POLARITY REVERSAL ELECTROLYSIS

ELECTROLYSE A INVERSION DE POLARITE

English Abstract

A process, apparatus and compositions for the preparation of decarboxylated derivatives of carboxylic acids which comprises performing polarity reversing electrolysis using an anode and a cathode on a solution of a carboxylic acid containing more than one carbon atom or salt of carboxylic acid or carboxylic acid ester or other derivative or precursor thereof, to decarboxylat said carboxylic acid or derivative and produce decarboxylated derivatives is described. More generally, the invention has utility in treating reactants that can undergo oxidation and reduction on changing polarity electrode surfaces to produce products different from direct electrolysis. The invention also has utility in the conversion of organic cations, radicals and anions such as carboxylic acids, fatty acids, alcohols, phenols, to renewable fuels, production of chemicals useful as chemicals and pharmaceuticals and producing alkanes, alkenes, hydrocarbon ethers, alkyl-aryl hydrocarbons, alcohols and hydrocarbon esters.

French Abstract

L'invention porte sur un procédé, un appareil et des compositions pour la préparation de dérivés décarboxylés d'acides carboxyliques, qui comprennent la mise en uvre d'une électrolyse à inversion de polarité à l'aide d'une anode et d'une cathode sur une solution d'un acide carboxylique contenant plus d'un atome de carbone ou d'un sel d'acide carboxylique ou d'un ester d'acide carboxylique ou d'un autre dérivé ou précurseur de celui-ci, pour décarboxyler ledit acide carboxylique ou dérivé et produire des dérivés décarboxylés. Plus généralement, l'invention a une utilité en traitement de réactifs qui peuvent subir une oxydation et une réduction sur des surfaces d'électrodes à polarité inversée pour produire des produits différents de ceux d'une électrolyse normale. L'invention a également une utilité dans la conversion de cations, radicaux et anions organiques tels que des acides carboxyliques, des acides gras, des alcools et des phénols, en combustibles renouvelables, la production de produits chimiques utiles comme produits chimiques et produits pharmaceutiques et la production d'alcanes, d'alcènes, d'éthers hydrocarbonés, d'hydrocarbures alkyl-aryliques, d'alcools et d'esters hydrocarbonés.

Claims

1. A polarity-reversal electrolysis process, comprising:
providing a reactor that comprises at least one pair of spaced electrodes;
providing a controlled polarity-reversing power supply that is constructed and
arranged to
provide polarity-reversed power to the electrodes;
providing to the reactor an electrically-conductive liquid reaction medium
that comprises
reactants, wherein the electrodes are at least partially immersed in the
reaction medium; and
operating the power supply such that the polarity of the electrodes of the
pair of
electrodes reverses at a frequency rate.
2. A product produced by the process of claim 1.
3. The process of claim I wherein the reactor comprises multiple separate
pairs of spaced
electrodes, each such pair supplied with polarity-reversed power by the power
supply.
4. The process of claim 1 wherein the reactants comprise a species that has
an anion, and
wherein the process produces a reactive radical intermediate at each electrode
during the anodic
cycle of each electrode.
5. The process of claim 4, wherein the reactants comprise a species that
has a carboxylic
acid group, and wherein the process produces a decarboxylated radical
intermediate at each
electrode during the anodic cycle of each electrode.
6. The process of claim 1 wherein the reactants comprise a species that has
a cation, and
wherein the process produces a reactive radical intermediate at each electrode
during the
cathodic cycle of each electrode.
7. The process of claim 6, wherein the cation comprises a hydrogen ion, and
wherein the
process produces a hydrogen radical intermediate at each electrode during the
cathodic cycle of
each electrode.
8. The process of claim 6, wherein the cation comprises a species that has
an alkali cation,
or an alkali earth cation, and wherein the process produces an alkali metal
radical intermediate at
each electrode during the cathodic cycle of each electrode.
9. The process of claim 1, wherein the process produces a hydrogen radical
at the cathode
electrode during the cathodic cycle of each electrode.
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10. The process of claim 1, wherein the process produces carbonium ions at
each electrode
during the anodic cycle of each electrode.
11. The process of claim 1, wherein the process produces carbanion ions at
each electrode
during the cathodic cycle of each electrode.
12. The process of claim 1, wherein the said spaced electrodes comprise one
or more
materials selected from the group consisting of platinum, nickel, palladium,
steel, copper, silver,
gold, carbon, zinc, iron, chromium, titanium, transition metals, natural
graphite, synthetic
graphite, boron doped diamond and glassy carbon, or particles thereof.
13. The process of claim 1 wherein the polarity reversal frequency is from
0.001 Hz to 3
MHz.
14. The process of claim 7 wherein the current density is from 0.001 to 4.0
Acm-2.
15. The process of claim 8 wherein the voltage is from 2 volts to 240
volts.
16. The process of claim 1 wherein reactive radical intermediates are
produced at each
electrode during the anodic cycle of each electrode or the cathodic cycle of
each electrode, and
the intermediates react with the reactants selected from a group of reactants
consisting of
compounds that contain an alkyl group, an alkene group, an alkoxy group, an
aryloxy group, an
aryl group, a hydroxyl group, a ketone group, an aldehyde group, a carboxyl
group, a nitrogen
group, a halogen group, an allylic group, or a nitrite group.
17. An apparatus for accomplishing polarity-reversal electrolysis,
comprising:
a reactor that comprises at least one pair of spaced electrodes;
a polarity-reversing power supply that is adapted to provide polarity-reversed
power to
the electrodes; and
a controller that controls at least the current, and the polarity reversal
frequency, of the
power supplied to the electrodes by the power supply.
18. The apparatus of claim 17 wherein the reactor comprises multiple
separate pairs of
spaced electrodes, each such pair supplied with polarity-reversed power by the
power supply.
19. The apparatus of claim 17 wherein the polarity reversal frequency is
from 0.001 Hz to 3
MHz.
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20. The apparatus of claim 17 wherein the current density is from 0.001 to
4.0 Acm-2.
21. The apparatus of claim 17 wherein the voltage is from 2 volts to 240
volts.
22. The apparatus of claim 17 further comprising at least one mechanism to
stir the contents
of the reactor.
23. The apparatus of claim 17 comprising a flow-through reactor.
24. The apparatus of claim 17 wherein the space between the electrodes is
from 0.1mm to 10
mm.
59

