Note: Descriptions are shown in the official language in which they were submitted.
TITLE: USE OF PEROXYACIDS/HYDROGEN PEROXIDE FOR
REMOVAL OF METAL COMPONENTS FROM PETROLEUM
AND HYDROCARBON STREAMS FOR DOWNSTREAM
APPLICATIONS
CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority under 35 U.S.C. 119 to Provisional
Application
U.S. Serial No. 62/774,625, filed on December 3, 2018.
FIELD OF THE INVENTION
The disclosure relates to the use of peroxyacid formulations, including but
not
limited to peracetic acid and performic acid, for enhancement of downstream
processes
through removal of soluble and particulate metal complexes from petroleum oils
and
refinery feedstocks and/or streams. This serves to minimize fouling, decrease
the
propensity for a solid stabilized emulsion and in turn, improve waste water
quality. The
methods and compositions are particularly useful for mitigation of heavy
metals in
petroleum oil and for offsetting potential solid loading resulting from use of
a metal based
H25 scavenger or other commonly applied metal-based additives. The methods and
compositions are also useful for enhancing coke quality via decreased metal
concentrations, reducing bacteria in slop oil and crude tanks, as well as
reducing
downstream catalyst poisoning.
BACKGROUND OF THE INVENTION
A survey of a random selection of desalters in the United States found that a
significant increase in iron concentration and filterable solids was observed
at the desalter
interface relative to the raw crude charge. This suggests that solids,
sediment or fine
particulate, are concentrating at the desalter interface and promoting
emulsion stability.
If not effectively managed, a decrease in the desalting efficiency of the unit
may occur,
in addition to other problems such as oil under-carry to the waste water
treatment plant
and increased slop oil generation. In addition, a number of United States
refiners
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processing light tight oil have reported intermittent "sludges" from iron
sulfide
contaminated crude oil that have caused negative effects on emulsion
stability. At this
time there remains a need for an enhanced solids removal agent or demulsifier
that can
promote partitioning of inorganic particulate, such as iron sulfide, from an
emulsion phase
to a water phase. This is essential to increase the lifetime of process
equipment
downstream of the desalter in a refinery, to ensure compliance with
environmental
regulations in streams processed by refinery waste water treatment plants and
to enhance
profitability.
Various methods have been used in an attempt to minimize the negative effect
of
entrained inorganics in the refining of crude oil. U.S. Pat. Nos. 4,778,589
and 4,789,463
disclose the use of hydroxycarboxylic acids as chemical aids for metals
removal in
refinery desalting processes. U.S. Pat. No. 4,833,109 to Reynolds discloses
the use of
dibasic carboxylic acids, particularly oxalic acid, for the removal of
divalent metals,
including calcium and iron. Wash water addition of hydroxyacids for removing
metals
during desalting processes is taught in U.S. Pat. Nos. 7,497,943, 4,778,589
and 4,789,463.
U.S. Pat. No. 5,271,863 teaches the use of a Mannich reaction product to
extract soluble
iron and other divalent metal naphthenate complexes from crude oils. U.S. Pat.
Nos.
5,114,566 and 4,992,210 teach the removal of corrosive contaminants from crude
oil by
adding a composition including certain organic amines having a pKb from 2 to 6
and
.. potassium hydroxide to the desalter wash water. The composition is stated
to effectively
remove chlorides from the crude oil at the desalter. U.S. Pat. No. 5,078,858
suggests the
addition of an oxalic or citric acid chelant to the desalter wash water.
Likewise, U.S. Pat.
No. 4,992,164 also suggests the addition of a chelant, particularly
nitrilotriacetic acid, to
desalter wash water. U.S. Pat. No. 5,256,304 is directed to the addition of a
polymeric
tannin material to oily waste water to demulsify oil and flocculate metal
ions. U.S. Pat.
No. 5,080,779 teaches the use of a chelant in a two stage desalter process for
the removal
of iron. Other methods involve the use of increased concentrations of emulsion
breakers
(aka demulsifiers).
While the methods referenced above have added technical knowledge to the art;
in practice they have had limited success. In addition, some methods for
removing metals
and contaminants result in entrained oil in water that can negatively impact
the waste
water treatment plant and result in large quantities of slop oil that must be
reprocessed. In
addition, the various methods are not effective at removing heavy metals such
as nickel
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and vanadium that are organometallically complexed. These inefficiencies
indicate that
improved methods for the removal of particulates, including metals, from
petroleum oil
sources are needed.
Peroxyacids, particularly peracetic acid, have been employed in the oil and
gas
industry as oilfield antimicrobials in water treatment applications. See for
example U.S.
Pat. Nos. 2010/0160449 and 7,156,178. In addition, US. Pat. No 9,242,879
discloses
their use for treatment of drilling fluids, frac fluids, flowback water and
disposal water.
Application of peroxyacids in the area of commercial well drilling operations
have been
limited to use as biocides in aqueous systems. Compared to other commercially
available
biocides, use of peracetic acid has a small environmental footprint, due in
part to its
decomposition into innocuous components (i.e., acetic acid, oxygen, carbon
dioxide and
water). There is a lack of teaching to suggest use of the biocidal
applications to enhance
particulate (including soluble and particulate metal complexes) and/or heavy
metal
removal from petroleum oil and refinery streams.
Accordingly, it is an object herein to identify chemical solutions to remove
metals
from petroleum oil sources. In addition, a further objective of the invention
is to develop
methods for solids stabilized emulsion control. There have been multiple
studies that
demonstrate adsorption of surface-modifying components in crude oil to fine
particulate,
resulting in increased interfacial activity. Increased emulsion stability and
viscosity
occurs as the concentration of surface-active material at an interface builds.
Herein is a
disclosure on a mechanism to prevent this phenomenon. Minimizing the
concentration of
particulate content in crude oil should ultimately facilitate better salt
removal and
dehydrating efficiency during emulsion resolution processes. Therefore, the
peroxyacid
formulations can also be considered emulsion breakers in their own right.
A further objective of the invention is to develop methods for removal of
organometallic complexes such as porphyrinic iron, nickel or vanadium or
calcium
naphthenates. These organometallic compounds are not readily removed by normal
desalting practices and can cause coker furnace fouling, finished products
outside of
specification and deactivation of hydroprocessing catalysts.
Other objects, advantages and features of the present invention will become
apparent from the following description in conjunction with the accompanying
Examples.
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BRIEF SUMMARY OF THE INVENTION
The present disclosure is related to the use of peroxyacids compositions and
methods of employing peroxyacids for removal of metals and particulate
contained in
petroleum oil, crude oil, slop oil, and other hydrocarbon streams in various
refinery
applications. The use of peroxyacid compositions and methods of employing them
in
various petroleum oil and refinery streams overcomes a significant need in the
art for
improved methods for removing particulate iron sulfide and zinc sulfide, along
with other
contaminants. These and other benefits are achieved by the methods disclosed
herein.
In an embodiment, a method for removing particulates in petroleum oil and/or
hydrocarbon feedstocks includes the steps of: mixing petroleum oil and/or
hydrocarbon
feedstock with water to form an emulsion comprising a hydrocarbon phase and a
water
phase; adding a peroxyacid composition to the emulsion, wherein the peroxyacid
causes
the
particulates to move from the hydrocarbon phase into the water phase; and
separating the
hydrocarbon phase from the water phase to remove the particulates and the
peroxyacid
composition from the emulsion. In an embodiment, the peroxyacid oxidizes and
chelates
the particulates in the emulsion, and wherein the particulates are soluble and
particulate
metal complexes. In an embodiment, the peroxyacid composition comprises a C1-
C22
peroxyacid, a C1-C22 carboxylic acid, and hydrogen peroxide. In embodiments,
the
peroxyacid is at least one of peroxyformic, peroxyacetic, peroxypropionic,
peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic,
peroxyoctanoic,
peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxy do decanoi c, or the
peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic,
peroxyascorbic,
peroxyhydroxyacetic, peroxyoxali c, peroxymalonic, peroxysuccinic,
peroxyglutari c,
peroxyadipic, peroxypimelic and peroxysubric acid. In embodiments, at least
100 ppm of
the peroxyacid is added to the emulsion, or up to about 10,000 ppm of the
peroxyacid is
added to the emulsion. In embodiments, at least one additional agent that is a
solvent, a
corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor,
metal chelant,
and/or wetting agents is added to the emulsion with the peroxyacid
composition. In
.. additional embodiments, the mixture of petroleum oil and/or hydrocarbon
feedstock in
water is resolved in an electrostatic desalting unit. In additional
embodiments, the
methods further include adding an effective amount of an emulsion breaker or
demulsifier
to aid in the separation of the oil from the water phase containing the
particulates. In still
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additional embodiments, the methods further include settling the petroleum oil
and/or
hydrocarbon feedstock in a tank to enable the water, peroxyacid composition
and
particulates to settle on the bottom thereof from the petroleum oil and/or
hydrocarbon
feedstock. In embodiments, the petroleum oil and/or hydrocarbon feedstock is a
produced
crude oil and is obtained from a pipeline that directs a flow of produced
crude oil. In
embodiments, the petroleum oil and/or hydrocarbon feedstock once separated
from the
water phase does not contain any peroxyacid composition. In embodiments, the
petroleum
oil and/or hydrocarbon feedstock comprise petroleum oil, crude oil, slop oil,
and other
hydrocarbon streams from a refinery application. In any of the embodiments,
the method
can exclude the use of phosphoric or phosphorus acids. In an embodiment, a
crude oil
emulsion treatment consists of: crude oil; a peroxyacid composition for
transferring
metals and particulates from a hydrocarbon phase to a water phase; and a
source of water.
