Improvements relating to the Desulphuration of Oils.
Year: 1892

page_text: Date of Application, 9th Aug., 1892-Accepted, 1st Oct., 1892
COMPLETE SPECIFICATION.
[Communicated from abroad by OTTO P. AMEND, of the City, County, and
State of New York, and JOSIAH H. MACY, of Harrison, in the County of
Westchester and State of New York, both in the United States of America.]
Improvements relating to the Desulphuration of Oils.
I, HENRY HARRIS LAKE of the firm of Haseltine Lake & Co. Patent Agents
45 Southampton Buildings in the County of Middlesex, do hereby declare the
nature of this invention and in what manuer the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
It is well known that in the effort to refine petroleum oils containing sulphur
compounds, as Ohio and Canadian oils, much difficulty has been experienced in.
eliminating the sulphur and in producing an oil that will not show sulphur reaction
after an interval of time.
Hitherto the majority of those attempting to desulphurize oil have mixed one or
more chemical agents with the oil while in liquid condition, and have depended
upon such chemicals to effect an entire elimination of the sulphur present in
accordance with what has been supposed to be the usual law of chemical action.
In some instances heat has been applied to hasten such action. Metallic oxides,
alkalies, fuming sulphuric and nitric acid have been used in this manner, without
effecting a satisfactory result.
Others, operating with the same end in view, have first vaporized the oil, and
then subjected the oil vapour to the action of various chemicals, in the presence of
heat, with a belief that the action of the chemicals upon the oil, while in a state of
vapour, was more satisfactory than when in a liquid condition. In the latter case
the heat applied has been somewhat higher than was necessary to complete a distil-
lation of oil, but we are led to believe that neither of these methods as hitherto
applied will so purify the oil that sulphur reaction will not develope after a short
interval of time, and this of necessity must be the case while sulphur remains in
the oil, as it does in both of the cases cited.
We have discovered that sulphur and all sulphur compounds can be removed
from the above named oils and that sulphur reaction does not occur in oil treated
by a proper process.
We attain the practical desulphurization of oils containing sulphur by vaporizing
the oil, and subjecting the oil vapor, together with the sulphur or sulphur compounds
contained in it, to a degree of heat above the boiling point of sulphur and by this
means vaporizing the sulphur and splitting up its compounds and then exposing
the vaporized sulphur and its split up compounds to the action of such chemical
agents or reagents as they have affinity for, or to such as will act upon or will
combine with them while in this vaporized, or split up condition, and then liquefying
the oil. When treated as described, it will be found that the sulphur and sulphur
compounds have been so changed that practically no sulphur can be found in the
oil, and it may be treated for further refinement by any of the well known methods
of treating petroleum oils.
The degree of heat required to vaporize sulphur at the ordinary pressure of the
atmosphere is 440° C. and we find that the heat needed to effect entirely satisfactory
work must be sufficiently above this temperature to insure the entire vaporization
of the sulphur and the splitting up of the sulphur compounds. We prefer a red
heat clearly distinguishable in day light, and have found temperatures between 700°
and 12000 centigrade very successful in practical working. We have selected
these temperatures by comparing the colors obtained with the colors specified by
competent technical authorities as corresponding to the temperatures named, the
colors ranging from a dark red to a bright orange.

