Improvements in and Apparatus for Refining Crude Petroleum and analogous Oils by Means of Fuming Sulphuric Acid.
Year: 1895

page_text: Date of Application, 6th Dec., 1805
Complete Specification Left, 5th Sept., 1896-Accepted, 14th Nov., 1896
PROVISIONAL SPECIFICATION.
Improvements in and Apparatus for Refining Crude Petroleum and
analogous Oils by Means of Fuming Sulphuric Acid.
I, JAMES YATE JOHNSON, of 47 Lincoln's Inn Fields, in the County of London,.
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by The Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the Empire of Germany), to be as follows:-
The general process hitherto used for refining, or purifying, the various fractions
of crude petroleum, and analogous oils (I will refer to these generally as oil),
consists in mixing them with concentrated sulphuric acid, then separating the
impurity, and subsequently washing the oil with water and alkali.
Recently attempts have been made to use fuming sulphuric acid, or oleum,
instead of concentrated sulphuric: acid, in the same way, but satisfactory results
have not been achieved.
My foreign correspondents have discovered the causes of failure and this
invention provides means whereby these causes. of failure are overcome and
satisfactory results obtained.
One cause of failure is due, with some oils;, to the difficulty of securing an
intimate admixture with the crude oil of the fuming sulphuric acid, or oleum, as
the latter immediately on coming into contact with some crude oils, rapidly forms
pitchlike bodies, so that if the mixing be effected in the usual way, small drops
form, consisting of an outer layer of pitch like body but possessing an inner
nucleus of practically unaltered oleum, which either takes no part in the purifica-
tion, or only does so after prolonged agitation. By this invention there is provided
a process for securing an intimate admixture of the oleum and crude oil, and an
apparatus in which it can be readily effected. The principle of the process consists
in mixing in the fuming sulphuric acid at the point of contact of streams of the
crude oil (or streams of air and of crude oil) whilst the said streams possess a
different velocity, so that considerable friction occurs between the streams whereby
the oleum is in a sense rubbed, or ground,. into a fine state of division, and
flowing on in the streams becomes most intimately admixed with the entire body of
crude oil.
°
Another cause of failure is due to the fact that, when treating some crude oils,
especially the heavier fractions with oleum, besides the ordinary pitch like compound
of acid with impurity, which separates out, other similar combinations are formed
in some cases which do not separate from the oil. If the oil containing such com-
binations be washed in the usual way with water and alkali without any steps being
first taken to remove the said combinations, then the impurities are regenerated
and impart a dark colour and objectionable smell to the product. My foreign
correspondents have discovered that the said combinations can readily be removed.
by treating the oil containing them with a small percentage of ordinary concen-
trated sulphuric acid. By working according to this invention the refined oil
obtained is lighter in colour, than can be obtained when using either concentrated
sulphuric acid alone, or oleum alone and ou exposure to light the refined product!
continuously becomes lighter in colour, whereas the product refined with ordinary
concentrated acid only, bleaches a little at first but afterwards becomes yellow.
There is also less oil lost when working in accordance with this invention.

page_text: It is not always necessary to employ both of the improved means described in
order to obtain the desired result, as in some cases, merely securing the intimate
admixture with oleum with the crude oil yields a highly refined product, whilst in
some cases the after treatment with a small percentage of concentrated acid, after
mixture with oleum in the ordinary way, is sufficient without the application of the
special mixing process.
The process and apparatus suitable for carrying it into effect can be conveniently
described more in detail, by the following example but the invention is not confined
to this example.
The apparatus consists of a cylindrical casing into which open concentric conical
nozzles (say two), there being a pipe for the admission of compressed air or crude
oil under pressure, connected with one nozzle and a pipe for the oleum terminating
in the other nozzle. Above the opening of the nozzles the casing is first conically
contracted and it then expands into funnel form and is provided with a lid. The
lower end of the casing is provided with slit-like openings through which the crude
oil enters the apparatus. The apparatus is placed at the lower part of a large
tank, or vessel, called the agitator.
The operation is commenced (the lid being open) by forcing compressed air
through the pipe therefor, and so through one of the nozzles into the crude oil.
Instead of using compressed air a stream of the oil itself can be forced in through
the said pipe and nozzle at the pressure of say two atmospheres, or more.