In embodiments, the treated crude oil emulsion further comprises at least one
additional
component that is a solvent, a corrosion inhibitor, an emulsion breaker or
demulsifier, a
scale inhibitor, metal chelant, and/or wetting agents.
In an embodiment, an emulsion treatment consists of: petroleum oil, crude oil,
slop oil, or another hydrocarbon stream in a refinery application; a
peroxyacid
composition for transferring metals and particulates from a hydrocarbon phase
to a water
phase; and a source of water. In embodiments, the treated emulsion further
comprises at
least one
additional component that is a solvent, a corrosion inhibitor, an emulsion
breaker or
demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
While multiple embodiments are disclosed, still other embodiments of the
present
invention will become apparent to those skilled in the art from the following
detailed
description, which shows and describes illustrative embodiments of the
invention.
Accordingly, the detailed description and its Examples are to be regarded as
illustrative
in nature and not restrictive.
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BRIEF DESCRIPTION OF THE DRAWINGS
The patent or application file contains at least one drawing executed in
color.
Copies of this patent or patent application publication with color drawing(s)
will be
provided by the Office upon request and payment of the necessary fee.
FIG. 1 shows a general diagram of a desalting process.
FIG. 2 shows a graph of iron removal by peracetic acid, sodium gluconate or
combinations thereof in both the hydrocarbon and water phases.
FIG. 3 shows a graph of nickel removal by peracetic acid, sodium gluconate or
combinations thereof in both the hydrocarbon and water phases.
FIG. 4 shows a graph of zinc removal by peracetic acid, sodium gluconate or
combinations thereof in both the hydrocarbon and water phases.
FIG. 5 shows a graph of iron removal by peracetic acid, sodium gluconate or
combinations thereof in both the hydrocarbon and water phases.
FIG. 6 shows a graph of zinc removal by peracetic acid, sodium gluconate or
combinations thereof in both the hydrocarbon and water phases.
FIG. 7 is a graph showing iron removal in a resolved water phase by various
peroxycarboxylic and carboxylic acids.
FIG. 8 is a graph showing nickel and zinc removal in a resolved water phase by
various chemistries.
FIG. 9 is a graph showing the amount (ppm) of filterable solids that remained
on
the top oil fraction after emulsion resolution using various chemistries.
FIG. 10 is a color photograph of four samples after centrifugation showing the
resulting resolved emulsions of EC2111A and EC6779A samples at 1000 ppm and
5000
ppm.
While the above-identified figures set forth several embodiments, other
embodiments are also contemplated, as noted in the discussion. In all cases,
this
disclosure presents the invention by way of representation and not limitation.
It should be
understood that numerous other modifications and embodiments can be devised by
those
skilled in the art, which fall within the scope and spirit of the principles
of the invention.
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention relates to the methods and application of peroxyacid
compositions for particulate and metal removal for improving or enhancing
downstream
processes for petroleum oil and refinery hydrocarbon feedstocks and streams.
The
methods of using peroxyacid compositions have many advantages over
conventional
demetallization technologies. For example, the methods can take place before,
after or
simultaneous with a desalting step. The effective removal of metals and
particulates
before a desalting process can significantly minimize the effects of these
contaminants on
the crude unit and further downstream operations. Having metals and
particulates
removed before a desalting step then promotes more efficient desalting as
well. Benefits
can include reduced crude unit corrosion, crude system fouling, energy costs
and
desalting process demarks, and finished product contamination.
The embodiments of this invention are not limited to particular methods or
peroxyacid compositions, which can vary and are understood by skilled
artisans. It is to
be further understood that all terminology used herein is for the purpose of
describing
particular embodiments only and is not intended to be limiting in any manner
or scope.
For example, as used in this specification and the appended claims, the
singular forms
"a," "an" and "the" can include plural referents unless the content clearly
indicates
otherwise. Further, all units, prefixes, and symbols may be denoted in its SI
accepted
form.
Numeric ranges recited within the specification are inclusive of the numbers
defining the range and include each integer within the defined range.
Throughout this
disclosure, various aspects of this invention are presented in a range format.
It should be
understood that the description in range format is merely for convenience and
brevity and
should not be construed as an inflexible limitation on the scope of the
invention.
Accordingly, the description of a range should be considered to have
specifically
disclosed all the possible sub-ranges, fractions, and individual numerical
values within
that range. For example, description of a range such as from 1 to 6 should be
considered
to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4,
from 1 to 5,
from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers
within that range,
for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example,
1.2, 3.8, 11/4,
and 43/4 This applies regardless of the breadth of the range.
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So that the present invention may be more readily understood, certain terms
are
first defined. Unless defined otherwise, all technical and scientific terms
used herein have
the same meaning as commonly understood by one of ordinary skill in the art to
which
embodiments of the invention pertain. Many methods and materials similar,
modified, or
equivalent to those described herein can be used in the practice of the
embodiments of the
present invention without undue experimentation. The preferred materials and
methods
are described herein. In describing and claiming the embodiments of the
present
invention, the following telininology will be used in accordance with the
definitions set
out below.
The term "about," as used herein, refers to variation in the numerical
quantity that
can occur, for example, through typical measuring techniques and equipment,
with
respect to any quantifiable variable, including, but not limited to, mass,
volume, time,
distance, wave length, frequency, voltage, current, and electromagnetic field.
Further,
given solid and liquid handling procedures used in the real world, there is
certain
inadvertent error and variation that is likely through differences in the
manufacture,
source, or purity of the ingredients used to make the compositions or carry
out the
methods and the like. The term "about" also encompasses amounts that differ
due to
different equilibrium conditions for a composition resulting from a particular
initial
mixture. The tenn "about" also encompasses these variations. Whether or not
modified
by the term "about," the claims include equivalents to the quantities.
The methods and compositions of the present invention may comprise, consist
essentially of, or consist of the components and ingredients of the present
invention as
well as other ingredients described herein. As used herein, "consisting
essentially of'
means that the methods, systems, apparatuses and compositions may include
additional
steps, components or ingredients, but only if the additional steps, components
or
ingredients do not materially alter the basic and novel characteristics of the
claimed
methods, systems, apparatuses, and compositions.
The term "actives" or "percent actives" or "percent by weight actives" or
"actives
concentration" are used interchangeably herein and refers to the concentration
of those
ingredients involved expressed as a percentage minus inert ingredients such as
water or
salts.
As used herein, the terms "preferred" and "preferably" refer to embodiments
that
may afford certain benefits, under certain circumstances. However, other
embodiments
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may also be preferred, under the same or other circumstances. Furthermore, the
recitation
of one or more preferred embodiments does not imply that other embodiments are
not
useful and is not intended to exclude other embodiments from the scope of the
invention.
As used herein, the term "waters" includes water in industrial and/or energy
.. service applications. Waters in industrial and/or energy service
applications include for
example: aquifer water, river water, sea water, produced water, fresh water,
water for
injection, secondary flooding water, hot water or feedwater, ethanol/bio-fuels
process
waters, pretreatment and utility waters, membrane system liquids, ion-exchange
bed
liquids, water used in the process/manufacture of paper, ceiling tiles, fiber
board,
.. microelectronics, E-coat liquids, electrodeposition liquids, process
cleaning liquids, oil
exploration services liquids, oil well completion fluids, oil well workover
fluids, drilling
additive fluids, oil fracturing fluids, oil and gas wells, flowline water
systems, natural gas
water systems, or the like.