Description

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POLARITY REVERSAL ELECTROLYSIS
FIELD
The invention relates to a process for producing decarboxylated derivatives
from
carboxylic acids by replacing the carboxylic group with hydrogen, an alkyl
group, an alkene
group, an alkoxy group, an aryloxy group, aryl group or hydroxyl group. The
invention relates
to novel compositions that can be obtained by the novel process. The
inventions also relates to an
apparatus for carrying out the process and producing the novel compositions.
More specifically,
the invention relates to a process for producing hydrocarbons and coupled
products to be used as
a chemical, pharmaceutical, lubricant, fuel or fuel additive from organic
anions and carboxylic
acids derived from the hydrolysis of triglycerides and esters. It also
concerns production of an
ether, an alkane, an alkene, an alkyl-aryl hydrocarbon, an alcohol and ester
compounds as
derivatives, and the use of the derivatives as pharmaceuticals, chemicals,
fuels or fuel blends.
The invention is particularly concerned with the field of renewable or biofuel
alternatives to
petroleum based fuels and chemicals, which are becoming increasingly scarce
and costly. The
fuels of the invention may be regarded as third generation renewables or
biofuels and/or
additives that have advantageous properties for storage and transportation,
have lower cold flow
and pour points, good performance and safety, utilize renewable and
sustainable materials as
feed stocks, burn more cleanly, preserve fossil fuels, are carbon neutral and,
most importantly,
can easily be adopted by most existing engines than the currently used methyl
esters of fatty
acids produced from triglycerides.
BACKGROUND
Biodiesel, methyl ester of fatty acids, and bioethanol are the main renewable
biofuels that
are currently available for commercial use. These biofuels can be easily
manufactured from
renewable feedstock (e.g. biomass, oils, fats) with existing technology.
However, many
applications that use standard fuels cannot easily be converted to use
biodiesel or bioethanol.
There are differences in the physical and chemical properties of biodiesel and
bioethanol
compared to standard fuels, such as differences in energy density,
flammability, boiling point
range (or lack thereof), shelf life, material compatibility and solvent
properties. The specification
of the fuel that may be used with many engines is very specific and may not
permit the use of
existing biofuel alternatives, such as biodiesel and bioethanol. There is
therefore a need for new,
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high density alternative biofuels and processes for producing renewable fuels
economically on an
industrial scale.
Electrolysis is known in the art as a method for performing chemical reactions
on a
laboratory scale and selected processes have reached industrial scales.
Electrolysis of carboxylic
and fatty acids and decarboxylation have been reported by Kolbe to form
alkanes, called the
Kolbe dimer. Laboratory experiments where a normal Kolbe reaction is prevented
by drastically
changed reaction conditions have been reported in the prior art, beginning
with Moest et. al.
(German patent 138442, issued 1903) who created alcohols, aldehydes and
ketones from fatty
acids using electrolysis.
Kronenthal et al focused on aliphatic ethers, and on methoxy-undecane in
particular (U.S.
Pat. No. 2,760,926, issued in 1956), but achieved yields of 40% or less while
consuming large
amounts of electricity (by at least a factor ten judging from the voltage
applied (90+ Volts).
More recently, however, in US20060773279P and W02007027669 the original Kolbe-
reaction was quoted as a means, among numerous other techniques, to create
useful
hydrocarbons utilizing fatty acids of renewable origin. However due to the
nature of the Kolbe-
reaction, the chain length would almost double in the process, creating a mix
of C30-C34
hydrocarbons that would need extensive conventional refining to yield useable,
liquid
transportation fuels. This may be contrasted with a one-step specialized Hofer-
Moest process,
where an alkene is produced, however at low current densities and at low
productivity
rates. However, even under these conditions considerable Kolbe dimer is
formed. Furthermore,
alkenes with teinainal unsaturation are readily subject to oxidation, and
decreases the oxidation
stability of the fuels. Additional recent publications are PCT/US2008/010707,
PCT Pub No.
W02009/035689, US Patent No. 8,444,846 B2,issued May 21, 2013 and JOSHI;
CHANDRASHEKHAR H.; Homer; Michael Glenn; United States Patent Application,
20120197050,A1,Publication, August 2, 2012.
There have been references related to the use of alternating current for the
electrolysis of
aqueous solutions using sine waves compared to direct current. For example US
Patent
2,385,410 issued September 25, 1945 to John Albert Gardner, describes a method
of producing
organic disulphides which consists in treating an aqueous solution of an
alkali metal salt or
alkaline earth metal salt of a mercapto thiazole or a dithiocarbamic acid by
electrolysis with
alternating current whereby the hydroxide of the alkali or alkaline earth
metal is liberated and
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the disulphide is formed by the union of the residues from two molecules.
However, generally,
those skilled in the art are aware that in direct current electrolysis,
electrons flow in the same
direction all the time, whereas in alternating current, the electrons flow one
way ( typically 1/60
of a sec in 60 Hz sine wave alternating current) and then they flow the other
way. To get any
electrolysis that is not immediately undone, direct current is required.
It would be possible to manufacture said liquid fuels by means of a regular,
crossed Kolbe-
electrolysis, e.g. using oleic acid and acetic acid as feedstock. This
procedure would yield a C18-
hydrocarbon and would maintain the configuration of the double bond of the
fatty acid.
However, it is believed that such a technique would be far less economical due
to the
consumption of acetic acid, the costly use of platinum anodes, and the low-
value byproducts.(i.e.
ethane and a doubly unsaturated C34 hydrocarbon in this case) generally
unavoidable in a
crossed or hetero Kolbe reaction.
It has been reported that many companies are cooperating with producers of
animal fat
and/or vegetable oils to create hydrocarbons from triglycerides, making
straight C16/C18
alkanes and propane (from the glycerol contained in fats/oils). However, this
process uses a
catalyst and totally hydrogenates feedstock at high pressures and
temperatures. It consumes large
amounts of hydrogen, requires catalysts and destroys all special
configurations of the fatty acid
originated double bonds. The process described in this invention can preserve
such double bonds
and can utilize the hydrogen generated by the electrolysis. The need for an
external source of
hydrogen is avoided.
SUMMARY
The invention provides a process for decarboxylation of a carboxylic acid and
anions
such as an aliphatic, cyclic, heterocyclic or aromatic carboxylic acids to
produce the
corresponding decarboxylated and anion-free derivatives, such as hydrocarbons
comprising
alkanes, alkenes, alkyl-aryl hydrocarbons, hydrocarbon ethers or hydrocarbon
esters in organic
solvents, and the use of the derivatives as pharmaceuticals, chemicals, fuels
or fuel blends. More
generally, the invention can be used to produce organic radical cations,
neutral radicals, cations
and anions as reactive intermediates for further reaction with added solvents
and other additives.
More specifically, the invention is directed for producing a fuel additive or
a fuel, which fuel
may be, for example, a third-generation biofuel or that can be blended. The
process may also be
used to manufacture conventional hydrocarbon fuels from renewable feed stocks.
In addition, the
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invention also discloses decarboxylated compositions that can be used by the
chemical,
pharmaceutical and fuel industry and apparatus for carrying out the invention.
The invention also includes compositions that can be produced by the inventive
process by
decarboxylation including hydrocarbon compositions, alkanes, alkenes, alkyl-
aryl hydrocarbons,
hydrocarbon ethers, hydrocarbon alcohols and hydrocarbon esters. Product
compositions can be
selected by selecting the initial reagents, solvents and additives.
The invention also discloses an apparatus for carrying out the inventive
process, in a batch
process, semi-continuous process and a continuous process.
In particular the invention provides a process for producing a hydrocarbon
composition
and chemicals which comprises the step of performing polarity reversing
electrolysis on a
solvent solution of an anion such as a carboxylic acid or salt thereof or
carboxylic acid ester or
other derivative or precursor thereof to decarboxylate said carboxylic acid or
derivative thereof,
and produce a decarboxylated derivative product.
In particular, the initial objective of the invention provides a process for
producing a
decarboxylated derivative, such as a saturated or unsaturated hydrocarbon,
which comprises the
step of performing polarity reversing electrolysis with an anode and a cathode
on a solvent of an
anion, a carboxylic acid or salt thereof or carboxylic acid ester or other
derivative or precursor
thereof to form a reactive radical intermediate or to decarboxylate said
carboxylic acid or
derivative, and produce the corresponding decarboxylated product or adduct
with the radical
intermediate. In addition, the process conditions can be adjusted to produce
alkyl-aryl
hydrocarbons, alkenes , ethers, alcohols and esters in addition to the
preferred alkane in one step.
Another inventive step is the composition of the solvent and carboxylic acid
concentration such
that the products of the electrolysis phase separates from the initial
homogeneous reaction
mixture and greatly simplifies the separation and purification of the
products. This avoids or
reduces substantially the need for separation by energy intensive
distillation. In addition, the
reaction medium containing solvents and salts can be reused to decarboxylate
additional
carboxylic acids without the need for additional reagents and solvents.
Furthermore, the polarity
reversal process overcomes the mass transfer limitations of direct current
electrolysis and
reduces electrode fouling by the products. Catalysts such as platinum,
palladium nickel can be
coated or impregnated onto the electrodes to further enhance the electrolysis.
By a precursor of a carboxylic acid (or of a salt or other derivative thereof)
is referred to a
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compound that will produce such a material under appropriate reaction
conditions, in particular
under the conditions under which electrolysis is to be carried out. An example
of a suitable
precursor is an ester that hydrolyses in situ. Other examples are carboxylic
acid derivatives that
allow for electrical conductivity and electrolysis, such as carboxylic acid
salts, carboxylic acids
and tertiary amines, both free and immobilized on solid supports that produce
carboxylate
anions. In addition, the tertiary amines can produce anions from the alcohol
solvents to produce
ethers during decarboxylation.
The invention also provides a product composition or compositions produced
directly or
indirectly by this process that can be used by the chemical, the
pharmaceutical and the fuel
industry.
The decarboxylated product compositions that is produced may be used to
prepare other
chemicals, pharmaceutical intermediates, fuels or fuel additives.
The process of the invention may further comprise the steps of purifying and
separating
the products from the reactive intermediates generated and decarboxylated
product
compositions from the reaction solvent. Additionally, the process of the
invention may further
comprise the step of adding the decarboxylated product alkane to a fuel to
produce renewable
fuel or as fuel additives to the fuel.
A further objective is to overcome the great limitation of mass transfer and
ion-transport
that limits the efficiency and productivity of direct current (DC)
electrolysis. In DC electrolysis
unidirectional ion transport is needed to complete the circuit. In AC
electrolysis, this mass
transfer limitation is avoided. Furthermore, the desired product is produced
only at the anode or
at the cathode, and undesired product is not used or wasted. Another objective
of the invention is
to improve the efficiency and productivity of electrolysis that is not
possible with DC
electrolysis, due to the fouling of the electrodes and decreased current
density of the electrolysis.
The above limitations can be overcome by disclosed invention as demonstrated
in the examples.
Furthermore, the use of different polarity reversing functions such as square
wave function
overcomes the limitations of sine wave AC electrolysis.
The decarboxylation of the anion or carboxylic acid group of the carboxylic or
fatty acid
by reverse polarity electrolysis generates a reactive intermediate such as a
decarboxylated radical
intermediate at both the anode and cathode during the anodic cycle of each
electrode, and
produces a hydrogen radical at the cathode during the cathodic cycle of each
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addition, carbocations (carbonium ions) can be produced at each electrode
during the anodic
cycle depending on the applied voltage and the ionization potential of the
molecule. Without
speculating on the mechanism of the invention, in order to understand the
invention, it is
possible, under some electrolysis reaction conditions, for the Kolbe reaction
to occur, whereby
the radical dimerises by reaction with another alkyl radical of the same type
to produce a Kolbe
dimer. If the frequency of the polarity reversal is low, there is sufficient
time for the radical to
react with another radical, dimerise and for the formation of the normal Kolbe
dimer product.
However, when the frequency of the polarity reversal is high, when the anode
changes polarity,
and the alkyl radical in the vicinity of the anode is now in the proximity of
the polarity changed
cathode. The cathode reduces hydrogen ions to hydrogen radicals that react
with the alkyl
radicals in the vicinity produced in the prior cycle to produce the alkane.
This allows for the use
of the hydrogen that is normally produced in the prior art Kolbe reaction to
react directly with
the alkyl radical and produce the alkane. This avoids the need to use a low
molecular weight acid
such as acetic, propionic or formic acid to produce a Kolbe low molecular
weight dimer.
Kolbe Electrolysis
2RCH2COONa +2 H20 ¨> RCH2CH2R + 2CO2 + 2NaOH +H2 (1)
Anode Cathode
2RC00- - 2e ---> 2RCOO= ---> 2R =+2CO2 --> R-R Kolbe Dimer (2)
= Represents free radical
It is known in the art that to form the normal Kolbe dimer with two alkyl
radicals, high
current densities and high carboxylate concentrations are needed presumably to
produce
sufficiently high concentrations of radicals available on the electrode
surface or in the vicinity
for reaction. It is also known that at low current densities and higher
electrode potentials, the
alkyl radicals abstract hydrogen from the neighboring carbon atom and form an
alkene, the
Hofer-Moest reaction.
2RCH2-CI7-000- -2e --> 2RCH2-CH2. -2e 42RCI12-CH2+ (3)
Carbo cation
2RCH2-CH2+ -> 2RCH=CH2 + H-H Ho fer-Moest (4)
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2RCH2-CH2+ H-H -> 2RCH2CI-13 Hofer-Moest (5)
2RCH2-CI-12+ 2CH30--> 2RCH2C112-0C1-13 Hofer-Moest (6)
The conditions used for electrolysis in the Hofer-Moest process can be
selected to generate
a low concentration of free radicals, which minimizes the occurrence of free
radical dimerization
and thereby reduces the Kolbe reaction, but is not prevented. However, low
current densities
result in low reaction and production rates, and the hydrogen is released and
lost with its energy.
Furthermore, hydrogen is still generated and released at the cathode and
requires schemes to
capture and utilize the hydrogen.
Electrolysis
2RCH2CH2COONa +2 H20 42RCH=CI-I2 + 2CO2 + 2NaOH +H2 (7)
The anode cycle
2RCII2CH2C00- -2e ¨> 2RCH2CH2. + 2CO2 (8)
The cathode cycle
211+ + 2e --> 21-1. (9)
21120 + 2e --> 2 OW + H2
2Na+ + 2e --> 2Na+ 2H20 -> 2 OH- + 112
The reaction on and in the vicinity of the anode and cathode
2RC1-12CH2- + 2H- -> 2RCH2CF12-H -> 2RCH2CH3 (10)
Non-Kolbe Alkane
Overall Reaction with polarity reversal electrolysis.
2RCH2CH2COOH + 2Na0H -> 2RCH2CH2COONa + 2H20 (11)
2RCH2CH2COONa + 2H20 -> 2RCH2CH3 + 2CO2 + 2NaOH (12)
Anode -Cathode
2RCH2CH2C00- -2e -> 2RCH2CH2. + 2CO2 (13)
2RCH2CH2. -2e -> 2RCI-12CH2+ -> 2RCH¨CH2 +11-H (14)
Carbocation on further oxidation at Anode
2RCH2CH2+ + 2CH30- -> 2RCH2CH2OCH3 (15)
2RCH2CH2. + 2e -> 2RCH2CH2- (16)
Carbanion on further reduction at cathode at cathode cycle
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2RCH2CH2- + 2H+ 4 2RCH2CH2-H (17)
In general, besides the carboxylate anion and hydrogen ion, metal ion or amine
cation, any
anion or cation that that can interact with the anode and cathode can be used.
Therefore, it is
preferred that the anions and cations present in the electrolyte solution are
restricted only to those
that are desired to prevent the formation of unwanted side products.
The invention can be described generally as given below.
Anode/Anode Cycle: A- is the anion
A- - e A- -e 4 A+ Carbocation (18)
A- + A. -> AA Kolbe Dimer
A. + B. 4 AB (19)
A+ + Nu- 4 ANu (20)
Nu- is a Nucleophile
Cathode/Cathode Cycle: B+ is the cation
B+ +e B. + e 4 B- Carbanion (21)
B. + A. -> AB (22)
B- +E-f- -> BE (23)
E+ is an Electrophile
Besides the radical reactions, A. and B., the carbocation and carbanion can
then react with
any nucleophile (Nu-) or electrophile ( E+) present in its vicinity to produce
the corresponding
products.
In the process of the invention, the free radicals such as the alkyl free
radicals generated by
decarboxylation of the fatty acid react with a nearby hydrogen radical
produced during the
cathodic cycle to produce an alkane. If a reactive solvent molecule is
present, such as an alcohol,
the alkoxy free radical or an anion can react with the alkyl radical to
produce an ether. The alkyl
radical may eliminate a hydrogen atom to form an alkene and an alkane. In
principle, the alkyl
radicals could also be further oxidized (i.e. loose another electron) and
become carbocations,
which may undergo structural changes before either reacting with the hydrogen
radical or
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hydrogen ion to form an alkane, with the solvent to form an ether or
eliminating a hydrogen
atom to form an alkene before the polarity reversal. A mixture of ethers, a
mixture of alkanes and
alkenes and esters can sometimes be obtained from the process of the
invention, and the
formation of the Kolbe dimer is minimized. The number of carbon atoms in the
alkanes and
alkenes is one less than the number of carbon atoms in the carboxylic acid
(the carboxyl group of
the fatty acid splits off as CO2).
A number of factors may influence the nature and concentration of the
radicals, cations
and anions that are produced during the polarity reversing electrolysis step.
These factors include
the size and shape of the electrodes, the material from which the electrodes
are made, the surface
characteristics of the electrodes, the distance separating the electrodes in
solution, the electrolyte
and solvents that are used, the concentration of the reactants such as
carboxylic acid, the
properties of the carboxylic acid salt, type of current, direct or with
polarity reversal, the
function and shape of the applied voltage and the polarity switch, the rise
and fall times of the
polarity reversal frequency, the symmetry of the polarity reversal function,
the electrode
potential voltage and the current density. In addition, the formation of
organic radical cations,
neutral radicals, cations and anions is specific to each molecule, and
dependent on the ionization
energy and the bond dissociation energy among other factors. Thus, the
electrolysis step may be
performed in a number of different ways in order to obtain the desired product
or products and to
produce the alkane, the alkene, ether or ester as described in the invention
and to minimize the
Kolbe dimer. I The conditions also influence the amounts of alkane, ether and
alkene that are
produced. If an alkyl ether is not desired, a non-alcoholic solvent can be
used. If an alkene is not
desired, current density, voltage, frequency of the polarity switch, polarity
switch function, and
voltage function can be changed to obtain predominantly the desired products.
The general reactions given in equations (18) to (23) is further illustrated
in Table I for
the different molecules that may form reactive intermediates for further
reaction to form
products. For example, acetic acid, CI-13COOH acetic acid radical CH3C00.
acetate
anion CH3C00- from Table I can undergo decarboxylation similar to the
experimental
examples given for oleic acid.
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Table I. Organic Radical Cations, Neutral Radicals, Cations, and Anions
Reactive Intermediates that may be generated and undergo reactions under
polarity reversal Electrolysis Conditions that may undergo further reaction.
Hydrocarbons
C
methane, CH4 methylene singlet, CH2 methylene triplet, CH2** methyl radical,
CH3. methyl cation, CH3 methyl anion, CH3"
C2
ethane, CH3CH3 ethane radical cation, CH3CH3+. ethyl radical, CH3CH2= ethyl
cation,
CH_3CR21 ethyl anion, CH3CH2"
ethylene, CH,CH7 ethylene radical cation CH_=C1V= vinyl radical, CH2=CFI*
vinyl
cation, CH2=CH
acetylene, HCCH dell- acetylene radical, HCC- acetylene anion, HCC"
C3
propane, CHiCH2CH3 propane radical cation, CH3CH2CH3+* Propyl radical,
CH3C1-12CH2 propyl cation, CH3CH2CH2+
cyclopropane, CH2(CH2)CH2 cyclopropane radical, CII2(CF12)CH2 6
isopropyl cation, (CH32CH+ isopropyl radical, (CII3)2CH=
propene, CH2=-CHCH3 propene radical cation, CH2¨CHCH3+= 1-deH-1-propene
radical,
CH3CH-----CH= 2-deH-propene cation, C1-i2=CNCH3 1-deH-1-propene cation,
CH3CH¨Clf
allyl cation, CI I2--CHCR2+ allyl radical, CI-12¨CHCH2, allyl anion, CH7¨CHCH2-
C4
butane, CH3CH2CH2CH3 butane radical cation, CH3CH9CH2CH3 1-
deH-butane radical,
CH3CH2CH2CH2*
2-dell-butane radical, CH3CH2CH(i)CH3 1-deH-butane cation, CH3CH2CH2CH2+ 2-deH-
butane cation, CH3CH7CH(+)CH3
2-methylpropane, (CH33CH 2-methylpropane radical cation, (CH3)3CII+.
isobutyl cation, (CH3)2CHCH2+ isobutyl radical, (CH3)2CHC1-12=
2-methylpropene, (CI-13)2C¨CH2 2-methylpropene radical cation, (CH3)2C----CW=
2-deH-1-
methylcyclopropane cation, CH2(CH+)CHCH3 3-deH-butene cation,
C1-12=CHCMHCH3 2-deH-methylpropene cation, CH2=CH(CH3)CH2+ 1-deH-1-
methylcyclopropane cation, CH2(CH2)CHCH3
t-butyl radical, (CH3)3C= t-butyl cation, (CH)3C
CS
2-methylbutane, (CH3)2CHCH2CH3 2-methylbutane radical cation,
(CH3A2CHC1-I2CH14= isopentyl radical, (CH3)2C(=)CH2CH3
isopentyl cation, (C1-12)2Ce-)C1-12CI13 1-
pentene, H2C¨CHCH2CH2CI13 1-pentene radical

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cation, H7C¨CHCH7CH9CH3+.
C6
2-methylpentane radical cation, CH3CH(CH3)CFI2CH2CH3+.
2 2-dimethylbutane, (CH3)3CCH1CH3 2,2-dimethylbutane radical cation,
(CH3)3CCH7CH3+.
Aromatics
Benzene, C6H6, Benzene Radical Cation, C6H6+ Benzene Radical Anion,C6H6-=
Toluene, C7148, Toluene Radical Cation, C7H8+. Toluene Radical Anion,C7E18-. ,
Phenyl Radical , C6H5. Tolyl Radical ,C6H7-*
Oxygen: Alcohols, Ethers, Aldehydes, Ketones, and Acids
C
methanol, CH30H methanol radical cation, CH30H+. methoxy radical,
methylperoxyl radical, CH300.
methoxy cation, CH30+ methanol onium cation, CH30H, methox, anion, CH30- 1-
deH-
methanol radical, CH2.0
formaldehyde, CH20 formyloxonium cation, CH,OH+ deH-formaldehyde cation, HCO
delI-formaldehyde anion, HCO" deH-formaldehyde radical, HCO=
formic acid, HCOOH 1-deH-formic acid radical, HOOD. formate anion , HC00-
C2
ethanol, CH3CH2OH 0-delI-ethanol radical, CH3CH90. ethoxy anion, CH3CII20-
methyl acylium cation, CH3C0+
ethyleneoxide, C2H40 deH-ethyleneoxide cation, C21430+
dimethylether radical, CH30CH7. dimethylether cation, CH3OCH7+
vinyl alcohol, CH2=-CHOH vinyl alcohol radical cation, CF17¨CH0H+. vinyloxy
radical,
CH2=CH0. vinyloxy anion, CH2¨CH0"
1-del-I-acetaldehyde cation, CH3C0+ 1 -deH-acetaldehyde radical, CH3CO.
2-deH-acetaldehyde cation, 0=CHCH2+ 2-deH-acetaldehyde radical. 0=CHCH2
acetic acid, CH3COOH acetic acid radical, CH3C00. acetate anion, CH3C00-
deH-acetic acid radical, HOOCCH) deH-acetic acid cation. H00CCH2+ 0-deH-
acetic
acid cation, CFI3C00+
C3
propanol, CH3CH2CH7OH propanol radical cation, CH3C1-12CH201I+4, 1 -
delI-propanol
radical, CH3CH7CH.OH
1-deH-propanol cation, CH3CH2CHNOH 2-del-I-propanol radical, CRICH.CH,OFI 2-
dell-propanol cation. CH3CH(+)CH70H
3-deH-propanol cation, CH2(+)CH2CH9OH isopropanol, (CH3)2CH0H isopropanol
radical
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cation, (CII-.1).2CHOH'=
methylethylether, CH3OCH7CH3 methylethylether radical cation, CH3OCH2CH3+=
deli-methylethylether radical, CH3CH,OCH7= deH-methylethylether cation,
CH3CH20C112+
pxopanal radical cation, CHICH7C0+. 1-defi-propanal cation, CH3CH2C0+ 1-deH-
plopana1 radical, CH3CH2CO=
acetone, CH3C=OCH3 del-l-propanone cation, CH3C¨OCH24 del-l-propanone radical,

