedure serves to re
to the isomerization reactor 14 through line 9. ' move any traces of benzene which remain after the ad
At or just before breakthrough, i.e., the time when sorption step. E?ectively, in this modi?cation, the bcn~
aromatics are no longer adsorbed in sieve case 1 to the zene containing hydrocarbon feed is adsorbed in two
desired extent, the adsorption step terminates and the heat steps: ?rst, the conventionaladsorption step and, sec
purge stage commences. The occurrence of break ondly, in the cooling step where the fresh sieve case acts
through may be established by observing the refractive as a trimmer.
index or ultraviolet absorption of the e?iuent stream. At In still another modi?cation, the separate cooling phase
breakthrough the refractive index increases abruptly. may be eliminated. This may be accomplished by pass
Breakthrough may also be determined from temperature ing feed directly to the sieve case after it has been heated
measurements Within the sieve bed. The zone where 15 by the purge gas. In this two-stage modi?cation, it is,
adsorption is taking place has a higher temperature than of course, essential that the cooling front, i.e. the wave
the rest of the bed, or a so-called temperature peak. of low temperature feed remain in front of the adsorption
When this temperature peak nears the exit end of the bed, front. The sieve case is cooled to the proper adsorption
breakthrough is imminent. temperature very rapidly and its higher initial tempera
In the heat-purge stage, represented by contacting zone 20 ture does not effect the sievate quality signi?cantly.
2, hot isomerate vapors are employed. The subsequent When isomerate is not available for purge and a purge
cooling stage is shown in zone 3. The isomerate vapors stream of a low heat capacity is used, it may be desirable
from an isomerization reactor 14 are heated to a tempera to use a 4-stage process. In this modi?cation, the heating
ture of about 650 F. by passing them successively and the purging take place in separate sieve cases and
through line 15 and furnace 13, the hot contacting zone 3 external means used to heat and cool. The reason for
and furnace 10. Upon entering contacting zone 2 the this modi?cation is that with low heat capacity gases, a
hot isomerate vapor serves a dual function. Firstly, the very large volume would be needed to heat and cool the
molecular sieve in contacting zone 2 is heated to about sieve cases.
650 F.; and secondly, the aromatics adsorbed on the In practicing the present invention, molecular sieves of
sieve are purged. The hot isomerate vapors now contain 30 front about 6 to 15 Angstrom size are preferred. Molecu
ing the aromatic desorbate, i.e., the material adsorbed lar sieves of this range of pore sizes are highly selective
during the adsorption step, leave contacting zone 2, of aromatics and ole?nic hydrocarbons over other com
and are cooled in condenser 11. This mixture may be pounds found in light naphthas. For example, a Linde
used as a high grade gasoline. After the purging is 13X sieve may be effectively employed. Such a sieve may
complete, the molecular sieve is cooled in contacting zone 35 be prepared by reaction of a sodium silicate having a
3 by passing through it cool isomerate, i.e., isomerate high ratio of sodium to silica, eg. sodium met-asilicate
heated to 250 F. in furnace 13. It should be noted that with a sodium aluminate having a soda-to-alumina ratio
the isomerate for cooling enters the contacting zone in of from 1:1 to 3:1, the proportion of sodium silicate
the same direction as the isomerate purge, and, in each solution to sodium aluminate solution being such that the
case, the flow is countercurrent to that used in adsorption. 40 ratio of silica-to-alumina in the ?nal mixture is at least
This procedure is advantageous because any residual ad 3:1 and preferably from about 4:1 to about 10:1. Pref
sorbate, i.c., aromatics or ole?ns, that remains in the erably the sodium aluminate solution is added to the
lower part of the sieve may be removed by the isomerate sodium metasilicate solution at ambient temperatures
in contacting zone 3. By the time the isomerate reaches while employing rapid and efficient agitation so as to en
the lower part of zone 3 it is su?iciently heated to act as 45 sure the formation of a precipitate having an essentially
a clean-up. In this third stage, the contacting zone 3 is uniform composition throughout. The resulting homo
cooled to about 250 F., a temperature suitable for a sub geneous paste is heated to about 180 to 215 F. for a
period as long as 200 hours or more to ensure that the
sequent adsorption stage. The isomerate leaves contact crystals thereby formed will have the desired pore di
ing zone 3 through line 12 and passes to the heating and
purging stage as described above. 50 ameter of from about 10 to 11 Angstroms. After the
period of heat soaking, the precipitated sodium alumino
Many modi?cations of the above described process silicate is ?ltered and water washed and then dried and
can be made within the scope of the present invention. activated in a calcining zone preferably at a temperature
For instance, the cooling gas may be passed through the of about 700 to 900 F.