The term "weight percent," "wt.%," " wt-%," "percent by weight," "% by
weight,"
and variations thereof, as used herein, refer to the concentration of a
substance as the
weight of that substance divided by the total weight of the composition and
multiplied by
100.
Peroxyacid Compositions
The methods employ at least one peroxyacid or a peroxyacid composition.
Without being limited to a particular mechanism, peroxyacids and peroxyacid
compositions are able to increase the hydrophilicity of particulate materials
(including
soluble and particulate metal complexes) in petroleum oil and refinery streams
to enhance
their removal from the oil/water emulsions. This beneficially allows the acid
to oxidize
and chelate organometallic complexes and metal-based particulates, which is
distinct
.. from use of other acids (i.e. acetic, phosphoric, or phosphorus acids which
are excluded
from the peroxyacids and peroxyacid compositions disclosed herein) which are
only able
to chelate reactive metal complexes. The approximate amount of peroxyacid
required to
achieve the desired amount of metal or particulate removal from an oil stream
can be
determined by one skilled in the art by taking into account characteristics of
the stream
being treated. In an aspect, the concentration of peroxyacid sufficient to
demetallize a
petroleum oil or refinery stream can range from 1 ppm to 10,000 ppm, between
about
1,000 ppm and about 5,000 ppm, or ranges there between. In an aspect, the
concentration
of peroxy acid sufficient to demetallize a petroleum oil or refinery stream
can be at least
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about 100 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least
about 3,000
ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000
ppm, at least
about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least
about 10,000
ppm, or ranges there between.
Suitable peroxyacids include both organic and inorganic peroxyacids as set
forth
herein. Organic peroxyacids, include for example peroxycarboxylic acids that
generally
have the formula RCO3H, where, for example, R is defined as an alkyl, alkenyl,
alkyne,
acyclic, alicyclic group, aryl, arylalkyl, cycloalkyl, aromatic, heteroaryl,
heterocyclic
group, or hydrogen. The R-group can be saturated or unsaturated as well as
substituted or
unsubstituted. Peroxyacids can be made, for example, by the direct action of
an oxidizing
agent on a carboxylic acid, by auto-oxidation of aldehydes, or from acid
chlorides, and
hydrides, or carboxylic anhydrides with hydrogen or sodium peroxide.
Any suitable CI-Cm peroxyacid, such as a peroxycarboxylic acid can be used. In
some embodiments, the CI-Cm percarboxylic acid is a Ci, C2, C3, C4, C5, C6,
C7, C8, C9, C10,
Cii, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25,
and/or C26 percarboxylic
acid. In some embodiments, a CI-C22 peroxyacid is preferred, or combinations
thereof.
Peroxyacids may include short chain and/or medium chain peroxyacids. As used
herein, a "short chain peracid" refers to a peroxyacid having a carbon chain
between 1
and 4 carbons. Short chain peracids have the benefit of often being highly
miscible in
water at 25 C. Examples of short chain carboxylic acids include formic acid,
acetic acid,
propionic acid, and butyric acid. Peroxyacetic (or peracetic) acid is a
peroxyacid having
the formula: CH3C000H. Generally, peroxyacetic acid is a liquid having an
acrid odor
at higher concentrations and is freely soluble in water, alcohol, ether, and
sulfuric acid.
Peroxyacetic acid can be prepared through any number of methods known to those
of
skill in the art including preparation from acetaldehyde and oxygen in the
presence of
cobalt acetate. A solution of peroxyacetic acid can be obtained by combining
acetic acid
with hydrogen peroxide. In a preferred embodiment, the compositions of the
invention
employ a Cl to C4 peroxyacid.
As used herein, the phrase "medium chain peracid" refers to a peroxyacid
having
a carbon chain between 5 and 22 carbons in length. Further as used herein, the
phrase
"medium chain carboxylic acid" can refer to a carboxylic acid that has a
critical
micellization concentration greater than I mM in aqueous buffers at neutral
pH. It is also
common for medium chain carboxylic acids to have an unpleasant odor. Medium
chain
carboxylic acids exclude carboxylic acids that are infinitely soluble or
miscible with water
at 20 C. Medium chain carboxylic acids include carboxylic acids with boiling
points (at
760 mm Hg pressure) of 180 to 300 C. In an embodiment, medium chain
carboxylic
acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of
200 to 300
C. In an embodiment, 20 medium chain carboxylic acids include those with
solubility in
water of less than 1 g/L at 25 C. Examples of medium chain carboxylic acids
include
pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,
decanoic
acid, undecanoic acid, and dodecanoic acid.
Peroxyacids useful in the methods described herein include meta-
chloroperoxybenzoic, peroxyformic, peroxyacetic, peroxypropionic,
peroxybutanoic,
peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic,
peroxynonanoic,
peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of
their
branched chain isomers, peroxylactic, peroxymaleic, peroxyascorbic,
peroxyhydroxyacetic, peroxyoxalic, meta-chloroperoxybenzoic, peroxymalonic,
peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric
acid and
mixtures thereof. Inorganic peroxyacids such as peroxymonosulfuric acid
(Caro's acid)
are not excluded from the peroxyacid and/or peroxyacid compositions.
In some embodiments more than one peroxyacid can be employed. For example,
in some embodiments, the composition includes one or more Cl to C4 peroxyacids
and
one or more C5 to C22 peroxyacids. In one aspect of the invention the ratio of
short chain
peroxyacid to medium chain peroxyacid can be about 1:1 to about 10:1.
As referred to herein, a peroxyacid composition also includes an organic acid
(i.e.
corresponding carboxylic acid) and an oxidizing agent. In various aspects, the
peroxyacid
composition can be formed by an organic acid and an oxidizing agent. The
compositions
can be pre-formed. In other aspects, peroxyacid compositions may be generated
in situ.
Additional description of exemplary in situ methods for peroxyacids is
provided for
example in U.S. Patent Nos. 9,845,290, 9,518,013, 8,846,107 and 8,877,254.
Oxidizing Agent
The peroxyacid compositions may also include an oxidizing agent. Most often
the
.. oxidizing agent is hydrogen peroxide. Hydrogen peroxide, H202, provides the
advantages
of having a high ratio of active oxygen because of its low molecular weight
(34.014
g/mole) and by being compatible with numerous substances that can be treated
by
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methods of the invention because it is a weakly acidic, clear, and colorless
liquid. Another
advantage of hydrogen peroxide is that it decomposes into innocuous water and
oxygen.
The peroxyacid compositions can include any desired ratio of hydrogen
peroxide.
In some embodiments, the hydrogen peroxide in the percarboxylic acid
composition has
a concentration from about 0.5 wt-% to about 25 wt-%, preferably from about
0.5 wt-%
to about 1 Owt-%. In other embodiments, the hydrogen peroxide has a
concentration from
about 1 wt-% to about 2 wt-%. In still other embodiments, the hydrogen
peroxide has a
concentration at about 0.5 wt-%, 1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, 5 wt-%, 6 wt-
%, 7 wt-
%, 8 wt-%, 9 wt-%, or 10 wt-%. In yet other embodiments, the hydrogen peroxide
has a
concentration at about 1 wt-%, 1.1 wt-%, 1.2 wt-%, 1.3 wt-%, 1.4 wt-%, 1.5 wt-
%, 1.6
wt-%, 1.7 wt-%, 1.8 wt-%, 1.9 wt-%, 2 wt-%, 2.1 wt-%, 2.2 wt-%, 2.3 wt-%, 2.4
wt-%,
2.5 wt-%, 2.6 wt-%, 2.7 wt-%, 2.8 wt-%, 2.9 wt-%, 3 wt-%, 3.1 wt-%, 3.2 wt-%,
3.3 wt-
%, 3.4 wt-%, 3.5 wt-%, 3.6 wt-%, 3.7 wt-%, 3.8 wt-%, 3.9 wt-%, or 4 wt-%.