This
compressed stream of air, or oil, causes a violent motion of the oil in the apparatus
upwards from the slit-like openings. A circulation is thus set up as the oil is
drawn into the apparatus at the slit-like openings and is burled upwards centrally.
The oleum is allowed to run in through the other pipe and nozzle and as it emerges
from the nozzle it is caught between the two streams of oil, or of air and oil, and
by the friction between them it is rubbed into a very fine state of division and
passes forward mixed with the liquids into the mass of the oil in the agitator.
When the admixture is complete the lid is closed. If compressed air is being used,
or if now air instead of oil be forced into the apparatus then as the lid is closed
the air will stream out of the apparatus at slit-like openings and will agitate the
mixture in a manner similar to that hitherto customary. The pitchy particles of
impurity rapidly ball together and at the end of this agitation with air rapid settling
of the impurity results.
The lid prevents the impurity from entering into the apparatus and stopping up
the nozzles and the apparatus is so constructed that the pitchy matter settling
upon it readily runs off."
When agitating with oil the tank, or agitator, should only be supplied with oil
sufficient to stand from say three, to five, feet above the apparatus; the rest of the
oil being forced through the nozzle or nozzles under pressure as aforesaid.
When it is desired to stir more continuously some of the mixture can be pumped
out of the agitator when full and be forced in again through the apparatus under
pressure. The pitchy particles are so finely divided that no risk is incurred of
their choking the apparatus, or pump. The pump should be of cast iron in all its
parts and be protected from contact with the air by means of petroleum, or
lubricating oil.
After the pitchy matter has been run off it is generally advisable, especially
with heavy cils as hereinbefore explained, to treat the product with about one, or
two, per cent. of concentrated sulphuric acid (containing about ninety-two to
ninety-six per cent. H₂SO). This can be effected in the same apparatus by running
in the concentrated acid through one of the nozzles, instead of the oleum, the lid K
being closed or open, as desired.
In the foregoing example no proportions are stated, nor figures given as to the
strength of oleum to be applied, for these vary considerably according to the oil
treated and the degree of impurity; but in general a quantity of oleum is used
about half that which has hitherto been used of concentrated sulphuric acid, and
the following strength of oleum have given good results with the classes of oil

page_text: mentioned: viz. :—with benzene 20 to 60 per cent. with petroleum 10 to 20 per cent.
with lubricating oil 5 to 20 per cent. and with vaseline 25 to 30 per cent. free
anhydride.
Dated this 6th day of December 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
Improvements in and Apparatus for Refining Crude Petroleum and
analogous Oils by Means of Fuming Sulphuric Acid.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of
London, Gentleman do hereby declare the nature of this invention (which has
been communicated to me from abroad by The Badische Anilin- & Soda-Fabrik
of Ludwigshafen-on-Rhine in the Empire of Germany) and in what manner the
same is to be performed to be particularly described and ascertained in and by
the following statement :-
The general process hitherto used for refining, or purifying, the various fractions
of crude petroleum and analogous oils (I will refer to these generally as oil)
consists in mixing them with concentrated sulphuric acid, then separating the
impurity, and subsequently washing the oil with water and alkali.
Recently attempts have been made to use fuming sulphuric acid, or oleum,
instead of concentrated sulphuric acid, in the same way, but satisfactory results
have not been achieved.
My foreign correspondents have discovered the causes of failure and this
invention provides means whereby these causes of failure are overcome and
satisfactory results obtained.
One cause of failure is due, with some oils, to the difficulty of securing an
intimate admixture with the oil of the fuming sulphuric acid, or oleum, as the
latter, immediately on coming into contact with some crude oils, rapidly forms
pitchlike bodies, so that, if the mixing be effected in the usual way, small drops
form consisting of an outer layer of pitchlike body but possessing an inner nucleus
of practically unaltered oleum, which either takes n part in the purification, or
only does so after prolonged agitation. By this invention there is provided a
process for securing an intimate admixture of the oleum and crude oil, and
apparatus in which it can be readily effected. The principle of the process consists
in mixing in the oleum, at the point of contact of streams of the crude oil (or streams
of air and of crude oil), whilst the said streams possess a different velocity, so that
considerable friction occurs between the streams whereby the oleum is in a sense
rubbed, or ground, into a fine state of division and flowing on in the streams becomes
most intimately admixed with the entire body of crude oil. In this way the oleum
is mixed with the oil in a state of fine subdivision, whereas formerly it was run in
as a mass and subsequent agitation was relied upon to subdivide the acid and bring
it into intimate contact with the oil.