contacting zone in the same direction as the feed. Run Another adsorbent which may be used in this applica
65
ning the isomerate through the molecular sieve in the tion in the Linde 10X sieve. This type of sieve is formed
cooling stage, of course, initially cools the inlet end of from 13X sieve by replacing 50% of the sodium with cal~
the sieve; this cool part of the sieve acts to strip any cium, and has a pore diameter of from about 8 to 9 Ang
residual aromatics, ole?ns and sulfur from the isomerate. stroms. The 10X form of sieve is superior to 13X in heat
This very clean isomerate, as it passes to the outlet end 60 stability. The following table compares the capacities of
of the sieve, is heated up and acts to further purge the the two type of sieve for benzene after heating in wet air
hot outlet end. As a result of this procedure the outlet containing 10% water at 1300" F. for varying periods of
end of the sieve case in the cooling stage is, thoroughly time.
stripped of adsorbate. This outlet end, since the feed TABLE I
and cooling streams are run through the contacting zone 65
in the same direction, becomes the outlet end in the ad
sorption stage. When the feed is passed through the con Benzene Capacity
at Equilibrium,
tacting zone, it is readily stripped of susbtantially all Type of Steve Wt. Percent
benzene, ole?ns and sulfur in the inlet end of the sieve.
Any traces of aromatics, ole?ns and sulfur remaining are 70 10X 13X
removed in the more thoroughly purged exit end of the
sieve. Such a procedure thereby improves cleanup of, Time, HIS. at1,300 F:
0_ 15. 5
the feed. The choice of which direction to use during the 3
65 14. 0
cooling step depends upon various factors. For instance,
when a large amount of purge is available, or if the purge 75
 3,063,934
5 6 ,
Brie?y, the mechanism of the purge is twofold. Firstly, TABLE IV .
the purge, i.e. isomerate, reduces the partial pressure of
the benzene and ole?ns and thereby provides a driving Analysis by gas chromatography: 10963522123???"
force for the desorption. Secondly, the isomerate purge RC4 _ .
is adsorbed, even at elevated temperatures, and displaces iC5 __ 11.6
the aromatics, ole?ns and sulfur on the molecular sieve. nC5 15.1
Brie?y, isomerization is the conversion of normal paraf 2,2-DMB ___ 1.9
?ns to their branch-chained isomers. The following data 2-MP, CP, 2,3-DMB ____________________ __ 19.1
are typical of the changes in composition occurring upon 3-MP __ 8.9
isomerization. 10 nC6 __________________________________ __ 17.0
TABLE H 24-DMP, MCP, 2,2-DMP _______________ __ 11.8
C6116 _________________________________ __ 5.7
Composition, Vol. Percent; Feed Isomerate 2,3-DMP, CH, 3,3-DMP ________________ __ 7.3
Z-MH, 3-MH __________________________ __ 0.5
Isopentane.____ 12.0 19. 7 15 3-EP ___._ 0.4
n-Peutane ____ __ __ 16. 3 4. 8
nCq ________ _s _________________ __ _____ __ 0.1
2-2 dimethyl buta ___ 2.1 20. 2
23 dimethyl butane, 2methy1 pentane and MCH __ _ __ c _ _ _ _ __ 0.3

cyclopentane ______________________________ __ 20. 2 25.0 C7H8 _____ __ 0.1

3-methyl pentane___ _______ __ _ 10. 3 7. 7
n~Hexane ___________ __ _ 19. 9 4. 8
Methyl cyc1opentane_-__
Cyclohexnne . _ _ _ _ _ _ _ _ _ _ _
_
_ _ _ _ _ __
12. 8
6. 4
2.8
15. 0
20 Inspections: Feedstock properties
Benzene 0.0 0.0 Gravity, API __________________ ________ 76.2