Additional oxidizing agents include for example, the following types of
compounds or sources of these compounds, or alkali metal salts including these
types of
compounds, or forming an adduct therewith: hydrogen peroxide, urea-hydrogen
peroxide
complexes or hydrogen peroxide donors of: group 1 (IA) oxidizing agents, for
example
lithium peroxide, sodium peroxide; group 2 (IIA) oxidizing agents, for example
magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide;
group 12
(JIB) oxidizing agents, for example zinc peroxide; group 13 (IIIA) oxidizing
agents, for
example boron compounds, such as perborates, for example sodium perborate
hexahydrate of the formula Na2[B2(02)2(OH)41.6H20 (also called sodium
perborate
tetrahydrate); sodium p eroxy b orate tetrahydrate of the foimula
Na2B2(02)2[(OH)4] = 4H20
(also called sodium perborate trihydrate); sodium peroxyborate of the formula
Na2[B2(02)2(OH)4] (also called sodium perborate monohydrate); group 14 (IVA)
oxidizing agents, for example persilicates and peroxycarbonates, which are
also called
percarbonates, such as persilicates or peroxycarbonates of alkali metals;
group 15 (VA)
oxidizing agents, for example peroxynitrous acid and its salts;
peroxyphosphoric acids
and their salts, for example, perphosphates; group 16 (VIA) oxidizing agents,
for example
peroxysulfuric acids and their salts, such as peroxymonosulfuric and
peroxydisulfuric
acids, and their salts, such as persulfates, for example, sodium persulfate;
and group VIIa
oxidizing agents such as sodium periodate, potassium perchlorate. Other active
inorganic
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oxygen compounds can include transition metal peroxides; and other such
peroxygen
compounds, and mixtures thereof
Methods of Use
Methods of using peroxyacids (or peroxyacid compositions) to treat petroleum
oils and hydrocarbon feedstocks and/or streams are particularly useful for
mitigating
deleterious effects caused by heavy metal concentrations, emulsion stability
or high
particulate content. As referred to herein, the feedstocks include any
hydrocarbon
feedstock including for example crude oil, slop oil, heavy residua,
atmospheric or vacuum
residua, deasphalted oils derived from the crude oil or residua, shale oil,
liquified coal
and tar sand effluent, and the like and blends thereof As used herein,
"removing" the
metals and/or particulates from the petroleum oil and feedstocks (namely the
hydrocarbon
phase) is meant to include any and all partitioning, sequestering, separating,
transferring,
eliminating, dividing, removing, of one or more metal and/or particulate from
the
hydrocarbon phase to any extent.
In a particular embodiment particulates can include inorganic fines that are
naturally occurring in crude oil such as silt, clays, silicates and metal
oxides. These
inorganic materials may not reactive with the peroxyacids but can be removed
indirectly
during an emulsion resolution process treated with the additive (vide infra).
Particulates
can also include alkali metal salts, including but not limited to, calcium
carbonate
(CaCO3), calcium sulfate (CaSO4), iron oxides (Fe2O3 and Fe304), and barium
sulfate
(BaSO4).
In a particular embodiment, other heavy metals can include, but are not
limited to,
metal sulfides, metal chlorides, organo-porphyrins or other organometallic
complexes
that may react with the perovacid. Metals suitable for removal using the
process of this
invention (soluble or water insoluble) include, but are not limited to those
of Groups 1, 2,
4, 5, 8, and 10 of the Periodic Table. Exemplary metals include iron, zinc,
nickel,
vanadium, aluminum, magnesium, titanium, sodium, potassium, calcium, and
silicon.
The particulates can also include chloride salts, sulfur, oxides and sulfides.
Particulates
can also include inorganic molecules such as iron sulfide (FeS), zinc sulfide
(ZnS) and
aluminum chloride (A1C13) that are naturally occurring or arise from other
chemical
additives or corrosion processes.
In a particular embodiment, refinery applications include, but are not limited
to
raw crude processing, desalting, tankage treatment and dehydration, slop oil
resolution
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and mitigation, FCC desalter performance enhancement, and waste water
contaminate
removal and processing.
The methods of employing peroxyacids to remove fine particulates and metals
from petroleum oils and refinery feedstocks includes applying or adding a
peroxyacid to
a wash water source, a petroleum oil and/or hydrocarbon feedstock. As referred
to herein,
this includes, but is not limited to, crude oil, slop oil, and water in oil or
oil in water
emulsions.
The oil or feedstock to be treated should preferably be in a liquid state at
the
selected process conditions in order to facilitate contact between the oil and
the aqueous
extractant (i.e. the peroxyacid and/or water). As one skilled in the art
appreciates this may
be accomplished by heating the oil or by the addition of a suitable solvent,
e.g. a lower
boiling hydrocarbon oil, as needed. The petroleum oil or feedstock to be
treated is
delivered to a pipeline with a heat exchanger. In such embodiments, a water
supply line
connects to the flow of heated oil and is delivered with the oil.
The methods may comprise, consist of and/or consist essentially of one or more
of the following steps: add water and peroxyacid to a petroleum oil or
hydrocarbon
feedstock; add a peroxyacid to an emulsion of oil (hydrocarbon phase) and
water (aqueous
/ water phase); water-wet particulates; oxidize metals; chelate a metal;
separate the water
phase containing residual peroxyacid, water soluble metal complexes, and
particulates
from the hydrocarbon phase. In an embodiment, the peroxyacid can be added to
an
emulsion formed of a hydrocarbon phase and a water phase without further
addition of
water.
In another embodiment, the methods of adding a peroxyacid to the petroleum oil
or feedstock may precede a desalting step. A refinery's desalting unit is
designed to
remove entrained water, water-soluble contaminants and oil-insoluble
particulates from
crude oil. Crude oil is defined here as any hydrocarbon stream entering a
refinery that
will be processed through the desalter. This crucial step of the refining
process is
necessary to extend the lifetime of process equipment downstream of the unit,
render the
crude oil less corrosive, protect downstream refinery equipment from fouling,
and to
maximize throughput. The desalter achieves this by (1) providing crude oil;
(II) adding
wash water to the crude oil and mixing the two phases together to form an
emulsion; (III)
subsequently breaking the emulsion that is formed to provide an aqueous phase
and a
hydrocarbon phase containing a lower concentration of salt, particulate and
metals. The
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resolved hydrocarbon phase is commonly drawn off the top of the unit and sent
to a
fractionator tower. The water phase containing water-soluble metal salt
compounds and
sediment is discharged out the bottom of the unit and sent to a waste water
treatment plant
for processing. A general schematic of this process is given in FIG. 1.
Desalting is
traditionally enhanced by application of a high voltage electric field, heat,
and by the
addition of chemical additives such as emulsion breakers, solids-removal
agents, and
coagulants.
When effective desalting is achieved, entrained water in the crude oil will
coalesce
with the wash water and gravity settle to the bottom of the unit. This process
is used to
remove water-soluble salts such as sodium chloride, allow sediment to gravity
settle, and
to "water-wet" particulate. These three benefits are further elaborated on in
the following
discussion:
Benefit of Removal of Residual Salts. Water soluble salts in crude oil are
typically
chloride, sulfate or carbonate salts of sodium, magnesium, or calcium. If the
salts are not
effectively removed to the water phase, scale may result. This will reduce
throughput and
potentially increase operating costs. In addition, under the process
conditions downstream
of the desalter the salts will hydrolyze to form their acid analog, which will
accelerate
corrosion rates in the process vessels downstream of the unit and compromise
their
structural integrity.
Benefits of Removal of Sediment. Sediment is largely composed of naturally
occurring materials, such as silicas, clays, asphaltenes, and metal oxides,
resulting from
the geologic formation from which the crude oil was extracted or from
corrosion. This
material may gravity settle in the desalter if the particle size of the
sediment and
conditions within the unit (emulsion viscosity, crude oil retention times
etc.) are
favorable. Effective removal of this water-insoluble material will increase
throughput by
diminishing fouling rates and will increase profitability for the refiner by
decreasing the
frequency at which heat exchangers must be cleaned.
Benefits of Removal of Fine Particulate. Fine particulate, also known as
suspended solids, are hydrocarbon and water insoluble inorganics that are too
small to
gravity settle in the desalter. These inorganics are largely introduced into
crude oil from
the geological formation (sand, silt, alkali metal salts, etc.), from
corrosion processes
(FeS) or from upstream additives (metal based H2S scavengers, aluminum-based
coagulants, etc.). When suspended in a hydrocarbon phase, particulate can lead
to
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operational challenges. These challenges include plugged filters, low grade
coke quality,
increased fouling in process equipment, and shortened lifetime of fluid
catalytic cracking
(FCC) catalysts. In addition, fine particulate can act as an emulsifier and
exacerbate
emulsion stability at the desalter, which may lead to a decrease in desalting
efficiency
and/or an increase in the volume of slop oil generated.
