U.S. patent number 3,915,819 [Application Number 05/485,390] was granted by the patent office on 1975-10-28 for electrolytic oil purifying method.
This patent grant is currently assigned to Electro-Petroleum, Inc.. Invention is credited to Christy W. Bell, Arthur L. Speece, John K. Wittle.
United States Patent |
3,915,819 |
Bell , et al. |
October 28, 1975 |
Electrolytic oil purifying method
Abstract
Sulfur is removed from liquid hydrocarbon oils such as crude oil
by subjecting a mixture of the oil and an electrolyte to a direct
current field at a relatively high current and low voltage for
causing oxidation, reduction or other electrochemical reaction of
the sulfur or sulfur-containing material enabling ready separation
and removal of the sulfur from the oil.
Inventors: |
Bell; Christy W. (Berwyn,
PA), Wittle; John K. (Berwyn, PA), Speece; Arthur L.
(Phoenixville, PA) |
Assignee: |
Electro-Petroleum, Inc. (Bryn
Mawr, PA)
|
Family
ID: |
23927966 |
Appl.
No.: |
05/485,390 |
Filed: |
July 3, 1974 |
Current U.S.
Class: |
205/696 |
Current CPC
Class: |
C10G
32/02 (20130101) |
Current International
Class: |
C10G
32/00 (20060101); C10G 32/02 (20060101); C25B
001/00 () |
Field of
Search: |
;204/136 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2,229 |
|
May 1883 |
|
GB |
|
139,233 |
|
Mar 1920 |
|
GB |
|
Primary Examiner: Andrews; R. L.
Attorney, Agent or Firm: Haubner; J. Wesley
Claims
What we claim as new and desire to secure by Letters Patent of the
United States is:
1. The method of electrochemically removing sulfur from hydrocarbon
liquids including sulfur containing materials which comprises
mixing the hydrocarbon liquid with an ionizing organic solvent, and
subjecting the thus obtained mixture to an electrical D.C. field
having a voltage of about 2 to 120 volts and a current of at least
about 0.001 amperes per square centimeter, and recovering said
hydrocarbon liquid in which said sulfur containing materials have
been substantially reduced.
2. The method as defined in claim 1, wherein said current is not
more than about 25 amperes per square centimeter.
3. The method as defined in claim 2, wherein said hydrocarbon
liquid is crude oil.
4. The method as defined in claim 3, wherein said ionizing organic
solvent is selected from the group consisting of methanol, benzene,
toluene, xylene and glacial acetic acid.
5. The method as defined in claim 1, wherein said hydrocarbon
liquid is selected from the group consisting of crude oil, mineral
oil and petroleum and said voltage is in the range of about 2 to 10
volts.
Description
The present invention relates to the removal of sulfur from
hydrocarbon liquids, especially hydrocarbon oils such as crude
oil.
It is an object of the present invention to reduce the sulfur
content of hydrocarbon liquids, particularly crude oil.
It is another object of the invention to provide a process for
purifying crude oil and other hydrocarbon liquids which is readily
carried out at relatively low cost.
A particular object of the invention is to provide a process of the
above type wherein the sulfur content is reduced by electrochemical
means.
Other objects and advantages will become apparent from the
following description and the appended claims.
With the above objects in view, the present invention in one of its
aspects relates to the method of electro-chemically removing sulfur
from hydrocarbon liquids including sulfur-containing materials
which comprises mixing the hydrocarbon liquid with an ion-producing
compound selected from the group consisting of inorganic
electrolytes and ionizing organic solvents, and subjecting the thus
obtained mixture to an electrical DC field having a voltage in the
range of about 2 to 120 volts and a current of at least about 0.001
amperes per square centimeter, and recovering the hydrocarbon
liquid in which the sulfur-containing materials have been
substantially reduced.
In general, it has been found in accordance with the invention that
the use of relatively high current at low voltages in the
electrolyte-oil mixture promotes the oxidation (or reduction, as
the case may be) of sulfur contaminants in the oil, resulting in
precipitation or volatilization of sulfur compounds which are
thereby removed from the oil mixture.