Reid vapor pressure, p.s.i.g _____________ __ 9.47
RI at 20 C __________________________ __ 1.3810
Of course, the isomerate composition is dependent on Br. Index (Br. No. X 1000) mg. Brz/
the feed used and the operating conditions used, in the 25 100 gm. _____________________ __v_____, 57.0
particular isomerization reaction. Sulfur, weight percent _________________ __ 0.0028
The isomerate is uniquely suitable as a purge because Gum, gm ________ __I _______________ _.;___ 1.0

it is essentially free of aromatics, ole?ns and sulfur, and Color, Saybolt _______________________ __ +28
effects virtually complete desorption of these components Aniline pt., F _______________________ __ 135.0
from the molecular sieve. The molecular weight of the Distillation, F. at 760 mm.:
isomerate is Sll?'lClCIlt to readily displace the benzene at IBP ____________________________ __ 105
high purging temperatures; yet it is not so high as to re 5% ____________ _,_ ______________ __ 123

tard displacement by the benzene, ole?ns, and sulfur dur 50% ,________________ __ _______ ___, 137

ing the low temperature adsorption stage. This is of great 795% ______________________ __,____._. 161
import since these components destroy the aluminum 35 FBP ___________________________ __ 184
bromide isomerization catalyst.
Where there is a high percentage of benzene in the feed, A sieve process was carried out on the above feed as
i.e., on the order of 6%, substantially all of the isomerate follows: Adsorption took place at 250 F. This was fol
i.e. 1.5 w./w. is recycled back to the desorption step. lowed by heating the molecular seive by recycling de
However, where there is only, say, 2% benzene in the sorbate and vacuum desorption at 600 F. The sieve was
feed, it is still suf?cient to use 1.5 w./w. of isomerate then cooled by recycling sievate and thereby readied for
purge. In accordance with the invention, it is unneces reuse in adsorption. The following data show the operat
sary, and even undesirable, to separate the isomerate and ing conditions of this example:
the benzene since the desorbed benzene improves the
octane number of the isomerate gasoline. The avoidance 45 TABLE V
of fractionation eliminates an expensive and time-consum Adsorption: ~
ing step from the process. Pressure, p.s.i.g _____________________ _,_.._ 15
The particular cycle of the invention has the further ad Time, min. _ __ 55
vantage of minimizing the external heat needed for suc Food, w./100 w./cycle _______________ __,___ 84.6
cessful operation of the process. Using the isomerate 50 Bed temp., F. (end) __________________ __ 284
stream in the ?rst instant as a coolant for a desorbed mo Heating (Desorbate recycle) :'
lecular sieve, and then for purging, contributes to the Pressure p.s.'i.g'. ________________________.._ 30
overall heat economy of the process. I Time, min. _ g 30
The following data represent the broad operating limits Inlet temp., F; ___________________ _.'_..___ 650
of the process of the invention: 55 Amount, w./100 w/ cycle ___ _____________ __ 93.0
\Bed temp., F. (end) ___________________ _._ 620
TABLE III Vacuum:
Refrigeration temp., F. ________________ __ 45
Adsorption Operating Preferred Final pressure, mm. Hg abs _______________ ___ 100
Range Range 60 Time, min _____________________________ __ 30
Bed temp., F. (end) __________________ __ 585
