Dec.

1,- 1942,

' F; E. WILKINSON

2,303,970

METHOD FOR DESULPHURIZING MINERAL OILS

Filed Aug; 27, 1940

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2,303,970

Patented Dec. l, li942

UNITED STATES PATENT OFFICE

2,303,970
METHOD FOR DESULPHURIZING MINERAL
OIL S

Francis E. Wilkinson, Glendale, Calif.

Application August 27, 1940, Serial No. 354,339
6 Claims.

(Cl. 196---25)
at 3, it being understood that this agitator as well

This invention relates generally to the proc

essing of petroleum oil and the derivative prod
ucts of the oil and more particularly relates to
processes for the desulphurization of certain

petroleum products.

as the other apparatus referred to may be oi

any well known or standard type of apparatus
Si

commonly used in the industry.

For the purpose of 'cleaning the distillates

to be treated and to remove some of the sulphur

In present day practices great volumes of a
compounds and other coloring materials, what I
product known as pressure distillate is produced
have termed a rst treating solution, consisting
in the cracking of petroleum oils. This prod
of raw denatured alcohol, is introduced into the
uct, as an example, has a specific gravity of 47.1
Baum A. P. I., an initial boiling point of between 10 agitator 3 from a tank 4th'rough pipe 5 where the alcohol and distillate are thoroughly mixedl
204 and 210 F., and an end point from approxi
and agitated. This agitated mixture, from the
mately 3961 to 408 F. In appearance the dis
agitator 3, ows through pipe B to >a settling
tillate is dark reddish brown and it contains
tank, indicated at l, where I have found that the
varying quantities oi sulphur depending upon the
locality where the petroleum is produced. It 15 distillates which have become a yellowish color

is the ordinary practice to treat this distillate

separate and rise to the top of the settling tank

for the purpose of vlowering the sulphur content

leaving a residue of bottoms which contain sul

and decolorizing it, the sulphur content being re

phur compounds, sludges and very nearly all of

the first treating solution, that is, the raw de

quired to be reduced to four-tenths of 1% or
lower. Ordinarily a sulphuric acid and caustic 20 natured alcohol.
This rst treating solution of raw denatured
soda treatment is employed to accomplish this
alcohol may be recovered and reused in the sys
followed by a doctor solution treatment. These
tem. For this purpose the bottoms from the
treatments require considerable expensive ap
settling tank I are discharged through pipe 8
paratus and the process itself takes considerable
time, usually requiring in the neighborhood of 25 into a still 9 which is heated to approximately
from 170 to 190 F. to distill ol the alcohol
twenty-four hours to complete. After being
which passes through pipe I0 to a condenser II
treated the product is mixed with either casing
and from this condenser through pipe I2 to
head gasoline or straight run gasoline to bring
the first treating solution tank 4. The bottoms
down the initial boiling point and reduce the
sulphur content to less than one-tenth of 1% to 30 or residues from the still 9, including some water
carrying sulphur compounds and coloring mat
meet specications of rst structure gasoline and
ter, are discharged through pipe I3 to a sump
at the same-time provide a suitable gasoline that
or collector. The distillates from the settling
can be leaded by treatment with tetraethyl
tank 1 are discharged through pipe I4 to an agi
lead.
It is an object of this invention to provide a 35 tator or mixer I5 into which is introduced a
second treating solution from tank I6 through
simple method requiring a much shorter time
pipe Il.
than the common acid process and which is made
This second treating solution preferably' con
possible by the use of an organic material in
sists of solutions containing organic acids such
stead of sulphuric acid, which material is non
corrosive to the apparatus and which is Very 40 as a very dilute solution of oxalic, tartaric or
citric acids. Such treating solution is mixed in
cheap as compared to the materials used in other
the agitator I5 in the percentage of from ve
processes.
to ten per cent of the distillates being treated.
Referring to the drawing which is for illus
I have found that by adding a very small quan
trative purposes only, the gure illustrates dia
grammatically the flow sheet of one arrangement 45 tity of a neutral soap, for instance, approximate
ly three ounces of soap to one barrel of distillate
of apparatus which may be utilized in carrying
to the second treating solution that the amount
out my process.
oi such solution required may be greatly reduced.
More particularly describing my method or
I have found that certain by-products of
process, the distillates to be treated may be what
are commonly known as processed heavy pres 50 plants> in which fruit, particularly citrus fruit,
is processed for the forming of citric acid, pec
sure distillates and kerosene distillates from
tin and oils such as lemon oil can be used. As
cracking plants, al1 of which may be termed raw
for instance, the residue of clay, used in pro
untreated gasoline stock. In the drawing this
ducing such products, which clay is impregnated
raw stock from the tank, indicated at I, is intro

duced through pipe 2 into an agitator indicated 55 0r contains some of the chemicals or substances

2,303,970

of the fruit being' treated and the products there

from during the treatment above referred to,
I have found to be particularly efficient for the
purposes desired.