CH3C=OCH2!
propene' radical cation, H,C=COHCII3+. all I alcohol radical HOCH=CHCH_!
methylacetate, CH3COOCH3 methylacetate radical cation, CH3COOCH3+=
methyl-deH-acetate radical, CII300CCH2. methyl-dell-acetate cation,
CII300CCH7'
propanoic acid, CH3CH2COOH p_or panoic acid radical. CH3CH2COO=
2-deH-propanoic acid radical, CII3CH=COOII 2-deH-propanoic acid cation,
CH3CH(t)COOH
C4-05 Alcohols, Ethers
C4 2-methylpropanol, (CH3)2CHC1-120H 2-methylpropanol radical cation,
Lc_HD2CHCH20H+.
2-deH-2-methylpropanol radical, (CH32C=CH2OH 2-methylpropoxy radical,
f_CF13)2CHCH20.
t-butanol, (CH3)3COH t-butanol radical cation, (CH3)3C0H+.
t-butyloxy cation. (CH313C0+ 2-deH-isopropylmethylether cation, (CH3hCHOCH3 t-
butyloxy radical, (CH3)3CO
diethylether, CH3CH7OCH7CH3 diethylether radical cation, CH3CII2OCH7CH3+0
ethylvinylether, CH3CH2OCH=C H2 ethylvinylether radical cation, CH3 CH2 0 C
C5
methyl-t-butylether, (CH3)3COCH3 methyl-t-butylether radical cation,
(CH3)3COCH3+,
C4-05 Aldehydes, Ketones, Carboxylic Acids
C4 butyraldehydeõ CH3CH7CH2CHO butyraldehyde radical cation, CH3CH2CH2CH0+.
-dell-butyraldehyde radical, CH3CII2CH7CO= I-deH-butyraldehyde cation,
CH3CH2CH2C0+
2-butanone, CH3CH7COCH3 2-butanone radical cation, CH3CH2COCH3+.
methylpropionate, CH3CH7COOCH3 methylpropionate radical cation, CH3CH7COOCH3
C5
2-pentanone, CH3CH2CH2COCH3 2-pentanone radical cation. CH3CH7CH2COCH3+=
pentenol radical cation, CH3COH=CH2CH2CH2+.
Nitrogen
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methylamine. CH3NH? N-deH-methylamine radical, CH3N14. methaniminonium ion,
CH2NH2 methylamide anion, CII3NH- methylammonium radical, CH3NH30
2-aminobutane, CH3CH(N142)CH7CH3 2-aminopropyl radical, CH3CH(NH2)C1-12.
imine,
Cli2=NH
N-deH-ethanimine radical, CH3CH=N= acetonitrile, C1-13CN 1-deH-acetonitrile
radical,
NCC1-12. 1-deH-acetonitrile anion, NCCH2-
propylimmonium cation, CH3CH2CH=NII?' 2-aminopropyl cation, CH3CH(NH?)CII7'
dimethylamine. CH3NHCH3 dimethylamine radical cation, CH3NHCH3 dimethylamine

radical, CH3N=CH3
N-methylmethaniminonium cation, CH3NH=Cf19+
formamide, HCONH? formamidate anion, HCONH- N-methylacetamide,
CII3C=ONFICH3
N-methylacetamide radical cation, CH3C=ONHCH3+. N-methylacetamide radical,
CI3C¨ON=CH3
N-methylacetamide cation, CH3C=ON(+)CH3
N,N-dimethylacetamide, CH3C=ON(CH3)2 N,N-dimethylacetamide radical cation,
CH3C=ON(CH1)2+=
Halogens
difluorocarbene singlet, CF7 methylfluoride cation, CH2F+ methylchloride
cation,
CH2C1 methylchloride anion, CH2C1-
ethylfluoride, CH3C1-17F 1,1-difluoroethane, CH3CHF7
ethylfluoride radical cation,
CH3CH2F+.
fluoroethylene, CH2CHF 1-deH-1-fluoroethylene anion, CH9CF-
chloroethane, CH1C117C1 1-deH-1-chloroethane radical, CH3CH(.)C1
chloroethylene,
CH2CHC1
bromooethane, CH3CH2Br 1-deH-1-bromoethane radical, CH3CH(s)Br
anti-dichloroethane radical cation, anti-C7H4C12+e
allylchloride radical, C1CH=CHC1-12. 1-chloropropane radical, CICH2CH=CH3
chloroacetic acid C1CH COOH chloroacetate anion, C1CH,C00-
_
Allylie
allyl cation, CH2=CHCH2+ allyl radical, C1-12=CHCH7= allyl- allylalcohol
radical allylchloride radical 1-ehloropropane radical
Small Radicals and Ions
011 radical HOO radical HCO3 radical C01- radical
Stable Neutral Molecules
Hydrides: H20 HCN HNCO HOCN HNCS HSCN HF HCI
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Footnote: The above list of organic reactive intermediates (Table I) are
representative of the
cations, radicals and anions that can be formed by the disclosure and that can
react. Table data
is referenced from http://www.colby.eduichemistry/webmo/radcat.html.
In this embodiment, the radical, the carbocation can act as an electrophile
and
subsequently involved in the electrophoretic substitution reaction. In such a
reaction, the
electrophile substitutes one of the substituents on an aromatic group, for
example, hydrogen,
instead of the hydrogen generated by the electro-reversal, as shown below as a
non-limiting
example with benzene.
RC00- -e R. + CO2 (24)
R. -e R+ (25)
RIF + C6H6 C6H5R1 + 1-1 (26)
RI + C6H6 C6H5R1 + H. (27)
The H+ or the H. may then be consumed, further reacted, etc., in the reactor
in the vicinity
of the electrodes or in the bulk solution. In the embodiment shown above,
benzene is shown as
the aromatic solvent or additive, instead of water or n-hexane given in the
examples. Those
skilled in the art will appreciate that other aromatics such as toluene or non-
aromatic organic
solvents or additives may also be used, that will react with the radical or
the carbocation.
Electrolysis may be performed using a relatively low current density, medium
current
density or a high current density. If the current density is low, the
frequency of the electrode
polarity switch can be low. If the current density is high, the frequency of
the reverse polarity
switch may need to be sufficiently high to produce hydrogen radicals that will
react with the
alkyl radicals and minimize Kolbe dimer formation. Furthermore, the profile of
the function
generator of the polarity switch, sine wave, square wave or triangular wave or
other function will
determine the concentration of the reaction intermediates and the reaction
products on and
around the electrode at a particular instant. Typically, the electrolysis is
performed using a
current density of 0.002 to 4 A cm-2. It is preferred that the current density
be 0.01 to 1 A cm-2,
particularly 0.02 to 1.0 A cm-2. The voltage can be high, as high as 250 V for
high productivity,
especially in the industrial scale. Usually it is preferred to employ a low
voltage because of
efficiency, equipment availability, heat transfer and safety reasons, for
example less than 48V,
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particularly 3 to 15 V. The voltage may be chosen to achieve a balance between
economy (at
low voltage) and avoidance of by-products (at high voltages) and electrical
efficiency and the
symmetry of the polarity reversing function. As the voltage source, solar
panels producing direct
current can be used and avoid the use of inverters to convert alternating
current to direct current
and avoid the conversion losses, and allow the invention to be practiced in
remote locations to
produce fuels and chemicals.
A relatively low or high current density may be achieved in any suitable way,
for example
by selecting appropriate electrode distance, electrolyte concentration and or
cell voltage.
The anode and cathode of the apparatus used to perform electrolysis may be
composed of
materials that are the same as or different from one another, and each may be
independently
selected from carbon, natural graphite, synthetic graphite, conductive
polymers, platinum,
palladium, steel, copper, silver, gold, nickel, Ti/Ru02 or any transition
metal or transition metal
compound, or other materials mentioned herein. In addition, catalysts can be
deposited on the
electrodes in order to enhance the electrolysis efficiency and product
selection, such as the
deposition of platinum, palladium and other transition metal catalysts on
carbon electrodes. If the
anode and/or cathode comprises carbon, then it is preferred that it comprise
graphite or boron
doped diamond.
In one embodiment of the invention, the anode is composed of a material other
than
graphite. In another embodiment of the invention both the anode and cathode
are composed of
the same material. In this embodiment it is preferred that they both comprise
graphite.
In another embodiment of the invention the anode and cathode are composed of
different
materials. In this embodiment it is preferred that one of the materials
comprise graphite.
The material of the electrodes is often critical, and the surface
characteristics , the
frequency of the switch and the type of function in the frequency switch will
in general be
important and critical. It is preferred that the electrodes have a rough
surface, such as that
provided by graphite rather than the smooth or glassy surface usually provided
by, say, platinum.
Porous electrodes with high internal surface areas are specifically preferred.
This gives reaction
intermediates the location and time to react at the surface or vicinity of the
electrodes. A
composite electrode could be provided having a highly conductive core of one
material and a
coating of a material of a suitable roughness and surface area. Also, a
usually smooth material
could be treated to produce the desired roughness and eleetro-catalytic
activity to produce the