Temperature, F ___________________________ __ 70-500 200-350 Repressuring:
Pressure, p.s.i.g_______ _______ __ ___- 0-100 15-60
Flow Rate, w./w./hr ________________________ __ 0.1-5.0 0.5-3.0 Final pressure, p.s.i.g ___________________ ___ 25
Heating and Purge: Time, min _____________________________ __ 7
Temperature, F. (?nal)__ 500-800 550-650 65
Pressure, p.s.i.g___________ 0-100 0-415 Amount, w./100 w./cycle ___ _________ __,___ 3.5
Flow Rate, w./w./hr ____ -_ 0. 1-5. 0 0. 5-3. 0 Bed temp., F. (end) _____ __,____..,___-..__.._..,_ 585
Cooling:
Temperature, F. (?nal) ________________ __ 70-500 200-350 Cooling (Sievate recycle):
Pressure, p.s.i.g __________________ __ ___- 0-100 15-60 Pressure, p.s.i.g ________ __, ____ ___ _____ __,__,_ 30
Flow Rate, w./w./l1r _____________________ __ 0. 1-5. 0 0.5-3. 0
Time, min. __ > 30
70 Inlet temp., F _________________________ _._ 260
Amount, w./100 w./ cycle ________________ __ 93.0
Example I Bed temp., 'F. (end) ___________________ __ 300
The following feed was processed to show the advan In accordance with the invention, thevacuum desorp
tages of the invention: 75 tion was replaced by a purge step. Purge with an inert

gas, N2, and with sievate were carried on under the fol
vlowing operating conditions:
TABLE VI
Adsorption: ' ' '
Feed, w./100 w./cycle _________________ __ 152.3
Bed temp., F. (end) .; _______________ __
Pressure, p.s;i.g. ._'____'_;:_______________ __
Time, min. ' 55
Heating (Desorbate recycle):
Bed temp, F. (end) _________________ __.
Pressure, p.s.i.g. __.;...___; ______________ .__
Time, min; __________________________ __
Inlet gas temp, F. __________________ _..
Amount recycled, w./ 100 w./cycle ______ .._
Purge:
Purge used, w./w./cycle _______________ .._
Bed temp., F. (end) _________________ __
Pressure p.s.i.g. ___'_'.. ____ _..__' _________ __
Time, min. __________________________ __
Cooling (Sievate recycle):
' Amount recycled, w./ 100 w./cycle ______ __
Bed temp, F. (end) _________________ __
Time, min. ' '
Sievate makeup, w./ 100 w./ cycle ________ _._
Inlet gas temp., 'F. __________________ ..
Comparison of the above processes clearly shows the
superior benzene-removal obtained by means of the in
vention.
TABLE VII
Benzene in sievate,
Desorption method (all at 600 F.): >
Vacuum (100 mm.) ___________________ _... 0.17
Nitrogen purge (300 v./v.) ____________ __ 0.03
Sievate purge (120 v./v.) _____________ __ 0.007
35
The effect of the more complete desorption clearly im~
proved the siev-ate quality, and when sievate purge was
used, the benzene content was reduced well below the
target level, i.e., 0.02%.
Example 11
Under the following typical operating conditions, a
three-phase process was performed in accordance with
the invention. 1A3 pellets of a 13X Linde molecular sieve 4.5 and sulfur; cyclically interrupting the ?ow of said feed
were used. The feed is substantially the same as that
shown in Table IV. Hydrogenated C5/C6 Baton Rouge
virgin naptha was used as purge.
TABLE VIII
Adsorption:
\Final Bed temp, F. __________________ __ 280
Press, p.s.i.g __________ __'_ _____________ __
Feed/cycle, w./w. _____________________ __ 1.60
Time,min. ____ _;__'_'_____' _____________ __
Heat and Purge: .
Final bed Temp., F. ___t. _______ .__' _____ __
Press, p.s.i.g. '
Purge/cycle, w./w. __e __________________ __ 1.46
Time, min ______________ _.; _____________ _..