As an example, one and one

half pounds (l1/2 lbs.) of this clay product added

to a barrel of distillate produces an entirely sat

isfactory agent.
I have also found that the Wash water and
other solutions from the citrus fruit plants re
ierred to may be used as the second treating

agent above referred to.

From the agitator l5 the mixture of the dis
tillates and the second treating solution is dis
charged into a still I8 through pipe I9.'
Natural gas or other hydro carbon gas is passed

through a high frequency electrolyzer generally

indicated at 20. The gas coming' from any suit
able supply, not shown, is introduced into a tube
`2 equipped with an inner coil 22 and an outer

coil 22.

From the tube 2| the eleotrolyzed gas

the desired results may be accomplished in aliproximately two hours time.

I claim as my invention:

1. In the method of desulphurizing pressure

distillates and the like the steps of adding to the
distillate a quantity of an aqueous solution of
citrus fruit acid compounds; agitating the mix
ture; and distilling the resultant mixture to a
temperature of approximately 420 F.
2. In the method of desulphurizing pressure
distillates and the like the steps of adding to the
distillate an aqueous solution of citrus fruit acid

compounds; and distilling the resultant mixture

to the end point of gasolines.
3. In the method of desulphurizing pressure
distillates and the like the steps of adding to the
distillate a quantity of an aqueous solution of

citrus fruit acid compounds; distilling the re

sultant mixture at a temperature to vaporize the

gasolines therein; and cooling and condensing

then containing nascent hydrogen passes through

the vapors.

pipe 23 into the bottom of the still Where it bub

bles up through the liquid therein. The still I8
is operated at a temperature of approximately
420 F, which is the highest distillation tempera

4. In the method of desulphurizing pressure

distillates and the like the steps of adding an al

cohol to the distillate; agitating the mixture;

then allowing the mixture to settle; removing

ture for the products treated, the temperatures in

the entire system ranging from 120 to 420 F.

the mixture an aqueous solution of citrus fruit

with little or no pressure maintained on the sys

acid compounds; thoroughly agitating such mix

the lighter constituents to an agitator; addingto

tem. The residuum is relieved from the sill

ture; distilling the resultant mixture and dur
through pipe 24 and consists of sulphonated com 30 ing such distillation introducing into the mixture
pounds, water and sludge. The distillates from
a gas containing hydrogen resulting from the
the still are passed through pipe 25 to a con
electrolyzation of a hydrocarbon gas; and con
denser 26 and from the condenser pipe 21 to any
densing the distilled product.
'
suitable storage.
5. In the method of desulphurizing pressure
The condensed product has changed from a 35 distillates and the like the steps of adding to the
yellowish color, when introduced into the still,
distillate a denatured alcohol; agitating the mix
to from slightly lemon yellow to water white and
ture; then allowing the mixture to settle; remov
sweet smelling. If desired a subsequent Washing
ing the lighter constituents to an agitator; add
step of the character commonly used in other
ing to the mixture an aqueous solution of citrus
desulphurizing processes may be employed to re
fruit acid compounds and a soap; thoroughly agi
move any flocculent or suspended matter which
tating such mixture; distilling the resultant mix
settles with the water from the distillate.
ture and during such distillation introducing in
After the washing step, just above referred to,
to the mixture a gas containing hydrogen result
if desired the sulphur- content may be further
ing from the electrolyzation of a hydrocarbon
reduced by treating the distillate with doctor so
gas; and condensing the distilled product.
lution such as used in ordinary desulphurizing
6. In the method of desulphurizing pressure
methods. However, this is not ordinarily neces
distillates and the like the steps of adding to the
sary in View of the fact that with my treatment
distillate a denatured alcohol; agitating the mix
of the distillates with the organic material re
ture; then allowing the mixture to settle; remov
ferred to the sulphur content is reduced from ap- ' ing the lighter constituents to an agitator; add
proximately nine-tenths of one percent in the
ing to the mixture an aqueous solution of citrus
distillates when introduced into the still to ap
fruit acid compounds obtained from the washing
proximately three-tenths of Vone percent in the
of citrus fruit; thoroughly agitating such mix

finished product which latter percentage is less

than the required minimum percentage for the
mixture of the distillate with gasoline as is the
common practice for making motor fuel.
With my process, instead of requiring twenty
four hours or more as is the time required with
common methods now used for desulphurizing, 60

ture; distilling the resultant mixture and during

such distillation introducing into the mixture a
gas containing hydrogen resulting from the elec
trolyzation of hydrocarbon gas; and condensing
the distilled product.
FRANCIS E. WILKINSON.