page_text: We have found many chemical agents that will unite with sulphur wher
vaporized or split up, as for instance various metals; their oxides and sub-oxides
the hydrates and oxides of the alkalies have also given very good results, but we
prefer such agents or reagents as have an oxidizing effect among which, we have
found manganese dioxide, and other higher oxides of manganese; barium peroxide
the manganates and permanganates the chromates and bi-chromates, chromic iron
ore and binoxide of lead, to be very successful.
Binoxide of manganese is a cheap agent, and has given excellent results. We
have found it an advantage to use a caustic alkali that will stand the heat, as caustic
lime or barium, with the binoxide. We find that when using caustic lime with
binoxide of manganese, that much less binoxide is required, and the cost is thus
reduced. The color of the distillate is improved by the use of an alkali, and the
very offensive smell usually attending the distillation of oil containing sulphur or
sulphur compounds, is almost entirely done away with, as the oxygen of the
manganese operates to oxidize the sulphur fumes or the split up gaseous sulphur
compounds, while the caustic alkali apparently acts as a revivifier of the oxidizing
agent.
In some cases we may use one or more of the alkalies or alkaline earths as lime,
soda, potash, magnesia, barities strontia, etc. or their hydrates, (caustics) or
carbonates either separately or together and not with a metallic oxide.
The process will be fully understood by referring to the accompanying drawing,
which illustrates one means of carrying out our invention.
The numeral 1, represents a plain still such as is generally used for distilling
oil. 2, is the outlet for oil vapours passing from the still. 3, is the fire chamber under
the still, and 4, the ash pit. 5, represents the flue from the still furnace. It is shown
running behind the flue of the auxiliary furnace and side by side with it, yet
separated by a partition until they meet at the outlet of each at the smoke stack 6.
7, is the pipe that conveys the oil vapor with the heated sulphur and sulphur-
compounds, to the super-heater and chemical box 8. This box is made of thick
cast iron and has a thick pipe 9, cast with it which projects from one side near the
bottom and communicates with the oil vapor pipe 7, of the still. The box 8, is
held in position by a heavy iron clamp 10, which rests upon the top of the
furnace 11. The furnace 11, has a return flue somewhat similar to that of a
smelting furnace, with an opening leading from the furnace at 12, running thence
downward until it is about in line with the main flue 5, from the furnace of the
still. It then runs side by side with the flue of the still furnace until it opens into
the smoke stack.
The fire pot of the furnace 11, is made deep, so as to hold a considerable body
of fuel and its sides flare or diverge a little more on the side where pipe 9, is
exposed than on the other, with a view of heating the pipe very hot.
The box is so suspended that its lower part projects into the combustion chamber
of the furnace 11, of short distance, depending entirely upon the size of the box,
so that the lower part of the box and particularly the pipe 9, may be heated
throughout, as far as exposed in the furnace, to a bright red heat. Especial
care being exercised to see that the top of the pipe is so heated, as the currents of
gas tend to follow the upper side of the pipe. There is a space of several inches
above the pipe, and the brick work behind it is set out to almost touch the pipe,
that the flame may be forced first under and then over the top of the pipe to heat
it sufficiently and homogeneously.
The box 8, is provided with a perforated support 13, upon which the chemicals
are placed that combine with or act upon the sulphur and sulphur compounds,
when the latter are sufficiently heated. 14, is the outlet to the pipe 15 through
which the oil vapor passes to the condenser to be liquefied.
The operation is as follows: The oil to be desulphurized is put in the still 1.
The chemical or oxidizing agent to be used (say for instance, binoxide of
manganese) having been mixed with a little plaster of Paris, properly dried, and
cut or broken into small cubes or pieces is placed on the support 13, in box 8,

page_text: together with the caustic alkali (for instance, caustic lime) prepared in the same
manner. As a rule, they are placed in layers, alternately, although not always.
The auxiliary furnace is then fired up and when the box 8, and pipe 9, begins to
redden the fire under the still-1, is started. By the time the vapors begin to pass
over, the part of the box and the pipe exposed in the furnace will be bright red.
As the vapors are discharged from the still 1, they carry with them more or less
sulphur, and upon its admission into the red hot pipe 9, the sulphur and sulphur
compounds are heated to a degree above the boiling point of sulphur or
above 440° C. at the pressure of the atmosphere, this operates to vaporize the
sulphur and to split up the sulphur compounds which pass, while in this condition,
through the perforated support 13, into the immediate presence, of, and in contact
with, the chemicals placed upon said support. The binoxide of manganese (if this
is the oxidizing agent used) operating to thoroughly oxidize the vaporized sulphur
and the split up and vaporized sulphur compounds, which result is not obtained
when the oil vapor with its accompanying charge of sulphur is heated to any degree
of temperature below the boiling point of sulphur.
The oil vapour having passed through the chemicals in box 8, then passes from
said box through its outlet 14, and pipe 15, to condensers (not shown) wherein it is
liquefied. The oil thus de-sulphurized can then be treated by any of the well
known methods for treating petroleum distillate.
No especial form of apparatus is required to carry out this process, and no
pressure is indicated by gauge during the operation.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me
by my foreign correspondent, I declare that what I claim is :-
1. The process of de-sulphurizing oil which consists in vaporizing the oil con-
taining the sulphur and heating the oil vapor to a degree of heat at or above the
boiling point of sulphur, in exposing the oil vapor so heated to the action of one
or more chemical re-agents that will combine with sulphur or sulphur compounds
and then condensing the oil vapor.
2. The herein described process of de-sulphurizing oil which consists, in
vaporizing the oil containing sulphur or sulphur compounds and heating the
vaporized oil to a degree of heat at or above the boiling point of sulphur and then
exposing the vaporized oil so heated to the action of one or more alkalies and then
condensing the oil.
3. The process of de-sulphurizing oil which consists in vaporizing the oil con-
taining sulphur and heating the oil vapor to a degree of heat at or above the
boiling point of sulphur, in exposing the oil vapor so heated to the action of an
oxidizing agent capable of combining with sulphur or sulphur compounds and then
condensing the oil vapor.
4. The process of de-sulphurizing oil which consists, in vaporizing the oil con-
taining sulphur or sulphur compounds and heating the vaporized oil to a degree of
heat at or above the boiling point of sulphur and exposing the vaporized oil so
heated to the action of a hydrated (caustic) alkali and then condensing the oil
vapor.
5. The process of de-sulphurizing oil which consists in vaporizing the oil con-
aining the sulphur and heating the oil vapor to a degree of heat at or above the
boiling point of sulphur; in exposing the oil vapor so heated to the action of an
oxidizing agent and a caustic alkali and then condensing the oil vapor.
Dated this 9th day of August 1892.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.