July 28, 1964

c. N. KIMBERLIN, JR., ETAL

3,142,533

CONVERSION oF NAPHTHAS To MIDDLE nIsTILLATEs

Filed Aug. 18. 1959

-Jmo.z_5<
r.wnn

T3

dNvmmm.J

nEwm
.umm
nkT

mmzomoml( mQ2>mom

um
C@NmEb.SJ
nr
NNe0

m
w
m.

m
.m
v.

wm
w

m
M
n

J
.M
n..
/

VEN m

BY Mt/. 07%( PATENT ATTORNEY

Unted States Patent O

ICC

3,142,633
Patented July 28, 1964

3,142,633

of naphtha into middle distillate by catalytic treatment

with liquid hydrogen fluoride and in the further presence,

CONVERSION 0F NAPHTHAS T0 MIDDLE

DISTILLATES

if desired, of certain promoters such as boron iiuoride or

Charles Newton Kimberlin, Jr., Henry George Ellert, and

Howard Emerson Merrill, Baton Rouge, La., assignors
to Esso Research and Engineering Company, a corpo
ration of Delaware

Filed Aug. 18, 1959, Ser. No. 834,455

6 Claims. (Cl. 20S-46)
The present invention relates to distillate fuel manu
facture` and it pertains more specifically to the manufac

ture of high quality distillate fuels such as heating oils,

diesel fuel, jet fuels and the like from naphthas boiling
in the gasoline boiling range.
The principal object of the present invention is to
provide a process for converting low octane and/or un

other halide, iron fluoride, and similar compositions. In

one embodiment of the present invention, light virgin
naphtha is directly converted. In another embodiment,
naphtha may be thermally, catalytically or steam cracked

to a relatively low degree of conversion, forming sub

stantial quantities of olefins which are then passed to
In still another embodi

10 the catalytic conversion zone.

ment, low grade catalytic or Coker naphtha is fed di

rectly into the conversion Zone, or is mixed with virgin
or casinghead naphtha prior to conversion.
The catalyst employed in the present invention is an

hydrous liquid HF. This may, particularly when virgin

naphthas are being reacted, be augmented with BF3. In

this case from 0 to 60 mol percent, preferably, 25 to

stable naphthas into materials of higher value and higher
40 mol percent BFS based on HF, may be employed.
boiling range.
Hitherto, oil refineries have been generally operated 20 Lesser amounts of from 0 to 10 mol percent, but pref
erably, 0 to 2 mol percent BF3 may be employed in
to maximize naphtha production for use as gasoline

processing the more reactive catalytic and coker naphthas

or other naphthas containing oleiins.
Several critical conditions must be maintained in ac
anti-knock constituents to produce gasoline blends of
acceptable quality. However, with the introduction of 25 cordance with the present invention to obtain good yields
of middle distillates. Temperatures must be in the range
high compression ratio automobile engines, the octane
such that middle distillates rather than lubricating oil
requirements of gasoline have been steadily increasing,
range material on the one hand, or products boiling lower
thus severely narrowing the choice of constituents suit
motor fuel. Some naphthas are of substantially lower
octane value than others, but could be blended with high

able as gasoline blending agents.

Thus, much virgin

than middle distillates on the other, are formed. In gen

eral, temperatures should be in the range of from about

30
0 to 350 F., preferably, 32 to 250 F. Process
of gas oil, hitherto used as gasoline blends for engines
temperature is determined by the nature of the feed, the
of moderate compression ratio, can no longer be used
catalyst composition and the catalyst concentration.
for this purpose. Similarly, refinery processes such as

naphtha and naphthas resulting from catalytic cracking

uidized coking of residua, and visbreaking operations

produce naphthas that are unstable and sludge forming,
and are of too high sulfur content for satisfactory use
as fuels.

Concomitant with the increasing accumulation of these

relatively low value naphthas in the refineries, there has

Normally, temperatures in the range of 160 to 250

F., preferably, 175 to 225 F. are employed in process

ing virgin naphthas using HF-BF3 catalyst, While lower

temperatures in the range of 25 to 150 F., preferably,
75 to 125 F. give satisfactory results in processing
catalytic or coker naphthas or other unsaturated feeds.