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desired product.
The anode and cathode of the apparatus in which electrolysis is to be
performed may be
arranged in such a manner that when they are placed in the solvent, the
closest spacing between
the anode and cathode in the solvent is from 0.1 to 10 mm. It is preferred
that the closest spacing
between the anode and cathode in solution is from 1 to 3 mm, in order to
obtain high current
densities and have sufficient space for the release of the products from the
electrodes or for
reactant flow in a flow through reactor. Multiple electrodes can be arranged
so that the total
surface area of the electrode can be increased to increase productivity.
The electrolysis step in the process of the invention is typically carried out
on a solvent
solution of a carboxylic acid, or salt or other derivative thereof, wherein
the total concentration
of the carboxylic acid and/or derivative in the solvent solution is usually
around 2 molar, more
usually at least 1 molar, for example about 1 molar. The precise value will
often depend on the
ability of a solvent to keep the material in solution. In the case where the
reactants phase
separates, the electrolysis reaction can be carried out under sonication or an
externally generated
emulsion by mechanical mixing such as by using a mechanical homogenizer or a
fluidizer that
generate emulsions by cavitation.
In principle any solvent or alcohol may be used as the solvent for the
electrolysis process,
provided that it is a liquid at the temperature at which the reaction is to be
performed. It is
preferred that the solvent dissolves the carboxylic acid, and the product
alkane is insoluble or
sparingly soluble so that the product hydrocarbons phase separate from the
reaction solution.
This phase separation greatly facilitates the separation of the alkane or
products from the reaction
vessel by simple decantation from the solvent or by removal from the bottom,
and makes the
process an economically competitive separation process compared to separation
by distillation.
If the decarboxylated product is soluble in the solvent or solvent mixture,
the product can still be
separated by conventional distillation to recover the solvent and product.
Any solvent or solvent mixtures can be used for the process. Alkyl alcohols
are more
preferred, especially saturated, linear or branched C1 ¨05 alkyl alcohols.
Alcohols that are
particularly suitable include methanol, ethanol, n-propanol, i-propanol, n-
butanol, s-butanol or t-
butanol, ethylene glycol, especially methanol, ethanol and n-propanol.
It is not essential for the solvent or alcoholic solution to be anhydrous. Up
to 10% or more
by volume of the solution may be water, more typically up to 8% by volume, and
more
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preferably up to 4% by volume. In another embodiment, the solvent solution is
anhydrous. In
another embodiment the solvent is water or primarily water.
The solution of the fatty acid, or salt thereof, may comprise an alkali metal
or alkaline
earth metal hydroxide salt (especially Li0H, NaOH, KOH or in some situations
Ca(OH)2
although the latter material may have insufficient solubility in some
solvents), or an amine salt
from a tertiary, secondary, primary amine or an ammonium salt. A concentration
of at least 0.5
M, preferably at least 1 M, particularly about 2 M will usually be suitable to
achieve the desired
current density, the metal ions and anions being the principle charge carriers
during electrolysis.
If a carboxylic acid is initially added to the solvent solution, then the
alkali metal or alkaline
earth metal hydroxide salt may be added to deprotonate the fatty acid in-situ.
In one embodiment
of the process, electrically conductive inorganic salts, particularly alkali
metal (especially
sodium and potassium) chlorides, sulfates, persulfates, perchlorates,
carbonates and acetates are
excluded from the solvent solution.
The electrolysis step generates heat and with heat the solvent solution may
cause reflux of
the solvent. It is preferred that electrolysis be performed at the reflux
temperature of the solvent
or the reactor immersed in a cold liquid bath or a jacketed reactor to remove
the heat. It will
usually be satisfactory to carry out the polarity reversing electrolysis at
atmospheric pressure. In
some situations, however, a high pressure might be desirable in order to allow
a higher
temperature to be used without excessive bubbling and for product selection
and to increase the
rate of reaction.
The process of the invention converts a carboxylic acid or salt thereof, into
an alkane or
alkene or a mixture of an alkane, and alkene or alkyl-aryl compound depending
on the initial
reactants used.. An ether can be produced depending on the polarity reversal
electrolysis
conditions and solvent used. In addition some esters may also be produced. The
term carboxylic
acid refers to any organic compound, aliphatic, cyclic, heterocyclic, or
aromatic, that contains a
carboxylic acid that can be decarboxylated by this invention to produce the
decarboxylated
product. The term fatty acid as used herein refers to an organic compound
having a single
carboxylic acid attached to an aliphatic chain, which may be branched or
unbranched and may be
saturated or unsaturated. Typically, the fatty acid has at least 8 carbon
atoms. The aliphatic chain
of the fatty acid may be branched or unbranched, and typically the fatty acids
are derived from
triglycerides and lipids from oils and fats from plant and animal sources by
hydrolysis using
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acids, bases or at high temperatures and pressures with water and steam and is
known in the art.
Suitable unbranched saturated carboxylic acids include one or more of butanoic
acid,
pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,
decanoic acid,
undecanoic acid, dodecanoic acid, tridecanoic acid, dodecanoic acid,
tetradecanoic acid,
pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid,
nonadecanoic
acid, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid.
Suitable monounsaturated fatty acids include one or more of cis-5-dodecenoic
acid,
myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid,
and nervonic acid.
Suitable polyunsaturated fatty acids include linoleic acid, alpha.-linoleic
acid, linolenic acid,
arachidonic acid, eicosapentaenoic acid, and docosahexaenoic acid.
The term salt of a fatty acid refers to the carboxylate salts of the fatty
acid (e.g. sodium
oleate). The counter cation to the carboxylate anion is typically an alkali
metal cation, an alkaline
earth metal cation, ammonium or alkylated ammonium ( NR4 where each R is
independently a
C1-4 alkyl group). In particular, the counter cation is preferably selected
from one or more of
lithium, sodium, potassium, rubidium, and ammonium. More preferably, the
counter cation is
sodium or potassium.
In one embodiment of the invention, the use of alkali metal salts of propionic
acid
(particularly sodium propionate), caprylic acid (particularly potassium
caprylate), lauric acid
(particularly sodium laurate), myristic acid (particularly sodium myristate),
oleic acid
(particularly potassium oleate), stearic acid (particularly potassium
stearate), tridecanoic acid
(particularly potassium tridecanoate), pentadecanoic acid (particularly
potassium
pentadecanoate), heptadecanoic acid (particularly potassium heptadecanoate)
can also be used
depending on the desired physical properties.
In one embodiment, the fatty acid, or salt thereof, is unsaturated, more
preferably is
monounsaturated or polyunsaturated. Preferably, the fatty acid, or salt etc.
thereof, is
monounsaturated and has a double bond. More preferably, the fatty acid is
derived from
vegetable oils, animal fats, and waste oils containing high free acid content
by hydrolysis that is
generally known in the art of triglyceride and ester hydrolysis.
Analysis of experimental results reveals that alkanes, ethers, alkenes and
cyclo- alkenes
are formed during the reaction based on the reaction conditions used in a
ratio based on the
frequency, voltage and current density with straight chain fatty acids. This
ratio varies
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significantly, however, depending on the fatty acids involved, as well as on
the reaction
conditions of the inventive steps and departs from the prior art expected
Kolbe dimer product
and Hofer-Moest process and product compositions.
If the product compounds of the electrolysis constitute a fuel, rather than
act solely or
mainly as a fuel additive or chemical, it is preferred that the alkanes,
ethers, the alkenes, aryl-
alkanes, or the ethers, alkanes and alkenes together constitute at least 15%
particularly at least
40%, preferably at least 75%, and more preferably at least 90% by weight of
the total fuel
composition.
Thus, the invention provides a fuel composition comprising an ether and an
alkane
compound represented by formula AB, ANu or BE as defined in Equation, (19),(
20) and (23)
above.
In particular, the amount of the alkane, the ether, or the amount of alkene,
or the amount of
ether plus the amount of alkene, present may be for example at least 20% by
weight of the
composition, preferably at least 30, 40, 50, 60, 70, 80, 90 or 95%.
In the use or in the composition of the invention, the fuel composition may
include one or
more of a lubricity additive, combustion improver, detergent, dispersant, cold
flow improver,
dehazer, demulsifier, cetane improver, antioxidant, scavenger or a pollution
suppressant typically
used in the industry.
The hydrocarbon or hydrocarbon chain can be derived from any suitable feed
stocks, and
in particular from any biomass feedstock or in any way from biomass. For
example, the
hydrocarbon or hydrocarbon chain can be derived from a saturated fatty acid,
or salt or other
derivative from plant and animal origin triglycerides.
The composition can be formed by a process including electrolysis. Moreover,
it can be
formed by a process further including catalysis to further change the
properties to meet the
specification of a particular use by further transformation or reformation.
The polarity switching electrolysis can be performed in a batch, semi-
continuous, or
continuous mode of operation.
The product may be a hydrocarbon, alkyl-aryl hydrocarbon, hydrocarbon-ether
mix which
may be subjected to one or more further processing steps including but not
limited to distillation,
catalysis and crystallization. Thus, the ether and the hydrocarbon may be
further separated or
purified and/or reacted. The result may be a pure hydrocarbon and/or pure
ether useful as
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synthetic fuel components.
The core manufacturing process is preferably therefore a non-Kolbe
electrolysis of fatty
acid salts (for instance sodium, potassium), performed in solution in a
solvent or a lower alcohol
(methanol, ethanol, isopropanol etc.) using a simple electrolysis cell with,
for example, two or
more graphite electrodes with relatively small nominal spacing in between
(about 2 mm) and
medium to high current density (less than approximately 0.05-0.2 Acm-2) under
near reflux
conditions, where evaporation heat can be used to discharge excess heat
created by the current
involved. The current density may be increased from 0.01 to 2 Acm-2 provided
the heat can be
removed by reflux or by cooling of the reactor, with minimal production of the
Kolbe dimer at a
high production rate.
It is believed that polarity reversing electrolysis has not previously been
used directly to
produce the alkane from the decarboxylation of a carboxylic acid. Acetic acid
and formic acids
have been used to produce alkanes by cross Kolbe electrolysis to create
alkanes with fewer
carbon atoms beyond the fatty acid. In fact, such a process is not used today
to create any
hydrocarbons or fuels at any significant scale, let alone biofuels due to the
cost of acetic acid and
formic acid. The formation of an alkane by cross Kolbe reaction with formic
acid is uncertain.
Also, very few hydrocarbons today are being created commercially at any scale
from biomass
feed stocks, except using gasification and Fischer-Tropsch processes, which
work very
differently from electrolysis and by high temperature catalytic
decarboxylation using hydrogen
gas.
Further technical details relating to preferred embodiments of the invention
follow.
An intermediate bio-fuel, lubricant or renewable chemical composition
according to the
present invention can have the following structures:
Ether, RCH2CH2OR (I)
Alkane, RCH2CH2-H (II)
Alkene, RCH2=CH2 (III)
Alcohol, RCH2CH2-0H (IV)
Alkyl-Aromatic, RCH2CH2Ar (V)
The residues R, R' , Ar can represent one or more selected from the group
consisting of a
single H as well as any branched or unbranched, saturated or unsaturated alkyl
group including,
but not limited to methyl, ethyl, n-propyl, iso-propyl, allyl, all 4 butyls, E-
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pentyl, all possible isoprenyls, octyls, nonyls, decyls, undecyls, dodecyls,
tridecyls, tetradecyls,
pentadecyls, pentadecenyls, hexadecyls, heptadecyls, heptadecenyls and
heptadecadienyls and
aromatic groups.
The alkyl chain R! can be an alkoxyalkane or aryloxy, such as the phenoxy
group, and can
comprise one or more selected from a group consisting of H, methyl, ethyl,
propyl/iso-propyl,
allyl, and all isomers of butyl, butenyl, pentyl, pentenyl and hexyl or
aromatic group.
Hydrocarbon compositions, aliphatic as well as aliphatic-aromatic are a main
product of
the core process. Ethers and alcohols are the other products of the core
process. Both are formed
in varying amounts . These ethers can be used together with those hydrocarbons
as a novel fuel
mixture, with properties similar to B20/50/80 (i.e. a 20/50/80%
biodiesel/petroleum fuel mixture
or sequence) while performing better (higher energy content, lower cold filter
plugging point
(CFPP), less aggressive solvent properties, etc.). In this case the core
process need be the only
process employed. When water is used as an additional reagent, alcohols are
produced,
represented by formula (IV), and can be used as specialty chemicals as well as
fuel additives.
. When aromatic solvents or additives are used as an additional reagent, alkyl-
aryl products are
produced, represented by formula (V), and can be used as specialty chemicals
as well as fuel
additives and fuels.
Alternatively, these ethers can be seen as intermediates that can be refined
further, for
instance into hydrocarbons using a catalytic process. The resulting products
may be "pure"
hydrocarbons (i.e. having no more than traces of other compounds). This is
possible for
applications where fuels containing ethers are unappealing for whatever
reason. If catalytic
processing is not desirable for any reason, the hydrocarbon/ether mixture can
also be separated
by means of conventional distillation or other suitable means.
Currently, ethers are not commonly used in diesel type of formulations. The
processes
used to prepare ethers based on gasification are very different from the
invented process in that,
for example, gasification and associated processes used to form ethers cannot
easily produce
other, for example longer-chain, ethers. The mixed alkyl-aryls are expected to
contain favorable
fuel properties such as low freezing points and therefore can be used
advantageously as fuels,
especially jet fuels.
In addition, the invention produces hydroxyl compounds if water is used along
with the
other solvents that can be used as oxygenated fuels or chemicals such as fatty
alcohols.
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In contrast to prior art biodiesel formulations (the main renewable fuel for
diesel engines)
having two oxygen atoms per molecule, the present ethers preferably have only
one oxygen atom
per molecule, and thus have greater energy content. In other words, the energy
density of prior
art biodiesel fuel formulations is lower than that of the present biofuel
formulations. Moreover,
prior art biodiesel formulations have some undesirable properties, e.g. they
act as solvents that
attack rubber and other materials in engines, and they have a fairly high
melting range (e.g. palm
oil biodiesel without additives melts between 5 and I 0° C.). In
contrast, the present
biofuel having ethers as their only non-hydrocarbon component in general act
as very mild
solvents at best, and they generally have a much lower melting range than
biodiesel made from
the same feedstock. This results in the present biofuel melting at or below
well below--instead of
above--the freezing point of water.
Furthermore, the low oxygen content in the present biofuel helps making
internal
combustion burn more completely and thereby results in less toxic emissions
due to a cleaner
combustion. In addition, the low oxygen content fuels produced fuels with high
octane
numbers without undesirable material interaction properties.
The present fuel composition consisting mainly of hydrocarbons is also much
closer to
petroleum-based diesel fuel in terms of engine and fuel distribution network
material
compatibility as well as shelf life.
Alkenes
The invention also relates to a hydrocarbon composition comprising any
unsaturated
hydrocarbon, derived from any fatty acid or from any renewable source,
utilizing any of the
above or below described processes with or without variations with at least
one double bond with
cis- or "Z-" configuration.
The invention also concerns a hydrocarbon composition comprising any
hydrocarbon
manufactured using any one of the above or below described processes from any
fatty acid or
fatty acid derivative sourced from any non-fossil feedstock, characterized by
three to twenty-two
carbon atoms with any number of double bonds.
A particularly useful group of hydrocarbons forms another part of the present
invention:
short, medium or long chain alkenes, having one or more double bonds, with
either of the
general formulae (VI):
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R¨CH=CH¨W and R¨CH=CH¨(ClI2)n¨CH=CH---R" (VI)
where the double bond has a "cis" or "Z-" configuration, n and the length of
the R groups
preferably being such that the total number of carbon atoms is from 10 to 21,
and R and R' may
themselves contain further unsaturation. In the examples, Oleic acid,
CI13(CH2)7CH=CH(CH2)7COOH was used.
Those proficient in the art will, after reading this specification, appreciate
the significance
of this group of compounds specifically emphasized here, i.e. unsaturated
hydrocarbons having
to 21 carbon atoms and double bond(s) with cis- or "Z-" configuration. For
example, mention
may be made of heptadecenes of the general formula C17F134 or similar
compounds with more
than one double bond--at least one of which has cis-configuration--with
similar properties. The
above groups are found in oils and fats feed stocks. Furthermore, these
compounds can have
multiple uses as specialty chemicals.
These compounds differentiate themselves by the distinguished stereo chemistry
of that
particular middle double bond(s), which is always "cis" or "Z-" (same-sided),
while the stereo
chemistry of double bonds in refined petroleum feedstock is arbitrary in
almost all cases. The
hydrocarbons described immediately above, as well as those more generally
described by
formula (VI) can be directly derived by the manufacturing process that forms
part of the
invention. For instance, some members of the family of hydrocarbons in formula
(VI) are
unsaturated hydrocarbons with 17 carbon atoms, and can be derived from one
particular
unsaturated fatty acid, namely oleic acid, which is abundant in nature in both
vegetable as well as
animal fats and oils. The stereo chemistry of its double bond has a very well-
defined
configuration, practically 100% Z/cis, and the invented manufacturing process
preserves this
configuration after cleavage of the carboxyl group, reflected in the retained
cis-, or "1.
"configuration of the hydrocarbons created. This is of tremendous advantage,
as explained
below.
This distinguished stereo chemistry leads to a certain preferred spatial
molecular "bent"
geometry of these compounds, which ultimately lowers their melting point (MP)
significantly.
This can also be observed in nature in many vegetable oils, which, despite
having a fatty acid
spectrum that is dominated by C18 fatty acids, are liquid at room temperature.
Conversely,
animal fats with less oleic acid or other unsaturated fatty acids with cis- or
"Z-"configuration are
solid at room temperature. Furthermore, by using Alkyl-Aryl hydrocarbons as in
formula V, the
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melting point can be further reduced, and would allow for the resulting alkyl-
aryl hydrocarbons
to be used as jet fuels as well as non-freezing renewable biofuels. In
addition, this would allow
for the use of unsaturated trans fatty acids such as elaidic acid, vaccenic
acid and linoelaidic acid
as well, Furthermore saturated fatty acids such as, palmitic acid, C15H31 COOH
that generally
have high melting points and is the most common saturated fatty acid found in
animals, plants
and microorganisms, is widely available and can be used for producing low-
melting biofuels.
Hence hydrocarbons created from natural unsaturated fatty acids using the
present process
and having 17 or 15 carbon atoms melt far below zero or lower. At the same
time, they are
characterized by extremely low volatility and, hence, flammability (i.e. there
is far less chance of
igniting them accidentally during handling). This may be compared with
straight heptadecane (
C17H36), which has a melting point of 22° C. (72° F.), and
would, on its own and
without further refining, be practically unusable for diesel and, especially,
jet fuel and aviation
fuel.
Thus, the present C17 alkenes can provide an excellent blend stock for use
with
conventional diesel and jet fuel, and can even stand on their own and replace
conventional diesel
and jet fuel. Those of skill in the art will be aware that jet fuels require
lower melting points than
previously has been achievable with biofuels. Low melting points are required
due to the
extended stratospheric flights of jets, and accordingly, extended crossing
through regions with
very low temperatures.
Alkyl-Aryl Coupling
In addition, the invention can be used for alkyl-aryl coupling by using the
radicals
carboeations produced by decarboxylation. In addition to using methanol, added
water as a
reactant, or using hexane as a solvent, aryl compounds and solvents can be
used that are reactive
to the generated radicals and carbocations during the reverse polarity
electrolysis to produce
alkylated aromatics.
The present embodiments in addition, teach a method to produce alkylated
aromatics (AR)
products which may, for example, be used as components in lubricants or as
surface active
agents. The properties of the formed AR products depend on the structure of
both the alkyl and
aryl components as well as the number of alkyl components that are coupled to
a single aryl
component. Common methods of preparing AR compounds are based on the Friedel-
Crafts
alkylation which uses a catalyst to alkylate aromatic compounds. Such a
process can lead to the
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formation of monoalkylaromatics (MAR), dialkylaromatics (DAR) and
polyalkaromatics (PAR).
Because the properties of the MAR, DAR, and PAR may differ significantly from
each other, a
material with the desired properties is obtained by separating the different
compounds through
distillation and/or blending. One advantage of the present alkyl-aryl coupling
of the aromatic
component, or other component, is that by controlling the conditions and
parameters of the
electrolysis, one can control the degree of alkylation that occurs on the
aromatic group, and thus
control whether MAR products, DAR products, or PAR products are obtained and
thus provides
control over the properties of the synthesized compounds
In this embodiment the radical, the carbocation can act as an electrophile and
subsequently
involved in the electrophoretic substitution reaction. In such a reactionõ the
electrophile
substitutes one of the substituents on an aromatic group, for example,
hydrogen, instead of the
hydrogen generated by the electro-reversal, as shown below as a non-limiting
example with
toluene.
R1- + C7I Is C7I-17 RI -F Iff (28)
R1= + C7H8 C7H7 RI + H= (29)
The ITF or the II = may then be consumed, further reacted, etc., in the
reactor in the vicinity of
the electrodes or in the bulk solution. In the embodiment shown above, benzene
is shown as the
aromatic solvent or additive, instead of water or n-hexane. Those skilled in
the art will appreciate
that other aromatic or non-aromatic organic solvent or additives may also be
used, that will react
with the radical or the carbocation.
There are a large number of inexpensive carboxylic acid substrates that are
available to use
as the alkyl component of the alkyl-aryl coupling product. These carboxylic
acid substrates can
be coupled to a large number of possible aromatic compounds. The abundance of
inexpensive
substrates enhances the ability to control and fine-tune the properties of the
synthesized AR
compound to match the specific needs of the lubricant application (or any
other desired
application). The length of the alkyl group may affect the physical properties
of the material,
such as pour point, viscosity index, and flash point. The substitution on the
aromatic system may
increase the pour point, the viscosity index, and the flash point. The aryl
component of the alkyl-
aryl compound may affect the thermo-oxidative stability of the formed compound
(because the
electron-rich aromatic portion of the molecule can scavenge radicals and
disrupt oxidation