As will be understood, the sulfur components in crude oil may be of
various types. It is known that the sulfur content of petroleum may
vary from less than 0.1% to 10% by weight depending upon the
source. This sulfur may be present as free sulfur, hydrogen
sulfide, mercaptans, disulfides, cyclic sulfides or thiophenes. The
present refinery methods for removal of sulfur, such as
hydro-desulfurization, require the use of relatively cumbersome
apparatus and expensive processes. The electrochemical process of
this invention, on the other hand, is a relatively simple
inexpensive desulfurization method.
In the electrolysis of any particular oil-electrolyte mixture to
produce an electrochemical reaction in accordance with the
invention, under the same conditions certain sulfur compounds may
be oxidized, others may be reduced, some may be precipitated, some
may be volatilized and others may be deposited on the electrode
surfaces. From experiments carried out in the course of practicing
the invention, it appears that oxidation is the predominant
reaction, and oxidation products such as sulfonic acids and sulfur
oxides have been identified. The reduction of sulfur compounds has
been indicated by the production of H.sub.2 S volatilized during
the process.
The removal or reduction of sulfur in accordance with the
principles of the invention may be carried out using various
sulfur-containing hydrocarbon liquids or oils mixed with various
ion-producing compounds. For example, hydrocarbons such as mineral
oil and crude oil from various geographical sources have been
satisfactorily treated by the electrochemical process of the
invention.
The inorganic electrolyte with which the hydrocarbon liquid may be
mixed may be in the form of an aqueous solution of a salt or alkali
base in concentrations high enough to obtain an electrically
conducting system. Such solutions may contain, for example, a salt
or base such as sodium chloride, lithium chloride, potassium
chloride, strontium chloride, sodium nitrate, lithium nitrate,
potassium nitrate, sodium carbonate, potassium carbonate, calcium
carbonate, barium carbonate, sodium hydroxide, potassium hydroxide,
calcium hydroxide, and barium hydroxide.
Ionizing organic solvents which may be used in combination with the
hydrocarbon liquid include methanol, benzene, nitrobenzene,
toluene, xylene, and glacial acetic acid. Many other inorganic and
organic compounds will also be found suitable for use in practicing
the present invention.
In general, the electrolysis of the oil-electrolyte mixture is
carried out in a DC electrical field having a voltage in the range
of about 2 to 120 volts and a current of between .001 to 25 amperes
per square centimeter, with a preferred voltage range of about 2 to
10 volts being used in most cases. The concentration of the
ionizing compound employed in the mixture will depend mainly on the
spacing, surface area and configuration of the electrodes. For any
particular conditions, the amount of the ionizing material used
should be such as to provide a conductivity which results in a
voltage of the system in the range set forth above.
The process of the present invention will be illustrated by the
following examples, it being understood that the invention is not
intended to be limited thereby. In the experiments described below,
the electrolysis was carried out in a 100 ml flask equipped with
two standard platinum electrodes. The anode was a cylinder of
platinum mesh 1/2" in diameter and 2" long. The cathode was a mesh
cylinder 13/8" in diameter and 2" long.
EXAMPLE I
A 43.88 gram sample of crude oil designated Fleisher Lease oil
containing 6.13% by weight of sulfur was mixed with 54.06 grams of
distilled water containing 1.08 grams of reagent grade NaOH. The
mixture, which had a pH of 10, was subjected to electrolysis
carried out in the above described reaction vessel. The mixture was
subjected to a DC electrical field of 0.100--0.175 amperes, for a
total of 64 hours. While holding the current to a maximum of 0.175
amperes during the run, the voltage varied between 25 and 200
volts. At the termination of this experiment, it was found that the
sulfur content in the oil had been reduced to 4.57%.