grown up in recent years substantial demands for hy 40 Pressures are such that at least a portion of the catalyst
and the feed are maintained in the liquid phase. Catalyst
drocarbons boiling in the middle distillate range of about
to oil ratios are in the range of 0.1 to 5/ 1, and pref
300 to 750 F. The rapid growth of heating oil installa
erably 0.5 to f2.5/ 1, and contact times to 5 to 180 minutes
tions both here and abroad, and the rapid dieselization
are maintained. Again, these conditions will be deter
of transportation equipment has caused the supply of
mined by the reactivity of the naphtha feed, high catalyst
middle distillates to be out of balance with that of motor
to oil ratios and long contact times being required with
gasolines. However, operating crude oil and distillate
virgin naphthas with low catalyst to oil ratios and short
refinery processes to maximize middle distillates would
contact times being satisfactory for the conversion of
seriously interfere with the production of high quality
catalytic or coker naphthas. Specifically, catalyst to oil
naphthas. An object of the present invention is to pro
ratios of l to 5/ 1, preferably 2 to 4/ 1, and contact times
vide middle distillate fuels without interfering with maxi
50 of 30 to 180 minutes, generally 30 to 120 minutes, are
mum high quality and octane gasoline production.
employed in processing virgin naphthas. For catalytic
Thus, heretofore middle distillate fuels have been pro
and coker naphthas, catalyst to oil ratios of 0.1 to 1.5/1
duced as by-products in the manufacture of gasoline,
and contact times of 5 to 30 minutes are normally satis
and such fuels of relatively high quality could be obtained
factory.
directly from fractions of the virgin crude oil or from
An important problem arising out of the reaction and
the cracking of virgin crudes. The phenomenal increase 55
reaction conditions heretofore described is the formation
in demand for middle distillate fuels has presented a

serious problem to the oil refining industry.

Middle distillates, or distillate fuels, generally boil in
the range of about 350 to 750 F., the so-called heater

oils boiling in the range of 350 to 550 F., While diesel

fuels boil at about 400 to 650 F.

In accordance with the present invention, refinery im

of secondary reaction products, and in particular the

formation of dry gases, principally propane and isobutane,
decreasing the ultimate yield of desired product. It has

been found that the yield of desired middle distillates

can be increased by passing these light products back to
the reaction zone where either through mass action effects

or through their reaction with the catalyst system present,

they are converted into middle distillate. Suprisingly,
naphtha fractions into middle distillates. In a sense this 65 however, it has been found that if a portion of the de
sired middle distillate product itself is recycled, on the
is the reverse of the hitherto trend of petroleum refining
balance between gasoline and heating oil demands and
stocks are restored by catalytic conversion of low quality

where the gasoline fraction was the desired product, and

where low grade gasoline fractions were upgraded to high
anti-knock material by such processes as reforming or

isomerization.

The present invention involves principally conversion

order of 2 to 40% based on feed, the formation of the

light material is greatly reduced.

The objects of the invention and its advantages will

70 be more readily apparent from the more detailed descrip

tion hereinafter when read in conjunction with the ac

3,142,633

treated in a stirred Monel autoclave under the follow

companying drawing showing a preferred embodiment

thereof.

ing conditions:

Turning now to the figure, a naphtha feed comprising

low octane quality constituents, such as virgin naphtha, is
admitted through inlet 10, pump i2 and valve 14 into
mixer 16. Preferably, prior to admission to 16, the hy
drocarbon stream is admixed with concentrated, and pref

HF/oil wt. ratio ____________________________ __

Temperature,

0.2

F ___________________________ __ 150

Contact time, hrs ___________________________ __ 0.5

No BF3 was used. At these conditions 55.3 wt. percent

conversion of the naphtha was obtained. The wt. percent
yields based on converted naphtha were:

erably anhydrous liquid HF admitted through line 18 and

valve 20. The proportion of hydrouoric acid is prefer
ably in the range of 2 to 4 times by weight of the total

hydrocarbon fluids. Mixing ofthe acid and hydrocarbons

C3C., _______________________________________
______________________________________ _..
__

may be effected by any one of a number of methods, as

by use of special mixers or emulsitiers or by maintaining

350/650 F _______________________________ __ 98 9

0.9

Example III

high linear velocities in the lines.

Preferably, prior to addition of the acid to the hydro

The following experimental results were obtained in a

statistically planned study on the conversion of naphtha

carbon, boron liuoride is added to the former to the extent

to middle distillate. The experiments were carried out

in a Monel autoclave equipped with an efficient agitator.

of 25 to 40 mol percent. In general, if the hydrocarbon

feed is moderately or highly oleiinic, EP3 may be omitted,
whereas its presence is beneiicial and indeed essential when

A synthetic blend consistingof 45 wt. percent n-heptane

45~wt. percent n-heXane-l() wt. percent benzene was used

the hydrocarbon feed is low in olen content, as is the

to represent a light virgin naphtha feed.

case in virgin naphtha.

Recycle was

simulatedv by charging the respective product fraction with

The resulting mixture of acid, BF3 and hydrocarbon is

feed.
passed to heater 22 wherein it is heated to suitable reac
tion temperatures of the order of 175 to 225 F., and
[225 F., 2 HF/hydrocarbon wt. ratio, 20 wt. percent BFa on HF, 2 hr.
reaction time]
passed to reaction chamber 24, wherein it is maintained 25
for a period of 30 to 120 minutes at a pressure suicient
Feed Composition:

to maintain major portions of the catalyst and feed in

the liquid phase. Agitation by any known means may be
supplied, as by recirculation.