Another cause of failure is due to the fact that, when treating some crude oils,
especially the heavier fractions, with oleum, besides the ordinary pitch-like
compound of acid with impurity, which separates out, there are in some cases
formed other combinations which do not separate from the oil. If the oil, con-
taining such combinations, be washed in the usual way with water and alkali
without any steps being first taken to remove the said combinations, then the
impurities are regenerated and impart a dark colour and objectionable smell to
the product. My foreign correspondents have discovered that the said com-
binations can readily be removed by treating the oil containing them with a small
percentage of sulphuric acid of 75 to 100 per cent. H₂SO.

page_text: By working according to this invention the refined oil obtained is lighter in
colour, than can be obtained, when using either concentrated sulphuric acid alone,
or oleum alone, and, on exposure to light, the refined product continuously becomes
lighter in colour, whereas the product refined with ordinary concentrated acid only,
bleaches a little at first but afterwards reverts to yellow. There is also less oil
lost when working in accordance with this invention.
It is not always necessary to employ both of the improved means described in
order to obtain the desired result, as in some cases, merely securing the intimate
admixture of the oleum with the crude oil as herein before described yields a highly
refined product, whilst, in some cases, the after-treatment with a small percentage
of concentrated acid after mixture with oleum in the ordinary way is sufficient
without the application of the special mixing process.
The process according to this invention and apparatus suitable for carrying it
into effect are described more in detail, by the following example, with reference
to Figure 1 of the accompanying drawings, but the invention is not confined to
this example.
The apparatus consists of a cylindrical casing, into which open two concentric
conical nozzles D₁ and D. The pipe A for the admission of compressed air or
crude oil under pressure is connected with the inner nozzle D₁ and the pipe B for
the admission of oleum terminates in the other nozzle D. Above the opening of
the nozzles the casing is first conically contracted and it then expands at F into
funuel form, and is provided with a lid K. The lower end of the casing is pro-
vided with lateral inlets E through which the crude oil enters the apparatus.
apparatus is placed at the lower part of a large tank, or vessel, called the
agitator.
The
The operation is commenced (the lid K being open) by forcing compressed air
through the pipe A and so through the inner nozzle D₁, into the crude oil.
Instead of using compressed air a stream of the oil itself can be forced in through A
and D₁ at the pressure of say two atmospheres or more. This compressed stream
of air, or oil, causes a violent motion of the oil in the apparatus upwards from the
lateral inlets E to the upper part F. A circulation is thus set up as the oil is
drawn into the apparatus at the lateral inlets E and is drawn and forced upwards
centrally. The oleum is allowed to run in through the pipe B and nozzle D₂;
and as it emerges from the said nozzle it is caught between the two streams of oil,
or of air and oil, and by the friction between them it is rubbed into a very fine
state of division and passes forward mixed with the liquids into the mass of the oil
in the agitator. When the admixture is complete the lid K is closed. If the
supply of compressed air be continued (or if oil instead of air has been passed
through the nozzle D' if air instead of oil be then forced into the apparatus) as
the lid K is closed, the air will stream out of the apparatus at the lateral openings E,
and will agitate the mixture in a manner similar to that hitherto customary. The
pitchy particles of the acid impurity compounds rapidly ball together and at
the end of this agitation with air, rapid settling of the acid pitch-like matter
results.
The lid K prevents the acid pitch-like matter from entering into the apparatus
and stopping up the nozzles and the apparatus is so constructed that the acid pitchy
matter settling upon it at any part readily runs off.
When agitating with oil the tank or agitator should only be supplied with oil
sufficient to stand from say three to five feet above the apparatus, the rest of the
oil being forced through A and D₁ under pressure as aforesaid.
When it is desired to stir more continuously some of the mixture can be pumped
out of the agitator when full and be forced in again through the apparatus under
pressure. The pitchy particles are so finely divided that no risk is incurred of
their choking the apparatus or pump. The pump should be of cast iron in all
its parts and be protected from contact with the air by means of petroleum, or
lubricating oil.