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processes).
Manufacturing
A preferred manufacturing process will now be explained, by which, in
accordance with
the invention, renewable or non-fossil (i.e. not derived from fossilization)
feed stocks may be
converted into useful hydrocarbons, ethers, or a mix of the two.
R¨CR'R" __ O¨R" ' (VII)
The carbon chain in formula (VII) is determined by the type of renewable
feedstock being
used, and it typically has a chain length between three and twenty-two,
depending on the kind of
fatty acids that is decarboxylated in the process. Furthermore, Aromatic
groups such as toluene
or benzene may also be used as desired to obtain the desired properties for
R', R" or
Moreover, those of skill in the art will appreciate that general melting and
boiling ranges
correspond to molecular mass. In other words, the choice of chain length is
determined in
practice by final product requirements (e.g, broad liquid temperature range,
low flammability,
etc.). The fatty acid feed stocks can be obtained by the hydrolysis of fats
and oils as is known in
the art.
Fuels
The present invention relates to a composition that can be particularly used
as a biofuel,
the composition comprising one or more of an ether, alkyl-aryl hydrocarbon
compound and a
hydrocarbon or a hydrocarbon chain. The ether and the hydrocarbon are
preferably in a useful
ratio and mixed in liquid form at room temperature. Such a composition and
also the
compositions described below are particularly suitable as biofuel.
The ether and the hydrocarbon can be mixed in any suitable ratio, preferably
from about
1:99 to about 99:1, preferably from about 10:90 to about 90:10, more
preferably from about
20:80 to about 80:20, more preferably from about 30:70 to about 70:30, more
preferably from
about 40:60 to about 60:40 and more preferably about 50:50.
The described hydrocarbon-ether compositions can be used directly as fuel,
lubricant, or
they can be processed in a catalytic or other process using, for example,
modified alumina
(A1203) or similar catalysts at about 350-400° for a specified time, to
split the long alkyl
off as alkene and to recycle the short-chain alcohol. This can, at the same
time, be used to
rearrange the long alkyl chain into something more branched using more
sophisticated
catalysts/conditions, such as those that the person skilled in the art will be
aware of
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It is highly desirable to increase the branching of the long alkyl chain and
hence lower the
melting point of any resulting hydrocarbons longer than thirteen carbons
(which have a melting
point higher than desirable in a commercial product, especially for jet fuel
and aviation fuel.
Those skilled in the art will appreciate that, by substituting ubiquitous
fatty acids as
starting material for a high-performance biofuel, use of the invention
directly impacts the
alternative use of dwindling supplies of fossil fuels. It will also be
appreciated that, by producing
carbon-neutral biofuels, use of the invention can directly impact the
environment in a positive
way by reducing or eliminating carbon emissions. Thus, the invention can
preserve fossil fuels
while also protecting the environment.
In short, the invented hydrocarbon-ether and hydrocarbon compositions are more
similar
to conventional petroleum products than existing biodiesel, whilst being
advantageously derived
from similar natural and renewable sources, and whilst minimizing emissions of
fossil CO2, i.e.
whilst maintaining carbon neutrality.
Moreover, the ethers that are produced can, in accordance with one embodiment
of the
invention, be drawn off using suitable separation techniques, e.g. by
fractionation techniques
well known to those versed in the arts or any by other suitable process. These
materials can stand
on their own as biodiesel fuels or can be used as diesel fuel additives (e.g.
to improve pour-point
or cetane number, or to act as oxygenaters diminishing toxins in engine
exhaust, etc.).
Uses for the present compositions include their applications as fuel and
chemicals in any
application where petroleum or products are used today. Thus, the present
compositions may be
similar to those in conventional use, but are made in a different way, from
different sources, and
have improved properties, e.g. the invented compositions may exhibit naturally
ultra-low sulfur,
estimated 90+% carbon-neutrality, etc.
Lubricants and Chemicals
By the choice of the solvent or additives, lubricants and other chemical
intermediates may
be made by the above process. The choice is only limited by the selection of
the reactants and the
conditions of the polarity-reversal electrolysis.
The embodiments of the above recited patent application and invention are
summarized
further below.
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The Process
A process for the preparation of decarboxylated derivatives which comprises
performing
polarity reversing electrolysis using an anode and a cathode on a solvent of a
carboxylic acid
containing more than one carbon atom or salt of carboxylic acid or carboxylic
acid ester or other
derivative or precursor thereof, to decarboxylate said carboxylic acid or
derivative, and produce
the corresponding adduct hydrocarbons, alkanes, alkenes, alkyl ethers,
alcohols and alkyl-aryl
hydrocarbons. The polarity reversal electrolyses may be performed using a
frequency range
from 0.001Hz to 3 MHz at a current density of 0.001 to 4.0 Acm-2 . The
polarity reversal
electrolyses may be performed using a polarity reversal voltage function
selected from a sine
wave, square wave or triangular wave at a frequency range from 0.001Hz to 3
MHz at a current
density of 0.001 to 4.0 Acm-2 with a voltage range from 2 volt to 240 volts.
The polarity reversal
electrolyses may be performed using a polarity reversal voltage function that
is symmetrical or
unsymmetrical. The polarity reversal electrolyses may be performed using an
anode and a
cathode using materials comprising the same or different from one another
selected from the
group consisting of platinum, nickel, palladium, steel, copper, silver, gold,
carbon, natural
graphite, synthetic graphite or boron doped diamond.
The acid or carboxylic acid derivative may be selected from the group
consisting of
saturated or unsaturated aliphatic, aromatic, cyclic, heterocyclic acid or
mixtures thereof. The
carboxylic acid salt may be selected from the group consisting of an alkali
metal, an alkaline
earth metal salt, a salt formed by the alkali metal or alkaline earth
hydroxide, a tertiary amine, a
secondary amine, a primary amine or ammonia salt. The solvent may be selected
from the group
consisting of methanol, ethanol, propanol, isopropanol, butanol, pentanol,
water, dimethyl
sufoxide, acetonitrile, dimethyl formamide, formamide and N-methyl
pyrollidone, aromatics,
hexane or mixtures thereof
The total concentration of the carboxylic acid or salt thereof in the
alcoholic solution may
be maintained to be between 0.1 and 4 molar. The solvent solution of the
carboxylic acid or
derivative thereof may be treated with and in contact with a tertiary amine,
secondary amine,
primary amine or ammonia. The solvent solution of the carboxylic acid or
derivative thereof may
be treated and in contact with an amine immobilized on a polymeric or silica
support. The
solvent solution of the carboxylic acid or derivative thereof may be treated
and in contact with an
alkali metal immobilized on a polymeric or silica support. The tertiary amine
may be is selected
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from the group consisting of triethyl amine, diethyl cyclohexylamine, dimethyl
cyclohexyl
amine, piperidine, imidazole, benzoimidazole, and morpholine, or mixtures
thereof.
The polarity reversal electrolysis may be performed between 0 degrees and 100
degrees
Celsius. The polarity reversal electrolysis may be performed at substantially
the reflux
temperature of the solvent and solvent mixtures. The polarity reversal
electrolysis may be
performed between 1 bar and 100 bar pressure. The polarity reversal
electrolysis may be
performed in an apparatus having an anode and cathode wherein the closest
spacing between the
anode and cathode in the solvent is from 0.1 to 10 mm.
The carboxylic acid may be selected from the group consisting of saturated
fatty acid,
monounsaturated fatty acid, polyunsaturated fatty acid, aliphatic carboxylic
acid, aromatic
carboxylic acid, a derivative or precursor thereof, or mixtures thereof.
The process may comprise the step of separating the hydrocarbon from the
solvent by
phase separation. The process may comprise the step of separating the
hydrocarbon from the
solvent by distillation of the solvent. The process may comprise the step of
separating the
hydrocarbon from the solvent by freezing of the reaction mixture.
The carboxylic acid or derivative may be prepared by the hydrolysis of the
triglyceride
ester or the ester of the carboxylic acid. The triglyceride ester or ester may
be derived from
vegetable oils, animal fats, waste vegetable oils or waste animal fats. The
hydrocarbon may be
mixed with other hydrocarbons, alkyl-aryl hydrocarbons, hydrocarbon ethers or
fatty acid esters
or mixtures thereof to produce fuels, lubricants and chemicals. The
hydrocarbon may be a
saturated or an unsaturated alkane, an alkene, an alkyl-aryl hydrocarbon, an
ether or an ester
derivative.
The polarity reversing electrolysis may be carried out under vigorous
mechanical mixing
of the solution or under sonication in order to remove products away from the
electrodes. The
polarity reversing electrolysis may be carried out while the anode and cathode
are subjected to
mechanical vibration at 0.01 Hz to 100 kHz in order to remove reaction
products and expose
fresh electrode surfaces.
Product by Process
Also featured is a product by process composition. The product may be of
decarboxylated derivatives prepared by performing polarity reversing
electrolysis using an anode
and a cathode on a solution of a carboxylic acid containing more than one
carbon atom or salt of
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carboxylic acid or carboxylic acid ester or other derivative or precursor
thereof, to decarboxylate
said carboxylic acid or derivative to produce the corresponding decarboxylated
derivative. In
addition, the solution may comprise solvents and additives that can react by
radical coupling or
by carbocation coupling with the solvent molecule or additives such as aryl
additives, to form
decarboxylated aryl compounds.
The carboxylic acid may be selected from the group consisting of a saturated
or an
unsaturated aliphatic, aromatic, cyclic, heterocyclic, fatty acid or mixtures
thereof
The product by process composition of the polarity reversal electrolysis may
be generated
using a polarity reversal voltage function selected from a sine wave, a square
wave or a
triangular wave at a frequency range from 0.001Hz to 3 MHz at a current
density of 0.001 to 4.0
Acm-2 with a voltage range from 2 volt to 240 volts. The product by process
composition of the
polarity reversal electrolysis may be performed using a polarity reversal
voltage function that is
symmetrical or unsymmetrical. The product by process composition using a
polarity reversal
electrolysis process may be performed using an anode and a cathode comprising
materials that
are the same or different from one another, selected from the group consisting
of platinum,
nickel, palladium, steel, copper, silver, gold, carbon, natural graphite,
synthetic graphite or boron
doped diamond. Furthermore, the electrode surfaces may be coated with
particles of platinum,
nickel, palladium, copper, silver, gold and/or boron doped diamond, to
catalyze the reaction. The
above particles can be nanoparticles or micron-sized particles, or even a
coating of the metals on
internal surfaces of the electrodes. The coating of the metals can be
performed by using
electrolytic deposition of the metal ions or metal salts.
The product by process decarboxylated derivative may be further selected from
the group
consisting of saturated or unsaturated aliphatic, aromatic, cyclic,
heterocyclic, or mixtures
thereof. The carboxylic acid salt of the product by process invention may be
selected from the
group consisting of an alkali metal, an alkaline earth metal salt, a salt
formed by the alkali metal
or alkaline earth hydroxide, a tertiary amine, a secondary amine, a primary
amine or ammonia
salt. The solvent and solution for carrying out the product by process may be
selected from the
group consisting of methanol, ethanol, propanol, isopropanol, butanol,
pentanol, water, dimethyl
sufoxide, acetonitrile, dimethyl formamide, formamide and N-methyl
pyrollidone, aryloxy,
alkoxy, hexane or mixtures thereof In addition, additional reactants that can
react with the
decarboxylated radicals and carbocations, such as aromatic hydrocarbons and
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containing reactive groups, can be used to make novel adducts. The total
concentration of the
above carboxylic acid or salt thereof in the alcoholic solution or solvent is
preferably maintained
to be between 0.1 to 4 molar.
The solvent solution of the carboxylic acid or derivative thereof may be
treated with and
in contact with a tertiary amine, secondary amine, primary amine or ammonia
during
electrolysis. Furthermore, the amine can be immobilized on a polymeric or
silica support for easy
separation of the amine and the products. The tertiary amine may be selected
from the group
consisting of triethyl amine, diethyl cyclohexylamine, dimethyl cyclohexyl
amine, piperidine,
imidazole, benzoimidazole, and morpholine or mixtures thereof. The solvent
solution of the
carboxylic acid or derivatives can be treated and be in contact with an alkali
metal immobilized
on a polymeric or silica support.
The polarity reversal electrolysis may be performed between 0 degrees and 100
degrees
Celsius, or performed at substantially the reflux temperature of the solvent.
The polarity reversal
electrolysis may be performed between 1 bar and 100 bar pressure. The polarity
reversal
electrolysis may be performed in an apparatus having an anode and cathode, and
wherein the
closest spacing between the anode and cathode in the solvent is from 0.1 to 10
mm.
Furthermore, the separation of the hydrocarbon and reaction products from the
solvent
may be performed by phase separation or by distillation of solvent.
Furthermore, the
hydrocarbon and reaction products may be separated from the solvent by
freezing.
The carboxylic acid or derivative may be prepared by the hydrolysis of the
triglyceride
ester or ester of the carboxylic acid or other esters. The triglyceride ester
or ester may be derived
from vegetable oils, animal fats, waste vegetable oils or waste animal fats.
The hydrocarbons
produced by the product by process may be mixed with other hydrocarbons, alkyl-
aryl
hydrocarbons, hydrocarbon ethers or fatty acid esters or mixtures thereof to
produce fuels,
lubricants and chemicals. The hydrocarbon may comprise a saturated or an
unsaturated alkane,
alkyl-aryl, an alkene, an ether or an ester.
The polarity reversing electrolysis may be carried out under vigorous
mechanical mixing
of the solution or under sonication. The polarity reversing electrolysis may
be carried out while
the anode and cathode are subjected to mechanical vibration at 0.01 Hz to 100
kHz.
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Apparatus
Further disclosed is an apparatus for the preparation o decarboxylated
derivatives which
comprises performing polarity reversing electrolysis using an anode and a
cathode using a
polarity reversing device on a solution of a carboxylic acid containing more
than one carbon
atom or salt of carboxylic acid or carboxylic acid ester or other derivative
or precursor thereof, to
decarboxylate said carboxylic acid or derivative, by applying a voltage and
current function
sufficient to produce the corresponding decarboxylated hydrocarbon derivative.
The polarity
reversal electrolysis may be performed using a frequency range from 0.001Hz to
3 MHz at a
current density of 0.001 to 4.0 Acm-2. The polarity reversal electrolysis may
be performed using
a polarity reversal voltage function selected from a sine wave, square wave or
triangular wave at
a frequency range from 0.001Hz to 3 MHz at a current density of 0.001 to 4.0
Acm-2 with a
voltage range from 2 volt to 240 volts. The polarity reversal electrolysis may
be performed in an
apparatus using a polarity reversal voltage function that is symmetrical or
unsymmetrical.
The polarity reversal electrolysis may be performed in an apparatus using an
anode and a
cathode using materials comprising the same or different from one another
selected from the
group consisting of platinum, nickel, palladium, steel, copper, silver, gold,
carbon, natural
graphite, synthetic graphite or boron doped diamond, or particles thereof
The polarity reversal electrolysis may be performed in an apparatus containing
a
carboxylic acid or carboxylic acid derivative selected from the group
consisting of saturated or
unsaturated aliphatic, aromatic, cyclic, heterocyclic acid or mixtures
thereof. The carboxylic acid
salt in the polarity reversal electrolysis apparatus may be selected from the
group consisting of
an alkali metal, an alkaline earth metal salt, or a salt formed by the alkali
metal or alkaline earth
hydroxide, a tertiary amine, a secondary amine, a primary amine or ammonia
salt. The solvent
may be selected from the group consisting of methanol, ethanol, propanol,
isopropanol, butanol,
pentanol, water, dimethyl sufoxide, aromatic hydrocarbon, aryl-compounds,
phenols,
acetonitrile, dimethyl formamide, formamide and N-methyl pyrollidone, hexane
or mixtures
thereof. The total concentration of the carboxylic acid or salt thereof in the
solution may be
between 0.1 to 4 molar.
The solvent solution of the carboxylic acid or derivative thereof may be
treated with and
in contact with a tertiary amine, secondary amine, primary amine or ammonia.
The solvent
solution of the carboxylic acid or derivative thereof may be treated and in
contact with an amine
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immobilized on a polymeric or silica support. The solvent solution of the
carboxylic acid or
derivative thereof may be treated and in contact with an alkali metal
immobilized on a polymeric
or silica support. The tertiary amine may be selected from the group
consisting of triethyl amine,
diethyl cyclohexylamine, dimethyl cyclohexyl amine, piperidine, imidazole,
benzoimidazole,
and morpholine or mixtures thereof.
The polarity reversal electrolysis may be performed at between 0 degrees and
100
degrees Celsius. The polarity reversal electrolysis may be performed at
substantially the reflux
temperature of the solvent. The polarity reversal electrolysis may be
performed at between 1 bar
and 100 bar pressure. The apparatus may have a closest spacing between the
anode and cathode
in the solvent that is from 0.1 to 10 mm.
The carboxylic acid may be selected from the group consisting of saturated
fatty acid,
monounsaturated fatty acid, polyunsaturated fatty acid, aliphatic carboxylic
acid, aromatic
carboxylic acid, a derivative or precursor thereof, or mixtures thereof.
The hydrocarbon may be separated from the solvent by phase separation, by
distillation
of the solvent, phase separation, or freezing.
The carboxylic acid or derivative may be prepared by the hydrolysis of the
triglyceride
ester or the ester of the carboxylic acid. The triglyceride ester or ester may
be derived from
vegetable oils, animal fats, waste vegetable oils or waste animal fats. The
hydrocarbon may be
mixed with other hydrocarbons, alkyl-aryl hydrocarbons, hydrocarbon ethers or
fatty acid esters
or mixtures thereof to produce fuels. The hydrocarbon may comprise a saturated
or an
unsaturated alkane, an alkene, an ether or an ester derivative.
The apparatus may further comprise a mechanical mixer or a sonicator wherein
the
polarity reversing electrolysis is carried out under vigorous mechanical
mixing of the solution or
under sonication. The apparatus may further comprise a mechanical vibrator,
wherein the
polarity reversing electrolysis is carried out while the anode and cathode are
subjected to
mechanical vibration at 0.01 Hz to 100 kHz.
This disclosure features a polarity-reversal electrolysis process, comprising
providing a
reactor that comprises at least one pair of spaced electrodes, providing a
controlled polarity-
reversing power supply that is constructed and arranged to provide polarity-
reversed power to
the electrodes, providing to the reactor an electrically-conductive liquid
reaction medium that
comprises reactants, wherein the electrodes are at least partially immersed in
the reaction
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medium, and operating the power supply such that the polarity of the
electrodes of the pair of
electrodes reverses at a frequency rate. Also featured are products produced
by the disclosed
processes.
The reactor may comprise multiple separate pairs of spaced electrodes, each
such pair
supplied with polarity-reversed power by the power supply. The reactants may
comprise a
species that has an anion, and wherein the process produces a reactive radical
intermediate at
each electrode during the anodic cycle of each electrode. The reactants may
comprise a species
that has a carboxylic acid group, and wherein the process produces a
decarboxylated radical
intermediate at each electrode during the anodic cycle of each electrode.
The reactants may comprise a species that has a cation, and wherein the
process produces
a reactive radical intermediate at each electrode during the cathodic cycle of
each electrode. The
cation may comprise a hydrogen ion, and wherein the process produces a
hydrogen radical
intermediate at each electrode during the cathodic cycle of each electrode.
The cation may
comprise a species that has an alkali cation, or an alkali earth cation, and
wherein the process
produces an alkali metal radical intermediate at each electrode during the
cathodic cycle of each
electrode. Reactive radical intermediates may be produced at each electrode
during the anodic
cycle of each electrode or the cathodic cycle of each electrode, and the
intermediates may react
with the reactants selected from a group of reactants consisting of compounds
that contain an
alkyl group, an alkene group, an alkoxy group, an aryloxy group, an aryl
group, a hydroxyl
group, a ketone group, an aldehyde group, a carboxyl group, a nitrogen group,
a halogen group,
an allylic group, or a nitrile group.
The process may produce a hydrogen radical at the cathode electrode during the
cathodic
cycle of each electrode. The process may produce carbonium ions at each
electrode during the
anodic cycle of each electrode. The process may produce carbanion ions at each
electrode during
the cathodic cycle of each electrode.
The spaced electrodes may comprise one or more materials selected from the
group
consisting of platinum, nickel, palladium, steel, copper, silver, gold,
carbon, zinc, iron,
chromium, titanium, transition metals, natural graphite, synthetic graphite,
boron doped diamond
and glassy carbon, or particles thereof
The polarity reversal frequency may be from 0.001 Hz to 3 MHz. The current
density
may be from 0.001 to 4.0 Acm-2. The voltage may be from 2 volts to 240 volts.
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Also featured is an apparatus for accomplishing polarity-reversal
electrolysis, comprising
a reactor that comprises at least one pair of spaced electrodes, a polarity-
reversing power supply
that is adapted to provide polarity-reversed power to the electrodes, and a
controller that controls
at least the current, and the polarity reversal frequency, of the power
supplied to the electrodes
by the power supply. The reactor may comprise multiple separate pairs of
spaced electrodes,
each such pair supplied with polarity-reversed power by the power supply. The
polarity reversal
frequency may be from 0.001 Hz to 3 MHz. The current density may be from 0.001
to 4.0 Acm-
2. The voltage may be from 2 volts to 240 volts. The apparatus may further
comprise at least one
mechanism to stir the contents of the reactor. The apparatus may comprise a
flow-through
reactor. The space between the electrodes may be from 0.1mm to 10 mm.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 is a description of the apparatus and process flow diagram
illustrating a
manufacturing process of the invention that may be used in a batch as well as
continuous
process.
Figure 2 is a description of the apparatus and process flow diagram
illustrating a
manufacturing process of the invention that may be used in a batch as well as
continuous process
where the reaction mixture is subjected to sonication or mechanical stirring
to improve mass
transfer.
Figure 3 is a description of the apparatus and process flow diagram
illustrating a
manufacturing process of the invention using multiple electrodes that may be
used in a batch as
well as continuous process to increase productivity.
Figure 4 is a description of the apparatus and process flow diagram
illustrating a
manufacturing process of the invention using electrodes that may be used in a
flow through
continuous process.
Figures 5-8 are data.
Detailed Description
Figure 1, describes the cylindrical reactor 10, with a silicone rubber
sealable lid 12 for
inserting the anode 14 and the cathode 16 that is separated by a fixed inert
spacer 18 to maintain
a fixed electrode separation between the electrodes. Leads, 20 and 22 from the
power supply and
function generator, 24, are connected to the two electrodes. The ammeter 26 is
connected in
series to measure current and the voltmeter 28 is connected to the electrodes,
14 and 16, to