EXAMPLE II
A mixture of 7.14 grams of crushed limestone, 49.73 grams distilled
water, 43.03 grams of No. 6 fuel oil, and 0.48 gram Ca(OH).sub.2
and 38.78 grams distilled water was placed in the reaction vessel.
The mixture separated into an oil layer and water layer. A DC
current of 1 ampere was passed through the system at 15 volts for
nearly 12 hours, at which time the current had dropped to 0 and the
voltage rose to 45 volts. The sulfur content in the oil layer
before the electrolysis began was found to be 0.86%, whereas at the
end of the experiment the sulfur content was 0.60%.
EXAMPLE III
In this experiment, 46.7 grams of No. 6 fuel oil and 4.55 grams
calcium hydroxide were added to 76.58 grams distilled water, and
the mixture was heated to reflux without stirring. A direct current
of 1 ampere at 9 volts was passed through the solution. The current
dropped to 0 within 50 minutes. At this time a surfactant,
available commercially under the name Triton X-100, was added to
the mixture, and electrolysis was again initiated at 1 ampere and
20 volts. After 4 hours and 20 minutes the voltage had increased to
50 volts at 1 ampere. The system was allowed to run overnight,
during which time the current dropped to 0.4 ampere and the voltage
increased to 120 volts. The sulfur content of the oil layer before
the experiment was 0.86%, and after the experiment was found to be
0.51%.
EXAMPLE IV
To a solution consisting of 92.55 grams distilled water, 0.39 gram
Ca(OH).sub.2 and 5.7 grams limestone, there was added 38.75 grams
No. 6 fuel oil cut with 10% by weight of pentane to reduce
viscosity. The system was subjected to electrolysis at an initial
current of 1 ampere and 7 volts. During a period of 6 hours, the
current fell to 0 and the voltage increased to 75 volts. The sulfur
content of the oil layer was 0.86% before the experiment and was
found to be 0.49% after the experiment.
EXAMPLE V
A solution of 1.13 grams Triton X-100, 126.83 grams water and 10.39
grams calcium hydroxide was mixed with 73.95 grams No. 6 fuel oil.
The reaction mixture was heated to reflux and electrolysis was
started at 1 ampere and 20 volts. Within 2 minutes the voltage had
increased to 120 volts and the current dropped to 0.4 ampere. An
additional amount of 2.14 grams Triton X-100 was added and
electrolysis continued at 1 ampere and 20 volts. After 3 hours the
current had dropped to 0.4 ampere and the voltage increased to 120
volts. Again, 2.15 grams Triton X-100 was added and the
electrolysis continued at 0.5 ampere and 120 volts. Within 3 hours,
the current dropped to 0.2 ampere and the voltage remained at 120
volts. Before the experiment the sulfur content of the oil layer
was 0.86% and after the experiment it was 0.54%.
EXAMPLE VI
This was a control experiment which was carried out to determine
whether a reduction in sulfur content in the oil can be achieved
with a similar mixture is subjected to electrolysis at much higher
voltages.
A mixture of 122.12 grams distilled water, 10.14 grams calcium
hydroxide, 4.05 grams Triton X-100 and 73.31 grams No. 6 fuel oil
was prepared and mechanically agitated for several days. At the end
of this period, the oil layer was placed in the previously
described reaction vessel and subjected to a 2000 volt per
centimeter DC potential for several hours. At the end of this
period the oil was analyzed and found to contain the same sulfur
content as the original oil content of 0.86% sulfur.
EXAMPLE VII
To a mixture of 15 ml methanol and 51.13 grams mineral oil there
was added 8cc of thiophene. This mixture was subjected to
electrolysis at 0.1 ampere and 50 volts. The resistance rapidly
increased to 30 ohms within 56 minutes and the mixture changed from
an initial colorless condition to a yellow color. Gas collected
over the reaction mixture indicated SO.sub.2 and mercaptans were
present. The electrolysis was run intermittently for 4 days. During
this time 85 ml methanol was added to maintain liquid level. A
total of 8.7 ampere hours of electricity were used. During the last
two days of operation, the gas evolved from the reaction was found
to contain formaldehyde.