After the acid pitchy matter has been run off it is generally advisable, especially

page_text: with cracked products and heavy oils as hereinbefore explained, to treat the
product with a small quantity say about one or two per cent. of sulphuric acid
(containing about seventy five to one hundred per cent. H₂SO₁). This can be
effected in the same apparatus by running the said concentrated acid instead of
the oleum through the nozzle D, the lid K being closed or open, as desired.
Another arrangement of the apparatus is shewn in Figure 2 of the drawings.
The outer casing D3 of the apparatus C forms part of a system of pipes between
two agitator vessels, through which the oil circulates. A lid such as is described
with reference to the apparatus Figure 1 is unnecessary in the present apparatus
Figure 2.
2
The casing D, is constricted at Z, has branches W and X above and Q and R
below. These branches are furnished with valves V₁ V, V, and V, and connect
the upper and lower parts of the two agitator vessels not only with one another
but also the lower part of each agitator vessel with its upper part so as to enable
oil to be sucked from the bottom of either of the agitator vessels, and run into it
again at the top. The inner nozzle D₁ is connected by the pipe K with the force
and suction pump P. The suction tube J of this pump has branches E and F
each furnished with a valve H3 and H, and entering the agitator vessels S and T
respectively at their bottoms.. The outer nozzle D, of the apparatus is connected
with the vessel O containing the oleum which is run therefrom by the cock and
pipe shewn. The agitator vessels are furnished each with a pipe (M₁ and M,) for
compressed air or the like.
pump
With this arrangement of apparatus it is possible to work in the manner already
described with reference to Figure 1. Thus, the valves V₁, V₁ and H₂ being
opened and the valves V2, V3 and H. being closed, if the
P be operated a
portion of the oil is sucked from the vessel S through the pipe J and forced
through the inner nozzle D₁ of the mixing apparatus, causing a circulation of a
slower stream of the oil up through D. Between the two streams the required
quantity of oleum is run in through D, from the vessel O. This agitation is
continued so long as may be necessary to effect the required purification.
Compressed air is blown in, to stir the mass gently till the acid pitchy matter has
balled itself together and the rest of the procedure may be identical with that
already described with reference to Figure 1.
By closing the cocks which were open and opening those which were closed the
contents of the other vessel T can be similarly treated. The agitation can be
effected by oil under pressure instead of by compressed air.
Another method of working with this arrangement of apparatus is as follows:-
In the agitator vessel S the oil can be subjected to a preliminary treatment with
concentrated sulphuric acid in order to free it from water; stirring being effected
by means of compressed air or oil under pressure supplied through the pipe M₁.
The acid is then run off through the cock H, and the valves V₁ and V, are opened
and the suction and force pump P is put into action; whereby the petroleum is
forced through the mixing apparatus where it is intimately mixed with the oleum
in the manner hereinbefore described. The mixture passes on through the valve V,
into the agitator vessel T; in which the mixture can then be agitated with air or
oil under pressure until the pitchy matters ball together when they are allowed to
settle and are finally run off.
If it be necessary to treat the oil with ordinary concentrated sulphuric acid in
accordance with the second part of the invention the petroleum is worked over in
an analogous way through the mixing apparatus from the one vessel (S) to the
other (T) whilst the requisite quantity of such acid runs in from 0; it is again
mixed with air in the vessel T and finally the pitchy matters are run off. The
treatment with water and alkali can either be effected in the same vessel or in
another vessel. In the meantime a further portion of oil can be freed from water
in the vessel T and be further treated as described.
If desired a series of agitator vessels can be placed side by side with a mixing

page_text: apparatus between each pair and in each one a step of the operation can be effected;
so that the working can be continuous.
In the foregoing description of the mode of procedure no proportions are stated
nor are particulars given as to the strength of oleum to be applied, for these vary
considerably according to the oil treated and the degree of impurity; but in general
a quantity of oleum is used about half that which has hitherto been used of
concentrated sulphuric acid, and the following strengths of oleum have given good
results with following classes of oil viz. -with benzene oleum of 20 to 60 per cent. ;
with petroleum, oleum of 10 to 20 per cent.; with lubricating oil, oleum of 5 to
20 per cent.; and with vaseline, oleum of 25 to 30 per cent. free from anhydride.