The crude oil aforementioned and desalter emulsions may have high
concentrations of metals, including iron sulfide, and the methods disclosed
herein
beneficially removes those metals and particulates more efficiently than in a
typical
desalting operation. In addition, the peroxyacid formulation may enhance
overall desalter
performance by promoting increased removal of salt, sediment and fine
particulate from
the hydrocarbon phase.
In an embodiment, the peroxyacid is provided or introduced (e.g injected) into
a
pipe and/or tank upstream of the desalter to contact the hydrocarbon. In a
further aspect,
the peroxyacid is preferably injected upstream of a location where the treated
feed will
have adequate settling time to allow the water and hydrocarbon phases to
resolve and the
particulates to migrate to the water phase.
In another embodiment, the methods of adding a peroxyacid to the petroleum oil
or feedback may be before, simultaneous, or after the addition of wash water
to the crude
oil. The method of adding a peroxyacid may also be directly into a water
phase.
In another embodiment, the methods may also include the step of adding an
effective amount of at least one additional agent or component that is water
or a solvent,
a corrosion inhibitor, a demulsifier (such as an oxyalkylate), a scale
inhibitor, metal
chelants, wetting agents and mixtures thereof In a preferred embodiment, the
methods
may also include the step of adding an effective amount of an emulsion breaker
(i.e.
demulsifier) to aid in the separation of the oil from the water phase
containing the
particulates.
In another embodiment, the methods of adding a peroxyacid to the petroleum oil
or feedstock may precede a tankage dehydration step. This may relate to
dehydration of
a hydrocarbon or petroleum oil stream entering a refinery tank farm or static
settling of
an emulsion downstream of the desalter.
The contact time for the peroxyacid will vary depending upon the process and
wash water, petroleum oil and/or hydrocarbon feedstock to be treated. Here,
the
peroxyacid is simply added and mixed with the oil, and then is removed along
with the
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water phase and particulates. In an embodiment, the amount of peroxyacid added
to the
petroleum oil or feedstock will depend upon the oil or feedstock to be
treated. As one
skilled in the art appreciates, the amount of metals (e.g. iron) or
particulates in the oil or
feedstock can vary significantly. For example, slop oil may have a higher
concentration
of metals and particulates than crude oil. In an aspect, the concentration of
peroxyacid
provided is between about 1 ppm and about 50,000 ppm, between about 1,000 ppm
and
about 30,000 ppm, between about 1,000 ppm and about 20,000 ppm, or ranges
there
between. In an aspect, the concentration of peroxyacid is at least about 1
ppm, at least
about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least
about 4,000
ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000
ppm, at least
about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or
ranges there
between.
In an embodiment, one or more demulsifiers are added to the crude oil or wash
water. The peroxyacid may also act as a demulsifier.
In an aspect, the methods beneficially reduce the metals and particulate
content in
the petroleum oil or refinery stream by at least about 80%, at least about
85%, at least
about 90%, at least about 95%, at least about 99%, or complete removal. As one
skilled
in the art will ascertain the percentage of reduction of metals and
particulates will be
determined by the concentration of the materials in the oil and/or hydrocarbon
feedstock
to be treated, along with the concentration of peroxy acid employed. In a
further aspect,
the reduction of the metals and particulate content is achieved without any
residual
peroxyacid in the petroleum oil or feedstock. In a further aspect, the methods
beneficially
remove the metals and particulates from the hydrocarbon phase of the emulsion
with little
or no additional hydrocarbon entrainment into the aqueous phase.
Additional Methods of Use
The methods of using peroxyacids and peroxyacid compositions to remove fine
particulates from petroleum oils and refinery feedstocks and/or streams are
also useful in
various additional applications. The methods of mitigation of other metals
using the
peroxyacids are also useful for minimizing fouling, resolving emulsions and
improving
waste water quality associated with petroleum oil and refinery feedstocks. The
peroxyacids can be added to the oil and feedstocks to remove metals and
particulates and
are effective to improve the waste water from the system due in part to its
decomposition
17
into innocuous components (i.e., acetic acid, oxygen, CO2 and H20). Moreover,
the
biocidal efficacy of the peroxyacids can also improve the waste water.
The methods are also useful for enhancing coke quality via contaminate
removal.
Highly crystalline needle coke that can be used for anodes in the aluminum and
steel
industry is more valuable than fuel grade coke. The crystal structure does not
foini in the
presence of metal contaminants. Removing metals with peroxyacids promotes a
higher
grade of coke.
The methods are also useful for mitigating fine particulates resulting from
use of
metal based H2S scavengers in aqueous and hydrocarbon streams. The methods are
also
useful for mitigating fine particulates resulting from Aluminum and Zinc based
chemical
additives. The peroxyacids added to the oil and feedstocks to remove metals
and
particulates beneficially remove various types of particulates from these
streams,
including solids imparted by the various chemical additives used in the
processing of the
oil.
In addition, the methods are useful for mitigation of downstream catalyst
poisoning and fouling, resulting in elongation of catalyst lifetimes. The
peroxyacids
added to the oil and feedstocks to remove metals and particulates beneficially
removes
these poisons from the oil and feedstock, taking them out of the downstream
product
which minimizes downstream catalyst poisoning and fouling. As various metals
and
contaminants can poison or deactivate catalysts, it is beneficial to remove
the various
metals and particulates with the peroxyacids.
Still further the methods are useful for reducing bacteria in slop oil and
crude
tanks. In an aspect, the combination of removing bacteria, contaminants, and
particulates
from slop oil and crude tanks is beneficial, as these sources are known to
have greater
amounts of iron and would therefore benefit from treatment with the
peroxyacid.
All publications and patent applications in this specification are indicative
of the
level of ordinary skill in the art to which this invention pertains.
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EXAMPLES
The foregoing may be better understood by reference to the following examples,
which are presented for purposes of illustration and are not intended to limit
the scope of
this invention. It should be understood that these Examples, while indicating
certain
embodiments of the invention, are given by way of illustration only. From the
above
discussion and these Examples, one skilled in the art can ascertain the
essential
characteristics of this invention, and without departing from the spirit and
scope thereof,
can make various changes and modifications of the embodiments of the invention
to adapt
it to various uses and conditions. Thus, various modifications of the
embodiments of the
invention, in addition to those shown and described herein, will be apparent
to those
skilled in the art from the foregoing description. Such modifications are also
intended to
fall within the scope of the appended claims. The following materials were
used in the
experiments set forth in the Examples:
EC6818A ¨ 15% peracetic acid with 10% hydrogen peroxide in water
EC6779A - 21% peracetic acid with 3% hydrogen peroxide in water
EC2472A ¨ primary emulsion breaker used to promote oil-water separation
R-3461 ¨ 30% sodium gluconate in water
EC2111A ¨ glacial acetic acid
EC2483A ¨ malic acid
EC2580A ¨ heavy metal removal agent (polymeric material)
EC 2345 A ¨ reverse emulsion breaker/flocculent
CORR11540A ¨ upstream application sodium gluconate corrosion inhibitor and
deoiler
EC9008B ¨anionic and non-anionic surfactant blend
The portable electric desalter (PED) screening uses an Interav Model EPPT-228
apparatus. The following test method was used:
Method for replicating refinery desalting applications were employed by
preparing water-in-oil emulsions by blending a fixed volume of water and crude
oil under
controlled conditions. The emulsion was prepared as follows:
1. Charge 8
prescription bottles (6 oz.) with 10 mL of deionized water. Add
the metals removal agent directly to the water phase (dosage to be based on
total volume
of water + crude oil).
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2. Gently layer raw crude oil into each prescription bottle so that the
total
volume of liquid is equivalent to 100 mL. Add the appropriate metals removal
agent
directly to the hydrocarbon phase (dosage to be based on total volume of water
+ crude
oil).
3. Use a microliter
syringe to add the appropriate amount of emulsion breaker
formulation to the hydrocarbon.
4. Cap the bottles loosely to prevent over-pressurization in the heated
water
bath. Place the containers into a water bath and equilibrate to 90 C for at
least 20 minutes.