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measure the applied voltage. Ports, 30, 31, 32 and openings, 34, 36 are
provided or made as
needed on the lid 12 for inserting a reflux condenser 38, ports for
thermometers and
thermocouples, 40, ports 34 for removing carbon dioxide and hydrogen generated
during the
reverse polarity electrolysis, ports for monitoring probes and sensors, 32,
ports for introducing
reactants 30, ports for removal of products 36, and ports 31 for introducing
nitrogen or other
inert gas as needed to flush the reactants. In addition, the reactor 10 is
provided with a magnetic
stirrer 44 for mixing the reactants during electrolysis. Additionally, the
reactor can be inserted in
a water or cooling bath 45 for reactor cooling and removing the heat of
reaction. In addition, the
reactor can be jacketed with a cooling jacket (not shown) for additional
cooling if needed. This
additional cooling most likely will be needed during scale up and
manufacturing.
The port for product removal 36 allows for easy removal of final products. The
port for
reactants 30 allows for the introduction of fresh batch of reactants 46 that
comprises the
electrolyte solution. In addition to the batch mode operation, the apparatus
described in Figure 1
may be used in a semi-continuous mode.
Figure 2, describes the cylindrical reactor 10 described in Figure 1, and in
addition
contains mechanical mixer ¨stirrer 60 and a sonicator 62 for additional
product mixing, that will
be useful during scale up and manufacturing. In addition, the reactor can be
jacketed with a
cooling jacket (not shown) for additional cooling if needed. This additional
cooling most likely
may be needed during scale up and manufacturing.
The port for product removal allows for easy removal of final products. The
port 30 for
reactants allows for the introduction of fresh batch of reactants. In addition
to the batch mode
operation, the apparatus described in Figure 2 may be used in a semi-
continuous mode
Figure 3, describes a rectangular electrochemical reactor 100 containing
multiple sets of
anode-cathode pairs, 102-112, 104-114, 106-116,108-118, connected to the Power
Generator/Function Generator 130 using the common leads 110 and 120, for
carrying out the
inventive process in a semi-continuous and continuous mode for scale up and
manufacturing.
Each of the anode-cathode electrode pairs are separated by insulating spacers,
132, 134, 136 and
138 and connected to a power supply and function generator 130 to provide the
voltage and
current necessary to carry out the reverse polarity reaction. Ports 142, 144
and 146 are provided
for introducing in a continuous, semi-continuous or batch mode, the reagents
and for removing
the reaction products, in a continuous, semi-continuous or batch mode.
Additional ports are
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provided for introducing any purging gases such as nitrogen 148 and for
removing product gases
150 such as hydrogen, carbon dioxide and any other gases. Additional ports 152
are provided
for thermometers, thermocouples and other sensors needed for monitoring the
progress of the
process. Additional cooling of the reactor may be provided by jacketing of the
reactor (not
shown). The reactant electrolyte 154 is contained in the reactor and immerses
the electrodes.
Figure 4, describes a rectangular or tubular electrochemical reactor 200
containing a
single set of anode-cathode pairs, 210 and 212, for carrying out the inventive
process in a semi-
continuous and continuous mode for scale up and manufacturing. The anode-
cathode electrode
pairs, 210 and 212, are separated by insulating spacers, 220 and 222 and
connected to a power
supply and function generator 230 using the leads 232 and 234 to provide the
voltage and
current necessary to carry out the reverse polarity reaction. Reactants enter
through port 240 in a
continuous, semi-continuous or batch mode, into the electrolysis chamber 270
between the
electrodes and after the desired electrolysis and the reaction products exit,
through port 242 in a
continuous, semi-continuous or batch mode from the product out port, 242. An
additional port
250 is provided for removing carbon dioxide and hydrogen. Further ports may be
introduced as
needed for monitoring the reaction conditions. An ammeter, 260, capable of
measuring DC and
AC current is connected in series, and a voltmeter, 262 , capable of measuring
DC voltage and
AC voltage is connected to the anode and cathode, 210 and 212. The rate of
reactant introduction
will be determined by the rate of the electrolytic reaction and the variable
used based in the
desired outcomes.
In the above figures, the carboxylic acids partially or fully neutralized with
the alkali metal
hydroxides dissolved in the solvent is introduced into the electrolytic
reactor containing the
graphite or other electrodes and subjected to polarity reversing electrolysis,
by applying the
appropriate voltage using a function generator. The electrolytic current and
applied voltage were
measured. The electrolytic cell is cooled by using cold water or by allowing
the solvent to reflux
to remove the heat of the reaction and the heat generated by the electrical
resistance. The current
density is dependent on the electrical conductivity of the solution and the
applied voltage, the
electrode gap, the temperature and progress of the electrolysis. The reverse
polarity function can
be adjusted to meet the requirements of the desired reactions.
The figures illustrate the present process in what is believed to be a largely
self-
explanatory process and apparatus. Pure fatty acid feedstock can be used, as
indicated or
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produced by the hydrolysis of esters. Non-Kolbe polarity reversing
electrolysis produces the
novel and useful biofuels and chemicals of the invention, as described herein,
typically including
a hydrocarbon, ether or hydrocarbon alcohol mix. Alternatively, the novel
biofuel produced by
electrolysis undergoes separation, e.g. phase separation or fractionation to
produce pure ethers,
pure hydrocarbons, pure alkyl-aryl products or alcohols as desired. Those of
skill in the art will
appreciate that the ethers, hydrocarbons, and alcohols can be further
processed into pure
hydrocarbons, using any suitable process such as cleavage or catalysis, as is
known in the art.
The hydrocarbons can be used as diesel, jet fuel, aviation fuel, lubricants or
similar chemical
product, or can be conventionally or otherwise suitably refined to produce
liquid propane gas,
gasoline, or other desired chemical products. In addition, the process is very
generic and can be
used to produce different chemical intermediates and compositions by selecting
the carboxylic
acid, aliphatic, aromatic, cyclic, heterocyclic and produce new compounds and
intermediate by
free radical coupling and electrophilic reactions. The products of this
invention can be difficult to
produce chemicals, chemical inteimediates and pharmaceutical intermediate and
even new
chemical entities that can be used as new drugs, that is difficult or
uneconomical to synthesize.
For those skilled in the art, additional configurations can be constructed on
order to
optimize the inventive apparatus, the inventive process and variations in the
product
compositions.
EXAMPLES
The invention will now be illustrated by the following, non-limiting examples.
Gas
chromatography/mass spectrometry was used to confirm production of a
hydrocarbons, an
alkene, and ether composition suitable for use as a biofuel and as chemicals.
The fatty acids used
in the examples below have been derived from naturally occurring vegetable
oils. The examples
are non-limiting in that any carboxylic acid can be substituted for the fatty
acid, and can
generally be produced by the hydrolysis of fats, oils and lipids.
The control oleic acid, Laboratory Grade, Formula Weight 282.46, CAS 113-80-1,
was
obtained from Consolidated Chemical, Allentown, Pennsylvania 18109, and used
as received.
The GC/MS analysis results of the control oleic acid is given in Figure 5 and
Table II. The
predominant oleic acid methyl ester, 11-Octadecanoic acid methyl ester peak is
at 9.72 min.
Other peaks are impurities from the sample bottle and the lid of the sample
bottle, especially the
siloxanes, 2-butoxy ethanol and 13-Docosenamide, (Z) used as anti-static and
release agents
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and was found in the GC/MS analysis. The oleic acid methyl ester was absent
from the products
to electrolysis, but new hydrocarbon peaks appeared as shown in Figures 6, 7
and 8 and
Identified in Tables III, IV and V in substantial amounts from the invention.
In GC/MS, the GC
separates compounds based on retention time, and each peak may contain more
than one
compound. The MS identified each peak and assigns a probability value for the
compound based
on comparison to chemical databases. The results clearly demonstrate the
utility and efficiency
of reverse polarity electrolysis compared to the direct current electrolysis.
More compounds are
formed and it is expected that reactions can be controlled by adjusting the
electrolysis reaction
conditions.
Table II . GC/MS Results of Fatty Acid and Peak Identities from Fig 5.
Figs Fig 5 Fig 5 Peak
Fatty
GC-MS Acid Fatty Acid Fatty Acid
Identifier
Peak
RT Area % Peak Identifier Identifier Quality
RT,
Peak min Min CAS tt
Probability
No.
1 4.378 9.86 Ethanol; 2-Butoxyethanol 000111-76-2 87, 72,
64
Benzenepropionic acid, 3,5- Prop acid his (1,1-dimethyl ethyl)-4-hydroxy-,
2 9.223 1.04 methyl ester)
006386-38-5 94
3 9.726 4.17 11-Octadecanoic Acid, methyl ester 052380-33-3 99
9-Octanedeconic acid (Z) methyl ester 0000112-62-9 99
cis-13-Octadecenoic acid, methyl ester 1000333-58-3 99
4 10.556 1.7 Hexanedioic Acid, bis(2-ethylhexyl) ester 000103-23-
1 70
Diisooctyl Ad pate 0001330-86-5 64
Hexanedioic Acid, bis(2-ethylhexyl) ester 000103-23-1 58
10.874 2.47 1,2 -Bis(trimethylsily1) benzene 017151-09-6 86
Anthracene, 9,10-dihydro-9,9.10-trimethyl 014923-29-6 53
2-Ethylacridine 055751-83-2 53
6 10.983 3.16 1,2 -Bis(trimethylsily1) benzene 017151-09-6 41
3',8,8'-Trimethoxy-3-piperidy1-2,2'-binaphthalene-1,1',4.4'-tetrone
127611-84-1 38
Phthalic acid, 4-methoxyphenyl 2-propyl ester
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1000315-57-0 35
7 11.512 17.86 Silane, 1,4-phenylenebis(trimethyl) 013183-70-5
59
Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl silane
1000283-54-9 59
Cyclotrisiloxane, hexamethyl 0000541-05-9 58
8 11.646 51.57 13-Docosenamide, (Z) 000112-84-5 97
13-Docosenamide, (Z) 000112-84-5 94
13-Docosenamide, (Z) 000112-84-5 94
9 11.855 2.24 1,2 Bis(trimethylsily1) benzene 017151-09-6 64
Cyclotrisiloxane, hexamethyl 000541-05-9 52
Cyclotrisiloxane, hexamethyl 000541-05-9 52
11.973 3.6 Trimethyl (4-2(2-methy1-4-oxo-2-pentyl phenoxyl silane
1000283-54-9 64
Silane, 1,4-phenylenebis(trimethyl) 013183-70-5 64
1,2 -Bis(trimethylsily1) benzene 017151-09-6 41
11 12.023 2.34 1,2 -Bis(trimethylsily1) benzene 017151-09-6 64
Cyclotrisiloxane, hexamethyl 000541-05-9 52
1,2-Benzenediol, 3,5-bis(1,1-dimethylethyl)
001020-31-1 50
Total 100.01
Example 1 (B6-31) Figure 6
Oleic Acid to Hydrocarbons Using Polarity Reversal
To 102 g of a 50/50 mixture by weight of oleic acid (0.18M) and methanol in a
bottle with
a magnetic stirrer and a lid added 4.2 g of a 10% (w/w) solution of sodium
hydroxide in
methanol and mixed well with the magnetic stirrer. A control sample of 5 g
solution was
removed for analysis. A pair of graphite electrodes,(EDM1-Poco, Saturn
Industries, New York)
2.5 xl5cm and 1 mm thickness, separated by 2mm, using polyethylene spacers was
introduced to
the bottle along with a thermocouple thermometer probe. The electrodes were
immersed in the
reactor such that 5 cm of the electrode pair was under the solvent solution.
The electrodes were
set so that the electrodes protruded through a silicone elastomer allowing for
sealing the contents
of the bottle as shown in Figure 1. The electrodes were then connected to a DC
power supply
and the voltage increased from 1.25V to 14.95V with the polarity reversal set
at 2.6 sec with a
polarity reversal switch(E-mechanical timing relay, Allied Electronics, USA)
and the current
measured. The current increased from 0.097A at 3.96 V to 0.39A at 12.69V to
0.46A at 14.95V.
The voltage was then set to 12.69V and the polarity reversal switch was set to
0.6sec. The initial