Cooling: ' '
8
What is claimed is: ,_ . -
1. An improved process for preparing a naphtha feed
for isomerization which comprises passing said naphtha
feed through a ?rst contacting zone containing a zeolitic
molecular sieve of from about 6 to 15 Angstrom size at
a temperature from about 70 to 500 F., adsorbing aro
275 matics, ole?ns and sulfur from said feed in said ?rst
15 contacting zone, withdrawing from said ?rst contacting
zone a naphtha essentially free of aromatics, ole?ns and
10 sulfur passing aromatic, ole?n and sulfur-free feed to an
583 isomerization reactor; cyclically interrupting the ?ow of
30 said feed into said ?rst contacting zone; heating isomer
30 ate by passing said isomerate through a second contact;
660 ing zone containing a previously heated and desorbed
60 molecular sieve, heating and purging said ?rst molecular
- sieve by passing said hot isomerate at a temperature of
1.3 from about 500 to 800 F. through said ?rst contacting
642 zone, thereby desorbing the adsorbed aromatics, ole?ns
30 and sulfur; withdrawing said isomerate vapors, desorbed
54
20 aromatics, ole?ns, and sulfur from said contacting zone;
and cooling said molecular sieve to about 70 to 500 F.
60 by passing cool isomerate vapors from said isomerization
351 reactor through said ?rst contacting zone, thereby pre;
30 paring said molecular sieve for another adsorption step.
5.8 2. The process of claim 1 wherein said molecular sieve
270 is of the formula 0.9:0.2M2O:Al2O3:2.5i0.5SiO2 where
M is a metal ion and n is its valance.
3. The process of claim 2 wherein said M is a sodium
30 10H.
4. The process of claim 3 wherein at least part of the
sodium ions are replaced by calcium ions.
wt. percent
5. In the process of claim 1 wherein said naphtha
feed is in the vapor phase in said ?rst contacting zone.
6. In the process of claim 1 wherein said naphtha feed
is in the liquid phase in said ?rst contacting zone.
. 7. An improved process for adsorption and desorption
of aromatics, ole?ns, and sulfur which comprises passing
a naphtha feed containing aromatics, ole?ns, and sulfur
40 through a ?rst contacting zone containing a zeolitic
molecular sieve of from about 6-15 A. size, adsorbing
said aromatics, ole?ns, and sulfur from said feed in said
?rst contacting zone, withdrawing from said first contact
ing zone a naphtha essentially free of aromatics, ole?ns,
into said contacting zone; heating hydrocarbon vapors
free of aromatics, ole?ns, and sulfur by passing said
' hydrocarbon vapors through a second contacting zone
containing a previously heated and desorbed molecular
50 sieve, heating and purging said molecular sieve in said
first. contacting zone by passing said hydrocarbon vapor
'10
through said contacting zone, thereby desorbing the ad
sorbed aromatics, ole?ns, and sulfur, withdrawing said
80
hydrocarbon vapors, desorbed aromatics, ole?ns, and
55 sulfur from said contacting zone and cool said molecular
642
sieve from about 70 to 500 F. by passing cool hydro
carbon vapors through said contacting zone in the same
.15 direction as in said desorption phase, thereby preparing
said molecular sieve zone for another adsorption step.
80
8. A process as in claim 7 wherein the naphtha feed

Final bed. Temp, F. ____ ...' ______ _-'_____ 296

Press, p.s.i.g_____________ __' ___________ __
Coolant/cycle, w./w. _____. ______________ __ 1.53
Time, min. ________ 5.-.. _______________ __ 80
65 andsaid purging is carried out at a temperature from
The sievat contained 001%. of benzene as compared
with 5.5% in the feed. 'The cycle capacity is 9.3 weight
7
benzene/ 100 weight sieve. Again it should be noticed
that the benzene content of the sievate was reduced well
beneath the target level desired. . 70 and 650 F., and said cooling is carried out to a tem
In actual plant operation, isomerate purge would be
used'rather thansievat'e.v The elie'ctivenessof desorption
would, however, be the same.