Confirm the PED heater block is set to 90 C and place the PED tubes inside.
5. After 20 minutes
of heating, pour the contents of Sample #1 into the first
blender jar. Attach a blender cap to prevent overflow during mixing.
6. Adjust the output voltage of the rheostat to an appropriate setting
(e.g., 50
% ¨ 100 % of full power).
7. De-gas the emulsion sample by turning the blended ON and OFF as
quickly as possible. Immediately after degassing, turn ON the blender and
emulsify the
sample for exactly 10 seconds. Warning: Adequate de-gassing and use of the
blender cap
should prevent blender contents from foaming over the rim of the container.
8. Pour the contents of the blender into the first PED tube. Attach the
electrode cap and tighten firmly by hand. Place the sample tube in the rack in
the Sample
#1 position.
9. Repeat Steps 7 ¨ 10 for each of the remaining samples, placing Sample #2
in the second position, etc. Use a clean blender container for each sample.
Once the emulsions are poured into glass tubes (100 ml centrifuge tubes),
which
are then placed into the heating block of a PED heater unit, the emulsions are
resolved
with the assistance of constant heating and intermittent application of an
electric field.
The water coalescence was performed as follows:
1. When all tubes
have been blended, place them inside the heating block in
the appropriate positions. Increase the set temperature of the heating block
from 90 C to
120 C.
2. Place the
electrode assembly cover plate over the heater block to complete
the electrical connection.
3. Adjust the voltage control dial to the appropriate output voltage to
apply
electric fields. Electric field applications are generally ten-minutes in
duration and the
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applied voltage is adjustable between 0 ¨ 4000 V. The first electric field
application is
normally 3000 V, but the value may vary depending on observations from
previous tests.
4. Current flow to the PED tubes is detected during the electric field
applications by toggling the eight individual switches located directly below
the ammeter.
Upon toggling each switch the needle should briefly deflect on the ammeter and
return to
the rest value.
5. After the first electric field application, confirm that voltage is no
longer
being applied by visual inspection of the warning light. Adjust the voltage
control to the
zero setting and remove the electrode assembly cover plate.
6. The volume of free water (in milliliters) that has separated in each PED
tube after 10 minutes have elapsed is recorded. Free water is recorded as the
highest
volume increment where a flashlight beam is transmitted through the PED tube.
If most
of the water has resolved remove the tubes from the heater block. If less than
10 mL of
water is observed repeat the voltage application until all the tubes have
resolved most of
the added water.
7. Transfer the PED tubes to a cooling rack.
8. Once the temperature is below 90 C the tubes can be opened. Sample the
water phase with glass pipettes taking care to leave behind as much oil as
possible. It
may be necessary to repeat the extraction.
9. Submit the water samples for analysis via ICP.
The steps permit the resolution of the emulsion to be observed as the volume
of
free water resolved at fixed intervals during the testing. At the end of each
test the
resulting water phase was collected and submitted for analysis by Inductively
Coupled
Plasma (ICP).
The following test method was used in the Examples for a Bottle Testing:
Bottle testing was performed to identify chemistries most effective at
migrating
metal content to the water phase following emulsion resolution. A known amount
of a
representative sample of the crude oil and 10-20 mL of distilled water were
placed in a
series of standard bottles. One of these samples remained untreated and was
used as a
reference blank while the others were treated with the evaluated chemistries.
The bottles
were agitated simultaneously and replaced in the water bath. At specific times
the amount
of separated water was observed and recorded. The times of dehydration is
according to
the retention time in the separations vessels of the plant. Finally, this
separated water was
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removed and submitted for analysis by ICP.
The methods for emulsion preparation were as follows:
1. Charge medicine bottles with 100 mL the emulsion of interest.
2. Determine the relative amount of water in each emulsion by conducting a
BS&W test per ASTM D-4007.
3. Use a microliter syringe to add the appropriate amount of emulsion
breaker formulation to the emulsion.
4. Use a microliter syringe to add the appropriate amount of metals removal
agent to the emulsion
5. Cap the bottles
and shake all the samples simultaneously on a mechanical
shaker.
6. If the emulsion
requires heat for treatment, place the bottles in a water
bath at the system temperature. Carefully loosen the caps on the bottles
before placing in
the water bath.
7. Observe and
record the water drop, interface and water quality observed
in each bottle. When most of the water has resolved sample it with a glass
pipette, taking
care to leave as much oil behind as possible.
8. Sample the water again if necessary, to remove as much oil as possible.
9. Submit the water samples for analysis by ICP.
EXAMPLE 1
Testing was conducted using the Portable Electric Desalter Screening methods
to
assess whether peracetic acid, sodium gluconate or combinations of the two
additives
could effectively migrate iron containing material from a crude oil fraction
into a water
phase. Metal content of a heavy crude oil sample, as reported by ICP, is shown
in Table
1.
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TABLE 1
Metal Total (ppm) Soluble
Aluminum (Al) 4.0 0.3
Barium (Ba) 2.0 0.1
Calcium (Ca) 14.5 2.9
Chromium (Cr) 0.2 0.1
Cobalt (Co) 0.4 0.4
Copper (Cu) 1.2 0.2
Iron (Fe) 40.3 4.5
Magnesium (Mg) 3.1 0.8
Manganese (Mn) 0.7 0.2
Molybdenum (Mo) 0.6 0.4
Nickel (Ni) 37.3 37.3
Potassium (K) 14.1 2.3
Sodium (Na) 64.2 8.7
Strontium (Sr) 0.9 0.1
Titanium (Ti) 0.8 0.3
Vanadium (V) 165.0 165.0
Zinc (Zn) 1.9 0.7
90 mL of the crude oil, 10 mL of deionized water and 50 ppm of EC2472A
(emulsion breaker) were added to 160 mL medicine bottles. EC6779A (peracetic
acid)
or R-3461 (sodium gluconate in water) were screened. The additives were added
to either
the water or hydrocarbon phase at a concentration of 0, 1000, or 5000 ppm
based on the
total volume as specified in Table 2. The peracetic acid sample used was off-
spec and
reported at 16% actives. The solutions were then heated to 90 C for 30 minutes
and then
emulsified using 50% shear power. The resulting emulsions were transferred
into PED
tubes, capped, heated to 120 C and shocked continuously for 40 minutes with
4000 V.
The resulting water phase was collected and submitted for ICP analysis. The
partitioning
of metals from the hydrocarbon phase to the water phase was analyzed. The
concentration
of Fe, Ni and Zn found in the water is given in Table 2.
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TABLE 2
FeS
Ratio of Dissolver Concentration
EC6779A Total and phase the Zinc
Medicine to R-3461 Dosage Fe dissolver Iron
(Fe, Nickel (Ni, (Zn,
Bottle Solution (ppm) was added to: ppm) PPnl) ppm)
3 1:1 5000 hydrocarbon 141 309 12.9
4 1:3 5000 hydrocarbon 105 71.2 6.98
0:1 5000 hydrocarbon 51.8 6.03 0.26
7 3:1 5000 water 109 279 14.9
8 NA 0 50.5 34.4 1.16
9 1:1 5000 water 129 624 6.01
1:3 5000 water 106 220 5.23
_
11 0:1 5000 water 57.3 140 0.63
12 1:0 1000 hydrocarbon 88.4 152 3.32
13 3:1 1000 hydrocarbon 79.1 45.5 2.27
14 1:1 1000 hydrocarbon 77.3 178 3.01
1:3 1000 hydrocarbon 64 - 130 1.12
16 NA 0 11.6 0.69 <0.25
17 0:1 1000 hydrocarbon 8.05 56.3 <0.25
18 1:0 1000 water 85.1 139 4.69
19 3:1 1000 water 80.4 92.6 3.4
1:1 1000 water 68.4 34 0.98
21 1:3 1000 water 59.8 27 0.93
22 0:1 1000 water 18.8 25.7 <0.25
Percent iron removal to the water phase, following addition of 0-1000 ppm of a
metals removal agent, is shown in FIG. 2. The brown (hydrocarbon addition)
versus blue
5 (vvater
addition) designations are used to define which phase the metal removal agent
was
charged into prior to emulsification. The blank sample, which contained no
metals
removal agent, had considerably less iron in the water at the conclusion of
the test than
the emulsions treated with EC6779A. By itself, R-3461 (sodium gluconate) was
not
effective at facilitating migration of iron to the hydrocarbon phase.