59

Naphtha _______________________________ _

29
12

Isobutane _________ __

5.2507650c F ________ __

Naphtba Converted to

Effluent mixture from reactor 24 is passed through con 30 Wt. percent ______________________________ __
Yields, Wt. percent on Naphtha Converted
duit 26 to separator 30 wherein it is separated into two
to C3 and 250 F. -l-z

liquid phases as by cooling and gravitation or centrifugal

Ca- ____________________________________ __

250/650 F _____________________________ __

means. The heavier or HF-BF3 acid phase may be re

cycled via conduit 32 to pump 34; a portion may con

32

52.6
47.4

50
50

It is evident from the above data that middle distillate

production is maximized and gas make minimized by re
cycling at least a portion of the butane or C4* and 250

tinuously be passed to an acid fractionator (not shown) or

other means for purifying and restoring the acid, all in a
manner known per se.

Returning to the upper layer, the hydrocarbon phase

is passed through line 36 to tractionator 38, preferably

E+ product fractions with unconverted feed.

by the following speciiic examples,

Example I

distillates to said reaction zone.

HF/oil wt. ratio ____________________________ __

2
BPB/oil wt. ratio ___________________________ __ 0.4 60

Z50-650 F. and light hydrocarbons, consisting essential

ly of propane and butanes, segregating the product from

Temperature, F ____________________________ __

the reaction zone into light hydrocarbons and middle dis

What is claimed is:

l. An improved process for converting naphthas to hy
with pressure release. In accordance with the present in 40
drocarbons boiling in the middle distillate range of from
vention, the light products, such as the butanes and pro
about 250 to about 650 F. which comprises treating said
pane, are recycled to reactor 24 via line 40. Similarly,
naphtha in a reaction zone in the liquid phase with anhy
from 2 to 60% by weight of the desired middle distillate,
drous hydrofluoric acid at a temperature in the range of
and which fraction boils between about 250 and 650
F., is recycled via line 42 to reactor 24, while unreacted 45 about 0 to about 350 F., whereby a substantial amount of
said naphtha is converted to middle distillates and light
hydrocarbon naphtha may similarly be recycled via line
hydrocarbons, segregating the product from said reaction
44. The middle distillate fraction is passed via line 46 to
zone into light hydrocarbons and middle distillates, and
a finishing plant or for further treatment not forming a
recycling light hydrocarbons, consisting essentially of pro
part of this invention.
pane and butanes, and a significant portion of said middle
The process of the present invention is further illustrated

2. An improved process for converting naphthas to hy

drocarbons boiling in the middle distillate range of from

about 250 to about 650 F. which comprises treating said
A virgin naphtha obtained from a South Louisiana
crude and boiling from 215 to 350 F. was treated ac 55 naphtha in a reaction zone in the liquid phase with an
hydrous hydrouoric acid at a temperature in the range of
cording to the method outline above. Experimental con
about 0 to about 350 F., whereby said naphtha is con
ditions were:
verted to middle distillates boiling in the range of about

Contact time, hrs ___________________________ __

tillates, and recycling said light hydrocarbons, and about

The reactor was a Monel autoclave equipped with an

2 to 60 percent based on feed of the middle distillate

product to said reaction zone.

eicient agitator. The developed pressure was held

through the treat. At these conditions the naphtha con
version was 71.6 wt. percent and the wt. percent yields,
based on naphtha converted were:

3. An improved process for converting naphthas boiling

in the range of about 16S-350 F. into middle distillates
which comprises treating said naphtha in a reaction zone

in the liquid phase with anhydrous hydrofluoric acid at a

C3- ______________________________________ __ 5.6
C.l _______________________________________ __ 39.5
C5 _______________________________________ __ 15.4
35o/65o F ________________________________ __ 395

Example II
A light catalytic naphtha obtained by cracking a South
Louisiana crude and boiling from 165 to 350 F. Was

temperature in the range of about 32 to 450 F., main

70 taining the reactants in a catalyst to oil ratio of 0.1-5/1
and at a Contact time of 5 to 180 minutes whereby said
naphtha is converted to middle distillates boiling in the
range of about Z50-650 F. and light hydrocarbons, con

sisting essentially of propane and butanes, segregating the

hydrocarbon product from the reaction zone into light

3,142,633
5

hydrocarbons and middle distillate and recycling said light

contains olenic hydrocarbons and 0 to 10% BFS, based

hydrocarbons and from about 2-60 percent based on feed

of said middle distillate product to the reaction zone.

on HF, is added to said zone, said temperature being in

the range of about 25 to 150 F.

4. The process of claim 3 wherein 0 to 60 mol percent

BF3, based on HF, is added to said reaction Zone.

5
5. The process of claim 1 wherein said naphtha feed

References Cited m the me of this Patent

UNITED STATES PATENTS

hydrocarbon is substantially paranicand about` 25 to

2,445,560

Caldwell ____________ __ July 2()l 1948

40% BFS, based on HF, 1s added to said zone, said tern-

2,463,372

Heim-ich _____________ __ Man 3, 1949

perature being in the range of from about 160 to about

250 F.

6. The process of claim 1 wherein said naphtha feed

10

2,684,325

Deanesly ____________ _* July 20J 1954

2,927,072

Gladrow et al. ________ __ Mar. 1, 1960

2,938,855

Mason et al. _________ __ May 31, 1960