The aboveexarnple is given only as an illustration of
, the invention and is, not intended to de?ne the process.
is passed through said contacting zone in the same direc
" tion as the hydrocarbon gas in desorbing. -
l5
9. In the process of claim 7 wherein said adsorbing
is carried out at a temperature from about 70 to 500 F.
about 500 to 800 F; f
10. In the process of claimrl wherein the adsorption
is carried out at a temperature from about 200 to 350 F.,
said purging is carried out at a temperature between 550
perature from about 200 to 350 F. '
11. An improved process for preparing a high octane
gasoline which comprises passing a naphtha feed through
a ?rst contacting zone containing a zeolitic molecular
sieve of from about 6-15 A. size at a temperature from
 3,063,934
10
about 70 to 500 F., adsorbing aromatics, ole?ns and contacting zone containing a molecular sieve substan
sulfur from said feed in said ?rst contacting zone, with tially saturated with aromatics, ole?ns, and sulfur, purg
drawing from said ?rst contacting zone a naphtha essen ing said aromatics, ole?ns, and sulfur with said product
tially free of said aromatics, ole?ns and sulfur, passing and withdrawing from said third contacting zone a high
said aromatic, ole?n and sulfur-free naphtha to an isom 5 octane gasoline.
erization reactor, isomerizing said aromatic, ole?n and 14. An improved process for preparing a high octane
sulfur-free naphtha in said isomerization reactor, passing gasoline which comprises passing a naphtha feed through
said isomerized product in a second contacting zone con- 7 a contacting zone containing a zeolite molecular sieve
taining a molecular sieve at a temperature from about of from about 6-15 A. size at a temperature from about
500 to 800 F., thereby heating said isomerized product 10 70 to 500 F., adsorbing aromatics, ole?ns and sulfur
and simultaneously cooling the molecular sieve in said from said feed in said contacting zone, withdrawing from
second contacting zone, passing said isomerized product said contacting zone a naphtha essentially free of said
to a third contacting zone containing a molecular sieve ole?ns and sulfur, and containing less than 0.02% aro
substantially saturated with aromatics, ole?ns, and sul matics, passing said aromatics, ole?n and sulfur-free
fur, purging said aromatics, ole?ns, and sulfur with said 15 naphtha to an AlBra isomerization reactor, isomerizing
product and withdrawing from said third contacting zone said aromatics, ole?n and sulfur-free naphtha in said isom
a high octane gasoline. erization reactor, passing said isomerized product to a
12. The process of claim 11 wherein said naphtha feed contacting zone containing an desorbed molecular sieve
is passed through the second contacting zone after said at a temperature of from about 500 to 800 F., thereby
cooling. 20 heating said isomerized product and simultaneously cool
13. An improved process for preparing a high octane ing the molecular sieve in said contacting zone, passing
gasoline which comprises passing a naphtha feed through said heated isomerized product to a contacting zone con
a ?rst contacting zone containing a zeolite molecular taining a molecular sieve substantially saturated with
sieve of from about 6-15 A. size at a temperature from aromatics, ole?ns, and sulfur, desorbing said aromatics,
about 70 to 500 F., adsorbing aromatics, ole?ns and 25 ole?ns, and sulfur from said sieve with said heated isom
sulfur from said feed in said ?rst contacting zone, With erized product and withdrawing from said contacting
drawing from said ?rst contacting zone a naphtha essen zone a high octane gasoline containing said desorbed
tially free of said ole?ns and sulfur, and containing less aromatics and said isomerized product.
than 0.02% aromatics, passing said aromatics, ole?n and
sulfur-free naphtha to an AlBra isomerization reactor, 30 References Cited in the ?le of this patent
isomerizing said aromatic, ole?n and sulfur-free naphtha UNITED STATES PATENTS
in said isomerization reactor, passing said isomerized
product to a second contacting zone containing a mo 2,415,315 Walter et a1 ____________ .... Feb. 4, 1947
lecular sieve at a temperature from about 500 to 800 F., 2,493,499 Perry _________________ __ Jan. 3, 1950
thereby heating said isomerized product and simulta 35 2,818,455 Ballard et al ___________ __ Dec. 31, 1957
neously cooling the molecular sieve in said second con 2,882,244 Milton _______________ __ Apr. 14, 1959
tacting zone, passing said isomerized product to a third 2,937,215 Bleich et al. __________ __ May 17, 1960