The following examples will serve to further illustrate the manner in which the
invention can be conveniently carried into practical effect.
To cracked Galician petroleum of a specific gravity of about 0.820 add about
one quarter per cent. of ordinary concentrated sulphuric acid (containing say about
ninety six per cent. H2SO4) and stir with air. This preliminary operation is
intended to extract the water from the oil. Next force a portion of the petroleum
through the inner nozzle D₁ of the apparatus whilst allowing oue per cent. of
oleum, (containing about 10 per cent. free anhydride S.03) to run in through D₂;
when the admixture is complete stir with air until the pitchy matters ball together,
allow these to settle and run off. Next treat with about one half to one part (by
weight) of ordinary concentrated sulphuric acid to one hundred parts of oil, mixing
in the acid either through the apparatus or by stirring with air. Allow the pitchy
matters to settle and run them off; the washing with water and alkali will be
effected in the usual way.
EXAMPLE 2.
TREATMENT OF PETROLEUM DISTILLATE WHICH HAS NOT BEEN CRACKED.
Free the oil from water as described in Example 1. Then mix one part (by
weight) of oleum (containing about 20 per cent. free anhydride SO3) to every
hundred parts of oil, by means of the mixing apparatus, substantially stir with
air, and allow the pitchy matters to settle; run these off and wash with alkali and
water in the usual way.
EXAMPLE 3.
TREATMENT OF A HEAVY OIL.
Mix three parts (by weight) of oleum (containing about 5 per cent. free
anhydride SO) with every hundred parts of heavy oil previously freed from
water; this admixture may be effected with air in the ordinary well known way.
Subsequently stir more gently with air until the pitchy matters ball together allow
these to settle as far as possible and remove them. Then stir again with air and
add about one part (by weight) of concentrated sulphuric acid per hundred parts
of oil. Allow the pitchy matter to settle and wash with water and alkali in the
usual way.

page_text: portion of the benzene itself through the inner nozzle of the apparatus. When
the mixture has settled remove the pitchy matters and wash the benzene with
water and alkali in the usual way.
The so called light crude photogene oil obtained from Thuringian-oil shale and
also ordinary benzene from coal tar can be refined in the manner described in the
last example. In the former case about two parts (by weight) of oleum (containing
about twenty per cent. free anhydride SO3) per hun fred of oil are used and in the
case of the coal tar benzene about four per cent. of oleum containing from 20 t
per cent.. free anhydride SO, may advantageously be applied.
25
Instead of air for the agitation of the crude oils other gases can be used, such as
carbonic acid, uitrogen or the natural gas which frequently occurs in petroleum
districts. This is especially to be recommended in the case of oils which beco ne
oxidized on treatment with air.
It should be noted that the nozzles are not necessarily of circular form. A.
stream from a nozzle of circular cross section has less surface exposure or less
surface exposed to contact than one flowing from a nozzle with a slit opening.
The cross section of the nozzle is a matter which can be regulated according to
judgment or circumstances.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The process of refining petroleum and analogous oils, which consists in causing
fuming sulphuric acid, or oleum, to pass between two streams, (one, or both, of
oil), moving at different velocities, and so reducing the said acid to a condition of
fine subdivision at the moment of admixture with the oil.
2. The method of refining petroleum and analogous oils by introducing fuming
sulphuric acid, or oleum, between two streams, (one, or both, of oil), moving at
different velocities the acid passing in through a nozzle surrounding the inner jet
of an injector.
3. The process of refining petroleum, or analogous oils, by first treating them.
with fuming sulphuric acid, or oleum, and afterwards removing such acid impurity
combinations, as have not directly separated out, by means of a small proportion of
non-fuming sulphuric acid.
4. In apparatus for the treatment of petroleum, or, analogous oils, with fuming
sulphuric acid, or oleum, an injector having an outer nozzle surrounding the nozzle
for the inner jet, both being in the injector casing to which the oil to be
refined bas access and the outer and inner nozzles being provided respectively with
means for passing therethrough fuming sulphuric acid, (or oleum), and a fluid
under pressure; substantially as herein before described.
5. The arrangements and combinations of parts constituting the apparatus
hereinbefore described and shewn respectively in Figures 1 and 2 of the
accompanying drawings.
Dated this 5th day of September 1896.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.