The inside of the reaction vessel and the stirring bar and cathode
were covered with a black deposit insoluble in carbon disulfide,
the total weight of the deposit being 0.30 gram. No deposit was
detected on the anode.
Analysis of the oil layer showed that initially, prior to
electrolysis, the sulfur content was 2.30% while the final oil
layer had a sulfur content of 0.625%.
EXAMPLE VIII
A sample consisting of 8cc thiophene, 46.12 grams mineral oil and
46.21 grams distilled water containing 1.17 grams sodium hydroxide
was mixed and electrolyzed at 0.175 ampere and 4 volts for 15.4
ampere hours. The aqueous layer turned yellow and a gray deposit
formed on the anode, while a black deposit formed on the cathode. A
brown deposit formed and floated on top of the liquid phases. At
the end of the experiment, 42.83 grams of mineral oil, 40.00 grams
aqueous phase, 0.54 gram deposit on the anode, 1.23 gram deposit on
the cathode and 0.22 gram brown residue were found. Upon standing
several days, the oil layer turned sky blue in color. At the start
of the experiment, the oil layer had 1.24% sulfur content, and at
the end it had 0.20% sulfur. During the experiment, the sulfur
content of the aqueous layer had increased from 0 to 2.96%.
EXAMPLE IX
Into the previously described reaction vessel there was introduced
46.14 grams mineral oil, 47.39 grams distilled water containing
1.13 gram calcium hydroxide and 8cc thiophene. A total of 12.86
ampere hours of DC current was passed through the system at 0.2
ampere and 7 volts. A brown solid phase began to separate from the
mixture as electrolysis proceeded. The pH of the system was
adjusted by the addition of 1.66 grams Ca(OH).sub.2 after 8.56
ampere hours of operation. Just prior to this addition, the
generation of gas was noted. At the start of the experiment, the
oil layer had 2.71% sulfur and a pH of 12. At the end of the
experiment, the oil layer had 0.252% sulfur and the pH was 5.
EXAMPLE X
To a 50.37 gram sample of mineral oil was added 7.75 cc dibutyl
disulfide and 43.5 grams methanol. The mixture was electrolyzed at
0.100-0.150 amperes and 50 volts for 64.5 hours or 9.97 ampere
hours. During the run no deposits formed on the electrodes and no
color changes were noted in the mixture. At the start, the oil
layer contained 3.75% sulfur, and at the end of the experiment it
contained 2.57% sulfur.
In all of the above experiments the current density of the system
was about 0.008 amperes/cm.sup.2. As previously indicated, it is
preferable in accordance with the invention to employ a current
density of at least 0.001 amperes/cm.sup.2 because it is
economically impractical to operate at lower current densities,
while a current density of more than 25 amperes/cm.sup.2 is not
feasible due to erosion of the anode surface and cavitation on the
electrode surface.
The Triton surfactant material mentioned in the Examples was used
to emulsify the oil so as to reduce fouling of the electrodes,
while at the same reducing the viscosity of the mixture to enhance
the electrochemical reaction.
As a result of our experiments, it appeared to be preferable to
maintain the pH of the mixture at a relatively high level, i.e.,
8-12, since it appeared that the electro-chemical reaction
proceeded at a more rapid rate at such a pH level. However, it is
not intended to limit the process of the invention to mixtures of
such pH levels, since satisfactory results are obtainable at lower
pH values. In adjusting the pH by the addition of a base, it is
desirable to use compounds such as Ca(OH).sub.2 to form insoluble
sulfur-containing compounds to facilitate the separation and
removal of these compounds from the mixture.
While the present invention has been described with reference to
particular embodiments thereof, it will be understood that numerous
modifications may be made by those skilled in the art without
actually departing from the scope of the invention. Therefore, the
appended claims are intended to cover all such equivalent
variations as come within the true spirit and scope of the
invention.
* * * * *