10 Migration
of Fe to the water phase is shown as proportional to the overall dosage
of EC6779A. 5000 ppm treats with EC6779A and 33% R-3461 solution gave upwards
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of 30% iron removal. Similar observations were observed with regards to Ni and
Zn
removal as shown in FIG. 3 and FIG. 4, respectively.
EXAMPLE 2
A second test was conducted to verify reproducibility of the observed trends
in
Example #1. A sample of light crude oil was used and total metals analysis by
ICP is
given in Table 3. The concentration of iron in the sample was abnormally high.
This was
likely a result of corrosion of the metal container the sample was stored in.
TABLE 3
Total Metal PPm
Aluminum (Al) 5.79
Barium (Ba) 12.3
Calcium (Ca) 53.6
Chromium (Cr) 0.131
Cobalt (Co) <0.012
Copper (Cu) 6.73
Iron (Fe) 170
Magnesium (Mg) 13.2
Manganese (Mn) 2.14
Molybdenum (Mo) 0.06
Nickel (Ni) 1.76
Potassium (K) 7.36
Sodium (Na) 199
Strontium (Sr) 1.92
Titanium (Ti) 0.159
Vanadium (V) 2.99
Zinc (Zn) 10.7
The only modifications to the Example 1 method were as follows. The additives
were added to either the water or hydrocarbon phase at a concentration of 500
ppm based
on the total volume as specified in Table 4. The solutions were then heated to
90 C for
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30 minutes and then emulsified using 80% shear power. The concentration of Fe,
Al, Ni,
and Zn found in the water is tabulated in Table 4.
TABLE 4
Fe Ni
Bottle Added to Ratio of EC6779A to R- Al (PPm) (nPin) Zn
3461 (nP111)
(PPnl)
1 hydrocarbon EC6779A 97.8 93.4 198 44.3
2 hydrocarbon 3 part EC6779A to 1
part R- 33.5 138 210 47.5
3461
3 hydrocarbon 1 part EC6779A to 1
part R- 3.76 118 168 18.7
3461
4 hydrocarbon 1 part EC6779A to 3
part R- 8.97 102 82 13.1
3461
hydrocarbon R-3461 9.36 7.94 2.71 0.46
6 water EC6779A 18.9 114 128 49.2
7 water 3 part EC6779A to 1 part R- 21.5
-- 108 -- 155 -- 40.3
3461
not not
8 blank detected 2.28 4.42 detected
9 water 1 part EC6779A to 1 part R- 11.4
125 r 88.4 40
3461
water 1 part EC6779A to 3 part R- 5.69 137 5.62
11.7
3461
11 water R-3461 3.56 10.2 1.15 0.45
not not
12 blank detected 1.9 1.01
detected
5
The percent iron and zinc removal results, based on the total concentration in
the
light crude, are broken out in FIG. 5 and FIG. 6, respectively. EC6779A was
again
observed to help facilitate Zn, Fe, and Al removal. Overall, there was a
significant
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increase in the concentration of the metals in the water phase relative to the
blank or R-
3461 treated emulsions.
EXAMPLE 3
Additional testing was completed to compare metal removal achieved by
EC6779A, EC6818A, EC2111A and EC2483A. Test methodology of Example 1 was
followed using 25 ppm of EC2472A and a sample of light crude oil from the
United
States. EC6818A, EC6779A, EC2111A and EC2483A were tested at 1000 ppm each and
compared to a blank. The emulsions were formed with 10% deionized water at 80%
Variac power. Total metals analysis by ICP is given in shown in Table 5 and
the results
shown in Table 6.
TABLE 5
WTS
metal ppm
Aluminum (Al) 0.515
Barium (Ba) 0.073
Calcium (Ca) 4.43
Chromium (Cr) 0.046
Cobalt (Co) <0.012
Copper (Cu) 0.139
Iron (Fe) 24.5
Magnesium (Mg) 1.18
Manganese (Mn) 0.117
Molybednum (Mo) <0.025
Nickel (Ni) 3.7
Potassium (K) 0.733
Sodium (Na) 13.7
Strontium (Sr) 0.084
Titanium (Ti) 0.055
Vanadium (V) 6.98
Zinc (Zn) 0.538
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TABLE 6
EC2472A
Aluminum Calcium Iron Nickel Zinc
Bottle (ppm) Additive (ppm) (ppm) (PPnl.) (ppm) (ppm)
1 25 blank <0.150 14.5 3.96 0.238
0.106
2 25 1000 ppm 17.1 17 98 - 123 3.36
EC6779A
3 25 1000 ppm 18.6 34.3 109 22.4 14.9
EC6818A
4 25 1000 ppm 14.4 16.9 46.9 7.56
0.524
EC2111A
25 1000 ppm 14.4 16.9 46.9 7.56 0.524
EC2483A
6 25 blank 1.03 112 7.19 0.951
0.473
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The percent iron removal to the resolved water is shown in FIG. 7. EC6818A
demonstrated the strongest performance under these conditions. EC2111A and
EC2483A
did not show competitive performance to the two formulations containing the
peroxy acid.
The same observation is observed with regards to Zn and Ni removal.
EXAMPLE 4
Example 3 testing was repeated under the same conditions to analyze increased
dosages of the chemistries and the effect of R-3461 on EC6818A and EC6779A
performance. The experimental design and concentration of metals found in the
resolved
water is shown in Table 7.
TABLE 7
Aluminum Iron Nickel Zinc
Additive
(1)Pm) (ppm) (ppm) (ppm)
2500 ppm EC2111A 20.8 27.5 8.23 2.93
2500 ppm EC2483A 4.9 34.8 1.15 0.567
blank 3,3 11.9 0.765 0.347
2500 ppm EC6779A 15.6 111 66.5 3.39
5000 ppm EC6779A 48.7 99.2 170 8.61
2500 ppm EC6779A with 2500 ppm R-3461 4.07 100 77.8 2.77
2500 ppm EC6818A 5.28 95 214 6.52
5000 ppm EC6818A 7.1 83.8 304 5.36
2500 ppm EC6818A with 2500 ppm R-3461 4.24 80.6 105 3.85
blank 3.27 17.6 26.8 2
Additional data regarding performance is shown in Table 8.
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TABLE 8
Aluminum Iron Nickel Zinc
Additive (Al) (Fe) (Ni) (Zn)
2500 ppm EC2111A 449 12 25 61
2500 ppm EC2483A 106 16 3 12
blank 71 5 2 7
2500 ppm EC6779A 337 50 200 70
5000 ppm EC6779A 1051 45 511 178
2500 ppm EC6779A with 2500 ppm R-3461 88 45 234 57
2500 ppm EC6818A 114 43 643 135
5000 ppm EC6818A 153 38 913 111
2500 ppm EC6818A with 2500 ppm R-3461 91 37 315 80
blank 71 8 80 41
The percent metals removal is substantially higher than expected based on the
ICP analysis of the crude oil. In addition, the blanks show considerably
different values
for Zn and Ni suggesting the homogeneity of the crude oil sample may be of
concern, R-
3461A did not boost the peroxyacid formulations' performances demonstrating
that the
use of sodium gluconate is not required in combination with the peroxyacid
compositions.
However, again, the two peroxyacid formulations outperformed the carboxylic
acids
EC2111A (acetic acid) and EC2483A (malic acid) as shown in FIG. 8.
Filterable solids analysis on the top oil fraction of the resolved emulsion
this
testing is shown in FIG. 9 and suggest that solids removal has been effective
relative to
the blanks with the peroxyacid formulations.
EXAMPLE 5
Bottle Testing methodology was used to assess efficacy of various metal
removal
agents. Characterization of the emulsion band formed while processing this
slate found
9300 ppm Fe, suggesting the Fe may play a role in emulsion stabilization. The
crude oil
(treated at the refinery with emulsion breaker) was homogenized and then 90 mL
aliquots
were transferred into five medicine bottles containing 10 mL of distilled
water each.
Three of the bottles were charged with one of the following metal removal
agents at 1000
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ppm: EC2111A, EC6779A or CORR11540A. The samples were emulsified using 100%
shear and transferred to a heating block set to 120 C. The emulsions were
then shocked
with 4000 V for 20 minutes to facilitate complete emulsion resolution. The
samples were
then cooled to ambient temperature. The resolved water phases were collected
for
analysis by ICP and the results are shown in Table 9. C0RR11540A, a solution
of R-
3461 with a surfactant, did not show performance relative to EC2111A and
EC6779A.