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temperature was 68 deg F. There was gas evolution from both electrodes and the
temperature
rose to 104 deg F within 50 minutes and the current increased to + and - 0.48
A. The solution
was clear. After 29 hrs the voltage was 12.46V and the current + and - 0.36A.
After 34 hrs the
voltage was 12.59 V and the current + and ¨0.19 A and there was gas evolution
from both
electrodes and the temperature 66 deg F. After 43 hrs, the temp was 66 deg F,
voltage 12.59V
and the current + or ¨ 0.15 A. There was a white precipitate at the bottom
covering to about 6
nun and there was gas evolution with stirring. After 48 hrs, there was an oil
layer at the bottom,
height 1.8 cm with a diameter of 5.4 cm corresponding to 41 cubic cm of oil
with greatly reduced
production of gas bubbles. After 72 hrs , the voltage was 12.63V and the
current + or ¨ 0.09A
and the electrolysis was stopped. The oil at the bottom was removed and 32.6g
of product oil
was recovered. The measured yield from oleic acid from 50 g was 42.1 g,
representing 79% of
the theoretical yield. Balance was in the supernatant and as not reacted oleic
acid. The
supernatant was further electrolyzed, and the supernatant produced more oil
that fell to the
bottom of the electrolytic cell, and an additional 5 g of oil was recovered.
The initial fraction of product oil, was placed in a 40 ml glass bottle and
placed in the
freezer at ¨minus 12 deg C along with the control sample and oleic acid. The
product oil was still
liquid, oleic acid froze, and the control sample had at the bottom the frozen
oleic acid and the
methanol was at the top as a liquid.
The product Oil, Control Sample and Oleic Acid were analyzed by GC/MS. The
results are
given in figure 6.
The analysis showed that part of the oleic acid had been transformed with
multiple product
peaks at 8.23, 8.85 and 8.89 min, that was not present in Figure 5. When
comparing the results
with a Direct Current normal Kolbe and non-Kolbe results given in Example 4,
figure 8, Table
V, it shows that the amount of products with retention times of 8.23, 8.85 and
8.89 min were
low for the normal Kolbe electrolysis. Additional compounds were fomied that
were not formed
with the normal DC Kolbe electrolysis, Example 4, fig.8. Table I gives the
GC/MS analysis by
dissolving 0.1% by weight of the product in n-hexane analyzed by a third party
independent
analytical laboratory. The retention times are in minutes and the peak heights
are normalized for
the relative percentage of each component. Each retention time and each peak
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Table Ill . GC/MS Results from Reverse Polarity Electrolysis and Peak
Identities from Fig
6.
Peak GC-MS Fig 6 Fig 6 Fig 5 Peak
B6-
No. RT 31 B6-31 Fatty Acid
Identifier
Area Peak
min % Peak Identifier Identifier
Quality
CAS #
Probability
1 4.376 4.76 Ethanol; 2-
Butoxyethanol 000111-76-2 91, 86, 72
2 7.455 0.63 Cyclododecene 001501-82-2 94
1000245-70-
E-1,9-Tetradecadiene 7 83
1000131-35-
E-7-Dodecen-2-o1=acetate 3 80
3 7.513 0.61 1-Pentadecane 013360-61-7 98
1-Pentadecene 013360-61-7 98
Cyclopentadecene 000295-48-7 94
1000245-70-
4 8.234 15.83 E-1,9-Tetradecadiene 7 96
Cyclododecene 001501-82-2 94
cis-9-Tetradecen-1-01 035153-15-2 74
8.284 3.07 1,9-Tetradecadiene 112929-06-3 87
Cyclododecene 001501-82-2 76
cis-9-Tetradecen-1-01 035153-15-2 74
6 8.335 1.58 Cyclododecene 001501-82-2 89
1,9-Tetradecadiene 112929-06-3 76
cis-9-Tetradecen-1-01 035153-15-2 74
7 8.41 4.79 Spiro(4,5)
decane 000176-63-6 87
8-Hexadecyne 019781-86-3 86
9.12-Octadecadienoic acid (Z,Z) 000060-33-3 80
8.63
1000131-10-
8 8.804 0.57 Z,E-3,13-Octadecadien-1-o1 4 83
1000131-10-
E-2-Octadecadecen-1-o1 2 81
Bicyclo(3.3.2) decan-9-one
028054-91-3 78
1000185-19-
9 8.854 4.68 (4-Methyl-pent-3-enyI)-cyclohexane 1 70
1000131-10-
Bicyclo(2.2.2) octane, 2-methyl- 2 55
9,17-Octadecadienal, (Z)
056554-35-9 47
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8.863
1000185=19-
8.896 5.47 (4-Methyl-pent-3-enyI)-cyclohexane 1 38
1,11-Dodecadiene
005876-87-9 38
1000245-71-
E-1,9-Hexadecadiene 4 38
8.913
11 9.081 2.34 1,11-Dodecadiene
005876-87-9 95
1000352-68-
()leyl alcohol, methyl ether 0 95
1,13-Tetradecadiene
021964-49-8 95
12 9.223 0.89 Benzenepropionic acid, 3,5- Prop acid his
(1,1-dimethyl ethyl)-4-hydroxy-, methyl ester)
006386-38-5 94
1000058-06-
8-(2,5-Dimethylanilino)naphtho-1,2-quinone 6 46
3,5-Di-tert-butyl-4-trimethylsiloxytoluene
018510-49-1 40
13 9.718 6.27 8-Octadecanoic acid Methy; Ester
002345-29-1 99
11-Octadecenoic acid, methly ester
052380-33-3 99
9-Octadecenoic acid, methyl ester
001937-62-8 99
9.726
10.556
1000332-57-
14 10.564 0.62 1,2-
Benzisothiazol-3-amine tbdms 2 38
1,2-Bis(trimethylsily1) benzene
017151-09-6 38
Silane, trimethyl (5-methy1-2-(1-
methylethyl)phenoxy)-
055012-80-1 38
10.816
10.866 3.12 Erucic
acid 000112-86-7 56
1000348-57-
Fumaric acid, 2-chloropropyl dodecyl ester 0 53
Erucic Acid
000112-86-7 53
10.874
10,983
16 10.992 5.25 Cycloheptadecanol
004429-77-0 48
9-Octadecenoic acid, (Z)-2,3 dihydroxypropyl ester methyl ester 45
000111-03-5
1-Cyclohexylnonene
114614-84-5 41
17 11.051 0.63
1,2 -Bis(trimethylsily1) benzene 017151-09-6 90
Silane, 1,4-phenylenebis(trimethyl)
013183-70-5 81
Silane, trimethyl (5-methyl-2-(1-
055012-80-1 53
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methylethyl)phenoxy)-
11,227
18 11.243 6.17 Benzene, 2-(tert-butyldimethylsily1) oxy)-1-isopropy1-4-
methyl-
330455-64-6 38
6-Octadecenoic acid(Z) 000593-39-5 38
9-Octadecenoic acid(Z)-,0-octadecenyl ester, )Z) 003687-45-4 38
Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl 1000283-54-
19 11.344 0.43 silane 9 59
1,2 -Bis(trimethylsily1) benzene 017151-09-6 53
Cyclotrisiloxane, hexamethyl 000541-05-9 52
20 11.411 0.61 Silane, 1,4-
phenylenebis(trimethyl) 013183-70-5 59
Cyclotrisiloxane, hexamethyl 000541-05-9 58
Cyclotrisiloxane, hexamethyl 000541-05-9 50
21 11.486 0.34 1,2 -
Bis(trimethylsily1) benzene 017151-09-6 59
Cyclotrisiloxane, hexamethyl 000541-05-9 58
Cyclotrisiloxane, hexamethyl 000541-05-9 58
11.495
11.512
22 11.646 26.92 13-Docosenamide, (Z) 000112-84-5 98
9-Octadecenamide, (Z) 000301-02-0 97
13-Docosenamide, (Z) 000112-84-5 93
11.855
11.864
11.939
11.973
12.023
23 12.107 4.41 1,2 -
Bis(trimethylsily1) benzene 017151-09-6 53
Silane, 1,4-phenylenebis(trimethyl) 013183-70-5 50
Trimethyl (4-2(2-methy1-4-oxo-2-pentyl ) phenoxyl silane
1000283-54-
9 47
Total 99.99
Example 2 (B3-25)
Oleic Acid 60 Hz Sine Wave Electrolysis
To 104 g of a 50/50 mixture by weight of oleic acid (0.18M) and methanol in a
reactor
with a magnetic stirrer and a lid added 5 g of a 10% (w/w) solution of sodium
hydroxide in
methanol and mixed well with the magnetic stirrer. A control sample of 5 g
solution was
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removed for analysis. A pair of graphite electrodes, 2.5 x 15cm and 1 mm
thickness, separated
by 2mm, using spacers was introduced to the reactor along with a thermocouple
thermometer
probe. The electrodes were immersed in the reactor and 5 cm of the electrode
pair was under the
solvent solution. The electrodes were set so that the electrodes protruded
through a silicone
rubber elastomer allowing for sealing the contents of the bottle as shown in
figure 1. The
electrodes were then connected to a AC power supply using a rheostat and the
AC sine wave
voltage increased to 32.5V AC. The AC current was 2.2 A. The temperature
increased from 25
deg C to 66 deg C in 5 minutes . The power was turned off and the rheostat
adjured to decrease
the voltage to 14.5 V AC giving 1.02A. The voltage was decreased to 11.5V and
the current
decreased to 0.75A AC. There was no gas evolution from either electrode. The
current
decreased from 0.75A AC to 0.3A AC within 48 hrs and upon electrolysis for 7
days dropped
to 0.05A AC. However, the solution was clear and there was no oil at the
bottom and there was
no gas evolution. This result was different from the reverse polarity example
1.
The final product, of was placed in a 40 ml glass bottle and placed in the
freezer at minus
12 deg C. along with the control sample and oleic acid. The product showed a
precipitate, and
the control sample had at the bottom the frozen oleic acid and the methanol
was at the top as a
liquid.
Example 3 (B5-49) Fig.7
Oleic Acid and Polarity Reversing Square Wave Electrolysis
To 100 g of a 50/50 mixture by weight of oleic acid (0.18moles) and methanol
in a bottle
with a magnetic stirrer and a lid was added 4.0 g of a 10% (w/w) solution of
sodium hydroxide
in methanol to provide a 1.4M solution of oleic acid and mixed well with the
magnetic stirrer.
A control sample of 4 g solution was removed for analysis. A pair of graphite
electrodes, 2.5
x 15cm and 1 mm thickness, separated by 2mm using spacers was introduced to
the bottle along
with a thermocouple thermometer probe. The electrodes were immersed in the
bottle such that 5
cm of the electrode pair was under the solvent solution with a gap for the
magnetic stirrer. The
electrodes were set so that the electrodes protruded through a silicone rubber
outside the reactor
allowing electrical connections and for sealing the contents of the reactor as
shown in Figure 1.
The electrodes were then connected to a Function Generator Maetec Model SFG
1000 set at
symmetrical square wave at 0.11 Hz, 20.5 Vpp. The voltage as measured at the
electrode

CA 02914929 2015-12-09
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initially at the start of the electrolysis was + 4.77 V and -4.69V and there
was gas evolution at
both electrodes. After 96 hrs there was a white gel at the bottom and the
voltage was and ¨
7.36 V with oil drops floating. At 120 his, the white gel had turned into oil,
and the oil layer was
1.5 cm thick. At 144 his, the voltage was + and ¨ 8.03 V and current + or ¨
0.04A and it was
stopped at + or ¨ 8.04 volts with current + or - 0.04A. The oil layer at the
bottom was 1.8cm
corresponding to a volume of 3.142x2.682.68x1.8 cubic cm or 38.2 ml of product
oil or 29.8 g of
product The theoretical yield from 50 g of oleic acid, allowing for
decarboxylation is 0.85*50
=42.5 g. This gives a theoretical yield of 29.8/42.5, 70% yield, comparable to
example I yield
of 79% from example 1.
The recovered product oil from the bottom of the cell was removed and
transferred into a
40 ml glass bottle and placed in the freezer at minus 12 deg C. along with the
control sample and
oleic acid. The product oil was still liquid, oleic acid froze, and the
control sample had at the
bottom the frozen oleic acid and the methanol was at the top as a liquid.
The product Oil, Control Sample and Oleic Acid were analyzed by GC/MS and the
results
are given in Figure 7 and the peaks identified in Table IV.
The analysis showed that greater part of the oleic acid had been transformed
with multiple
product peaks at 8.23, 8.85 and 8.89 min, and at 8.41 min, with the height of
the 8.23 mm peak
increasing substantially, that were not present in Figure 5. When comparing
the results with a
Direct Current normal Kolbe and non-Kolbe results given in Example 4, Figure
8, Table V, it
shows that the amount of products with retention times of 8.23, 8.85 and 8.89
mm were low for
the normal Kolbe electrolysis. Additional compounds were formed that were not
formed with
the normal DC Kolbe electrolysis in this invention.
Table IV . GC/MS Results from Reverse Polarity Electrolysis and Peak
Identities from Fig 7.
Peak GC-MS Fig 7 Fig 7 Fig 7 Peak
B5 1-
No. RT 49 BS 1-49 B5 1-49
Identifier
Area Peak
min Peak Identifier Identifier
Quality
CAS #
Probability
1 4.378 5.01 Ethanol; 2-Butoxyethanol 000111-76-2 91,
91, 72
46

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2 7.446 0.8 Z-11,6-Y=Tridecadiene
1000230-98-3 94
Z-1,8-Dodecadiene
1000245-70-7 83
E-7-Dodecen-l-o1 acetate
1000131-35-3 80
3 7.513 0.84 1-Pentadecane
013360-61-7 98
1-Pentadecene
013360-61-7 98
Cyclopentadecene
000295-48-7 94
4 8.234 21.47 E-1,9-Tetradecadiene
1000245-70-7 96
Cyclododecene
001501-82-2 94
cis-9-Tetradecen-1-01
035153-15-2 74
8.284 4.19 1,9-Tetradecadiene
112929-06-3 87
Cyclododecene
001501-82-2 76
cis-9-Tetradecen-1-01
035153-15-2 74
6 8.335 2.06 Cyclododecene
001501-82-2 89
1,9-Tetradecadiene
112929-06-3 76
cis-9-Tetradecen-1-01
035153-15-2 74
7 8.41 7.12 Spiro(4,5) decane
000176-63-6 87
8-Hexadecyne
019781-86-3 86
9.12-Octadecadienoic acid (Z,Z)
000060-33-3 80
8.63
8 8.804 1.06 Z,E-3,13-Octadecadien-1-o1
1000131-10-4 83
E-2-Octadecadecen-1-o1
1000131-10-2 81
Bicyclo(3.3.2) decan-9-one
028054-91-3 78
9 8.854 7.16 (4-Methyl-pent-3-enyI)-cyclohexane
1000185-19-1 70
Bicyclo(2.2.2) octane, 2-methyl-
1000131-10-2 55
9,17-Octadecadienal, (2)
056554-35-9 47
8.863
8.896 7.59 (4-Methyl-pent-3-eny1)-cyclohexane
1000185=19-1 38
1,11-Dodecadiene
005876-87-9 38
E-1,9-Hexadecadiene
1000245-71-4 38
8.913
11 9.072 3.23 1,11-Dodecadiene
005876-87-9 95
leyl alcohol, methyl ether
1000352-68-0 95
1,13-Tetradecadiene
021964-49-8 95
12 9.223 0.97 Benzenepropionic acid, 3,5- Prop acid bis
(1,1-dimethyl ethyl)-4-hydroxy-, methyl ester)
006386-38-5 94
8-(2,5-Dimethylanilino)naphtho-1,2-quinone
1000058-06-6 46
3,5-Di-tert-butyl-4-trimethylsiloxytoluene
018510-49-1 40
13 9.718 3.85 8-Octadecanoic acid Methy; Ester
002345-29-1 99
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11-Octadecenoic acid, methly ester 052380-33-3
99
9-Octadecenoic acid, methyl ester 001937-62-8
99
9.726
10.556
14 10.564 0.7
1,2-Benzisothiazol-3-amine tbdms 1000332-57-2 38
1,2-Bis(trimethylsily1) benzene 017151-09-6
38
Silane, trimethyl (5-methyl-2-(1-methylethyl)phenoxy)- 055012-80-1
38
15 10.766 0.34
10.816
16 10.866 2.93 Erucic acid
000112-86-7 55
Erucic acid
0000112-86-7 53
cis-10-Nonadecenoic acid 073033-09-7
46
10.874
17 10.984 4.25
Phthalic acid, neopentyl 2-propyl ester 1000315-56-3 25
Trimethyl (4-(2-methyl-4-oxo-2-pentyl) phenoxylsilane
1000233-56-9 25
1,2-Benzenedicarboxylic acid, diisooctyl ester
22
10.992
11.051
18 11.118 0.18 1,2 -
Bis(trimethylsily1) benzene 017151-09-6 59
Silane, 1,4-phenylenebis(trimethyl) 013183-70-5
59
5-methyl-2-phenylindolizine 036944-99-7
52
19 11.243 3.34
Cyclotrisiloxane, hexamethyl 000541-05-9 46
Cyclotrisiloxane, hexamethyl 000541-05-9
46
Trimethyl (4-tert-butylphenoxy) silane 025237-79-0
43
20 11.336 0.34
2,4,6-Cycloheptatrien-1-one, 3,5-bis-trimethyl silyl- 1000161-21-8 59
Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl silane
1000283-54-9 59
Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl silane
1000283-54-9 59
11.344
21 11.411 0.55 Trimethyl (4-
(1-methyl-1-methoxyethyl)phenoxy silane 1000283-54-8 59
1,2 -Bis(trimethylsily1) benzene 017151-09-6
59
Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl silane
1000283-54-9 59
Cyclotrisiloxane, hexamethyl 000541-05-9
58
11.486
22 11.487 0.34 Trimethyl (4-(1-methyl-1-methoxyethyl)phenoxy silane
1000283-54-8 59
1,2 -Bis(trimethylsily1) benzene 017151-09-6
59
Cyclotrisiloxane, hexamethyl 000541-05-9
52
48