This suggests again that the chelant is not effective in the absence of an
acid.
TABLE 9
Aluminum (Al) Iron (Fe) Nickel (Ni) Zinc (Zn)
Treatment (ppm) (ppm) (1)Pm) (ppm)
Blank 1 <0.75 <0.12 1.13 <0.25
EC2111A (1000 ppm) 7.72 3.55 14.8 1.66
EC6779A (1000 ppm) 9.86 1.51 7.67 0.39
CORR11540A (1000 ppm) <0.75 0.97 2.02 <0.25
Blank 2 <0.75 0.33 0.46 <0.25
EXAMPLE 6
The ability of peroxyacetic acid to remove metals from slop oil was analyzed.
A
sample of slop oil was received in the form of a stable emulsion. The emulsion
does not
resolve after prolonged periods of quiescent settling in the absence of
chemical treatment.
The sample received was homogenized and sampled into 100 mL aliquots. One
aliquot
each was treated with 1000 ppm of EC2483A or EC6779A. After 48 hours all the
samples contained emulsion except those treated with EC6779A.
EXAMPLE 7
The ability of peroxyacetic acid to remove metals from slop oil (as a stable
emulsion) was further analyzed. The emulsion does not resolve after prolonged
periods
of quiescent settling in the absence of chemical treatment. The sample
received was
homogenized and sampled into 100 mL aliquots. One aliquot each was treated
with 1000
or 5000 ppm of EC2111A (acetic acid) or EC6779A (peracetic acid). The treated
emulsions were stored for 24 hours. The two samples treated with EC6779A
contained
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1% resolved water. The samples were then centrifuged at 140 C for 30 minutes.
Pictures
of the resulting resolved emulsion are provided in FIG. 10. The EC6779A
samples
contained yellow water and significantly more oil free solids were observed at
the bottom
of the tubes. ICP analysis on the top oil fraction and the resolved water
phase are given
in Table 10.
TABLE 10
Al Ca Fe Zn
Water Analysis (ppm) (ppm) (PPnl) Ni V (ppm) pH*25 C
(ppm) (PPnl)
5000 ppm EC6779A 29.3 676 281 2.06 4.76 81.8 3
1000 ppm EC6779A 9.22 738 175 0.727 0.431 26.5
3
_
5000 ppm EC2111A 70.5 702 191 0.182 0.57 0.946
3
1000 ppm EC2111A 18.9 ' 738 159 0.175 0.156
1.53 3
Al Ca Fe Zn
Karl
Hydrocarbon (ppm) (ppm) (1)Pnl) Ni V
(ppm) Fischer
Skimmings (ppm) (1)Pm)
Water
5000 ppm EC6779A 101 122 288 32.8 98.6 21
0.34
1000 ppm EC6779A 73.6 60.9 249 36..8 114 23.2
0.48
5000 ppm EC2111A 16.4 7.42 45.6 39.4 120 7.71
0.35
1000 ppm EC2111A 26.4 23.1 70.8 38.2 119 9.43 0.1
Slop oil without 234 534 686 15 44.1 66.1
treatment
%Removal of Metals
to the Water Phase Al (%) Ca Fe (%) Ni (%) V
(%) Zn
(%) (%)
5000 ppm EC6779A 56 149 83 15 44 44
1000 ppm EC6779A 35 150 181 16 49 21
5000 ppm EC2111A 37 133 101 17 52 4
1000 ppm EC2111A 19 143 98 16 51 5
EXAMPLE 8
A gallon of a light crude oil from the Gulf Coast was collected for ICP
analysis.
An aliquot of this crude oil found 25 ppm Fe, 4 ppm Ni, and 1 ppm Zn. The
crude oil
was homogenized and then 90 mL aliquots were transferred into eight medicine
bottles
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containing 10 mL of distilled water each. The bottles were all charged with 25
ppm
EC2472A and the metal removal agents as outlined in Table 11.
TABLE 11
Filterable Solids on Top
Bottle Additive Oil Fraction (ppm)
1 blank 1768
2 1000 ppm EC6779A NA
3 1000 ppm EC6818A 1210
4 1000 ppm EC2111A 1800
1000 ppm EC2483A 1833
6 blank 2008
7 2500 ppm EC2111A 1490
8 2500 ppm EC2483A 2008
9 blank 1755
2500 ppm EC6779A 1396
11 5000 ppm EC6779A 1152
2500 ppm EC6779A with 2500 ppm
12 R-3461 2071
13 2500 ppm EC6818A 1501
14 5000 ppm EC6818A 1588
2500 ppm EC6818A with R-3461 1872
16 blank 976
5
The samples were emulsified using 80% shear and transferred to a heating block
set to 120 C. The emulsions were then shocked with 3000 V for 20 minutes to
facilitate
complete emulsion resolution. The samples were then cooled to ambient
temperature.
The top oil fraction was sampled for filterable solids (right column of Table
11) and the
10 resolved water phases were collected for analysis by ICP (Table 12).
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TABLE 12
Aluminu Iron Nickel Zinc
Bottle Additive In (PPIn) (PPIn) (ppm) (PPIn)
1 blank <0.150 3.96 0.238 0.106
2 1000 ppm EC6779A 17.1 98 123 3.36
3 1000 ppm EC6818A 18.6 109 22.4 14.9
4 1000 ppm EC2111A 14.4 46.9 7.56 0.524 '
_
1000 ppm EC2483A 14.4 46.9 7.56 0.524
6 blank 1.03 7.19 0.951 0.473
7 2500 ppm EC2111A 20.8 27.5 8.23 2.93
8 2500 ppm EC2483A 4.9 34.8 1.15 0.567
9 blank 3.3 11.9 0.765 0.347 '
_
2500 ppm EC6779A 15.6 111 66.5 3.39
11 5000 ppm EC6779A 48.7 99.2 170 8.61
2500 ppm EC6779A with 2500
12 ppm R-3461 4.07 100 77.8 2.77
13 2500 ppm EC6818A 5.28 95 214 6.52
14 5000 ppm EC6818A 7.1 83.8 304 5.36
.
2500 ppm EC6818A with 2500
ppm R-3461 4.24 80.6 105 3.85
16 blank 3.27 17.6 26.8 2
% Removal of Ni, Fe, Al and Zn is given in Table 13 and was approximated using
the
5 total metals analysis on the raw crude sample. R-3461 did not promote
metals removal
when coupled with the peroxyacids. EC6779A and EC6818A outperformed EC2111A
and EC2483A. It is unclear which peroxyacid formulation is more effective
based on
this testing.
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TABLE 13
% Migration from the Hydrocarbon
Phase
Aluminum Iron Nickel Zinc
Bottle Additive (AI) (Fe) (Ni) (Zn)
1 blank 2 1 2
2 1000 ppm EC6779A 369 44 369 69
3 1000 ppm EC6818A 401 49 67 308
4 1000 ppm EC2111A 311 21 23 11
1000 ppm EC2483A 311 21 23 11
6 blank 22 3 3 10
7 2500 ppm EC2111A 449 12 25 61
8 2500 ppm EC2483A 106 16 3 12
9 blank 71 5 2 7
2500 ppm EC6779A 337 50 200 70
11 5000 ppm EC6779A 1051 45 511 178
2500 ppm EC6779A with
12 2500 ppm R-3461 88 45 234 57
_
13 2500 ppm EC6818A 114 43 643 135
14 5000 ppm EC6818A 153 38 913 111
2500 ppm EC6818A with
2500 ppm R-3461 91 37 315 80
16 blank 71 8 80 41
The inventions being thus described, it will be obvious that the same may be
5 varied in many ways. Such variations are not to be regarded as a
departure from the spirit
and scope of the inventions and all such modifications are intended to be
included within
the scope of the following claims. The above specification provides a
description of the
manufacture and use of the disclosed compositions and methods. Since many
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embodiments can be made without departing from the spirit and scope of the
invention,
the invention resides in the claims.
The features disclosed in the foregoing description, or the following claims,
or
the accompanying drawings, expressed in their specific forms or in terms of a
means for
performing the disclosed function, or a method or process for attaining the
disclosed
result, as appropriate, may, separately, or in any combination of such
features, be utilized
for realizing the invention in diverse forms thereof.
36