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11.495
11.512
23 11.646 18.86 13-Docosenamide, (Z) 000112-84-5
97
9-Octadecenamide, (Z) 000301-02-0
95
13-Docosenamide, (Z) 000112-84-5
93
11.855
11.864
11.939
11.973
12.023
23 12.107 2.85 Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl silane
1000283-54-9 64
Cyclotrisiloxane, hexamethyl 000541-05-9
58
Cyclotrisiloxane, hexamethyl 000541-05-9
52
Total 100.03
Example 4: Direct DC Electrolysis Control, figure 8
Oleic Acid Direct Current Electrolysis -Normal Kolbe and non-Kolbe
Electrolysis
To 52 g by weight of oleic acid (0.18 molar) and 52 g methanol (1.70 molar) in
a reactor
with a magnetic stirrer and a lid added 4.4 g of a 10% (w/w) solution of
sodium hydroxide in
methanol and mixed well with the magnetic stirrer. A control sample of 5 g
solution was
removed for analysis. A pair of graphite electrodes, 2.5 x 15cm and 1 mm
thickness, separated
by 2mm, using spacers was introduced to the bottle along with a thermocouple
thermometer
probe. The electrodes were immersed in the bottle such that 5 cm of the
electrode pair was under
the solvent solution. The electrodes were set so that the electrodes protruded
through a silicone
rubber elastomer allowing for sealing the contents of the bottle as shown in
figure 1. The
electrodes were then connected to a direct current power supply and the
voltage and current were
measured . The voltage was then set at 12.6 volts, and the current was
measured at 0.20 A and
direct current electrolysis performed while the solution was stirred by the
magnetic stirrer
continuously. After 11 hrs, the DC voltage was 12.91V with and 0.03 to 0.04 A
with gas bubbles
from the electrodes. After 24 hrs, voltage was 13.1V and 0.01A current with
very little gas
evolution. After 58 hours, the voltage was 13.03V with 0.01A current with no
gas evolution and
49

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phase separation with a clear solution. The final product was analyzed using
GC/MS and the
results are given in figure 8.
The final product, of was placed in a 40 ml glass bottle and placed in the
freezer at ¨minus
12 deg C along with the control sample and oleic acid. The product showed a
precipitate, and
the control sample had at the bottom the frozen oleic acid and the methanol
was at the top as a
liquid.
The final product was analyzed using GC/MS and the results are given in Figure
8. A
comparison of the results of Fig 8, with Figures 7, 6 and 5 shows that reverse
polarity non-Kolbe
electrolysis produces more products and more efficient in converting oleic
acid to other
hydrocarbons and chemicals. Furthermore, the drastic drop in the current and
the very slow
reaction rates makes it impractical to use the direct current Kolbe and non-
Kolbe electrolysis
likely due to the coating of the electrodes with the products.
Table V . GC/MS Results from Direct Current Electrolysis and Peak Identities
from Fig 8
Peak GC-MS Fig. 8 Fig. 8 Fig. 8 Peak
B7-1
No. RI DC 87-1 DC B7-1 DC
Identifier
Area Peak
min Peak Identifier Identifier
Quality
CAS #
Probability
1 4.37 9.56 Ethanol; 2-Butoxyethanol 000111-76-2 76,
72, 64
7.446
7.513
8.234
2 8.243 4.46 Z-1,9-Tetradecadiene 100245-70-9 97
Cyclododecene 001501-82-2 95
E-2-Octadecadecen-1-o1 000506-42-3 93
8.335
8.41
3 8.63 1.44 1,13-Tetradecadiene 021964-49-8 91
E-2-Methyl-3-tetradecadecen-1-o1 acetate 1000130-81-2 78
Bicyclo(2.2.2) octane, 2-methyl- 000766-53-0 64
8.804
8.854

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8.863
8.896
4 8.913 1.37 1,9-Tetradecadiene
112929-06-3 64
(S) (+)-Z-13-Methyl-11-pentadecen-1-01 Acetate
1000130-84-8 60
Z-8-Pentadecen-1-o1 acetate
1000130-85-1 50
9.072
9.223 1.52 Benzenepropionic acid, 3,5- Prop acid bis
(1,1-dimethyl ethyl)-4-hydroxy-, methyl ester) 006386-38-5 94
Sarcosine, N-(3-phenylpropiony1)-isobutyl ester
1000321-41-2 46
Cyclohexanone, 2-((1,1'-biphenyl)-2-ylamino)
methylene)
018510-49-1 38
6 9.718 7.88 8-Octadecanoic acid Methy; Ester 002345-29-1 99
9-Octadecanoic acid Methy; Ester- E 052380-33-3 99
9-Octadecanoic acid Methy; Ester-E 001937-62-8 99
9.726
10.556
7 10.564 1.41 1,2-Bis(trimethylsily1) benzene 017151-09-6 42
Silane, 1,4 -phenylenebis (trimethyl) 013183-70-5 41
Cyclotrisiloxane, hexamethyl 000541-05-9 38
10.766
8 10.816 0.58 Trimethyl (4-(2-methyl-4-oxo-2-pentyl) phenoxylsilane
1000233-56-9 59
1,2 -Bis(trimethylsily1) benzene 017151-09-6 59
Methyltris(trimethsiloxy)silane 017928-28-8 59
9 10.866 7 Erucic acid 000112-86-7 46
Erucic acid
0000112-86-7 53
cis-10-Nonadecenoic acid 073033-09-7 46
10.874
1,2-Benzenedicarboxylic acid, mono(2-ethylhexyl)
10.984 2.77 ester
004376-20-9 38
1,2-Benzenedicarboxylic acid, diisooctyl ester 027554-26-3 38
1,2 -Bis(trimethylsily1) benzene 017151-09-6 38
10.992
11.051
11 11.227 2.63 2,4,6-Cycloheptatrien-1-one, 3,5-bis-trimethyl silyl-
1000161-21-8 59
Silane, 1,4-phenylenebis(trimethyl) 013183-70-5 59
1,2 -Bis(trimethylsily1) benzene 017151-09-6 59
11.243 000541-05-
9 46
000541-05-9 46
025237-79-0 43
11.336
11.344
51

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12 11.411 5.77 Silane, 1,4-phenylenebis(trimethyl) 013183-70-5
59
1,2 -Bis(trimethylsily1) benzene 017151-09-6
59
Cyclotrisiloxane, hexamethyl 000541-05-9
58
11.486
11.487
13 11.495
5.2 Trimethyl (4-(1-methyl-1-methoxyethyl)phenoxy silane 1000283-54-8 64
5-Methyl-2-trimethylsilyloxy-acetophenone 097389-69-0
59
Trimethyl (4-tert-butylphenoxy) silane 025237-79-0
53
11.512
14 11.646 47.32 13-Docosenamide, (Z) 000112-84-5
97
trans -13-Octadecenamide 010436-09-6
91
13-Docosenamide, (Z) 000112-84-5
89
11.855
15 11.864 0.9 1,2 -Bis(trimethylsily1) benzene 017151-09-6
59
2,4,6-Cycloheptatrien-1-one, 3,5-bis-trimethyl silyl- 1000161-21-8
59
4-Methyl-2-trimethlysilyloxy-acetophenone 097389-70-3
53
16 11.939 0.2 Cyclotrisiloxane, hexamethyl 000541-05-9
52
Trimethyl (4-2(2-methyl-4-oxo-2-pentyl ) phenoxyl
silane
1000283-54-9 50
Cyclotrisiloxane, hexamethyl 000541-05-9
50
11.973
12.023
12.107
Total 100.01
Example 5: Polarity Reversing Electrolysis with added water
To 240g of oleic acid added 184 g of methanol and mixed well using a magnetic
stirrer
and 60 g of a 10% w/w sodium hydroxide was then added slowly with mixing until
the
precipitated sodium salt dissolved. Distilled water, 15.3gm, was added drop
wise with stirring
using a pipette to produce a clear solution stock solution 5.
60 g of this stock solution 5 was added to a 150 ml electrolysis bottle
reactor containing a
pair of graphite electrodes, 2.5 xl5cm and 1 mm thickness, separated by 2mm
spacing and
containing a thermocouple and a thermometer. The electrodes were immersed in
the bottle such
that 2.2 cm of the electrode pair was under the solvent solution with a gap
for the magnetic
stirrer. The electrodes were set so that the electrodes protruded through a
silicon elastomer
outside the bottle allowing electrical connections and for sealing the
contents of the bottle as
shown in Figure 1. The electrodes were then connected to a polarity reversing
switch with a
52

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timer that was fed by two sets of 30 Volt power supplies, set at 17.5V. The
timer was set to
change the polarity to the electrodes every 0.1 sec (10 Hz). The voltage as
measured at the
electrode initially at the start of the electrolysis measured as AC was 16.4
V, and the
temperature rapidly rose from 83 d to 105 deg F, and there was gas evolution
at both electrodes.
The DC amps as measured at the power supply was 1.08 A and 1.10A. After 36hrs,
the solution
turned cloudy and the gas evolution between the electrodes, and at 40 hrs,
there was phase
separation with milky bottom layer and a cloudy top layer with the current at
0.46 amps. After
46 hrs, the current was 0.16 amps with the DC voltage at 17.3V, the measured
AC voltage at
19.7V with 1.6cm of white bottom phase and 0.8cm of top cloudy supernatant
phase. The yield
of product oil from the bottom phase was 24.8 g.
The recovered product oil from the bottom of the cell was removed and
transferred into
three 15 ml centrifuge tubes, and placed in the freezer at minus 12 deg C.
along with the control
sample and oleic acid. The product oil froze unlike the product oil from the
electrolysis in the
absence of water.
Example 6: With Hexane as Additional Solvent
To 61 g of this stock solution 5, and 6 g of n-hexane were added to a 150 ml
electrolysis
bottle reactor containing a pair of graphite electrodes, 2.5 xl5cm and 1 mm
thickness, separated
by 2mm spacing and containing a thermocouple and a thermometer. The electrodes
were
immersed in the bottle such that 2.2 cm of the electrode pair was under the
solvent solution with
a gap for the magnetic stirrer. The electrodes were set so that the electrodes
protruded through a
silicon elastomer outside the bottle allowing electrical connections and for
sealing the contents of
the bottle as shown in figure 1. The electrodes were then connected to a
polarity reversing switch
with a timer that was fed by two sets of 30 Volt DC power supplies, and the
voltage was
gradually increased from 2V to 14V. Gas evolution started at around 8V. The
timer was set to
change the polarity to the electrodes every 0.1 sec (10 Hz). The voltage as
measured at the
electrode initially at the start of the electrolysis measured as AC was 16.4
V, and the
temperature rapidly rose from 83 to 105 deg F, and there was gas evolution at
both electrodes.
The DC amps as measured at the power supply was 1.08 A and 1.10A. After 36hrs,
the solution
turned cloudy and the gas evolution between the electrodes, and at 40 hrs,
there was phase
separation with milky bottom layer and a cloudy top layer with the current at
0.46 amps. After 46
53

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hrs, the current was 0.16 amps with the DC voltage at 17.3V, the measured AC
voltage at 19.7V
with 1.6cm of white bottom phase and 0.8cm of top cloudy supernatant phase.
The yield of
product oil from the bottom phase was 24.8 g.
The recovered product oil from the bottom of the cell was removed and
transferred into
three 15 ml centrifuge tubes, and placed in the freezer at minus 12 deg C.
along with the control
sample and oleic acid. The product oil froze unlike the product oil from the
electrolysis in the
absence of water.
METHOD FOR ARYL-ALKYL COUPLING USING DECARBOXYLATION
In addition, the invention can be used for alkyl-aryl coupling by using the
radicals
produced by decarboxylation. In addition to using methanol, added water as a
reactants, or using
hexane as a solvent, aryl compounds and solvents can be used that are reactive
to the generated
radicals and carbanions during the reverse polarity electrolysis to produce
alkylated aromatics
and other alkyl-aryl compounds.
In this embodiment the radical, the carbocation can act as an electrophile and
subsequently involved in the electrophoretic substitution reaction. In such a
reactionõ the
electrophile substitutes one of the substituents on an aromatic group, for
example, hydrogen,
instead of the hydrogen generated by the electro-reversal, as shown below as a
non-limiting
example with benzene.
RIF + C6H6 -C6H5¨R1 +H
R1= + C6H6 C6H5 ¨R1 + He
The Ir or the H= may then be consumed, further reacted, etc., in the reactor
in the vicinity of the
electrodes or in the bulk solution. In the embodiment shown above, benzene is
shown as the
aromatic solvent or additive, instead of water or n-hexane. Those skilled in
the art will appreciate
that other aromatic or non-aromatic organic solvent or additives may also be
used, that will react
with the radical or the carbocation.
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Table VI. Summary of Reaction Conditions and Results
Electrode Area 12.5 sq.cm Electrode Separation 2 mm
Electrolysis Electrode
Electrode Electrolyzing Electrolyzing Electrolyzing Electrolyzing
Time Reversing Voltage Current Current Current Current
Frequency, Difference Amps Density Density Density/V
Cycles/sec, Hz Volts A/sq cm mA/sq cm
mA/sq cm/V
Example 1
Example 1 3.96 0.097 0.00776 7.76
1.960
0.40 Hz 12.69 0.39 0.0312 31.2
2.459
(2.6 sec/cycle) 14.95 0.46 0.0368 36.8
2.462
50 min Square Wave 12.69 0.48 0.0384 38.4
3.026
29 hrs 12.4 0.36 0.0288 28.8
2.323
24 firs 12.59 0.15 0.012 12 0.953
72 hrs 12.63 0.09 0.0072 7.2 0.570
min Example 2 32.5 2.2 0.176 176 5.415
60 Hz 14.5 1.02 0.0816 81.6 5.628
0.0167
sec/cycle) 11.5 0.75 0.06 60 5.217
48 hrs Sine Wave 11.5 0.3 0.024 24 2,087
7 days 11.5 0.05 0.004 4 0.348
1 hr Example 3 4.77 0.05 0.004 4 0.839
96 hrs 0.11 Hz 7.36 0.05 0.004 4 0.543
120 hrs 9.1 sec/cycle 7.5 0.05 0.004 4 0.533
144 hrs Square Wave 8.03 0.04 0.0032 3,2 0.399
1 hr Example 4 12.6 0.2 0.016 16 1.270
11 hrs Direct Current 12.91 0.035 0.0028 2.8 0.217
24 hrs 13.1 0.01 0.0008 0.8 0.061
58 hrs 13.03 0.01 0.0008 0.8 0.061
1 fir Example 5 17.5 0.2 0.016 16 0.914
1 hr 10 Hz 16.4 1.09 0.0872 87.2 5.317
36 hrs 0.1 sec/cycle 13.1 0.46 0.0368 36.8 2.809
40 hrs Square Wave 17.3 0,16 0.0128 12.8 0.740
46 hrs 17.3 0.16 0.0128 12.8 0.740
1 hr Example 6 2 0.2 0.016 16 8.000
1 hr 10 Hz 8 1.09 0.0872 87.2 10.900
0.1 sec/cycle 14 0.46 0.0368 36.8 2.629
36 hrs Square Wave 16.4 1.09 0.0872 87.2 5.317
40 hrs 17.3 0.46 0.0368 36.8 2.127
46 hrs 17.3 0.16 0.0128 12.8 0.740

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Amines as Bases
In addition, the invention and the inventive process can be carried out by
treating the
solution of the carboxylic acid or derivative thereof with a tertiary amine,
secondary amine,
primary amine or ammonia.
The invention can be carried out by replacing the alkali hydroxide with a
tertiary amine, a
secondary amine, a primary amine or ammonia salt in order to form the
carboxylate salt. The
amine base can be immobilized in a solid matrix and will allow for easy
separation of products,
such as using AMBERLYST A21 RESIN, a Divinyl Styrene copolymer with a tertiary
amine
functionality.
What is claimed is:
56

Representative Drawing