U.S. patent application number 15/130450 was filed with the patent office on 2017-03-09 for additives to enhance metal and amine removal in refinery desalting processes.
This patent application is currently assigned to Baker Petrolite LLC. The applicant listed for this patent is Baker Petrolite LLC. Invention is credited to Lawrence N. Kremer, Tran M. Nguyen, Jerry J. Weers.
Application Number | 20170066975 15/130450 |
Document ID | / |
Family ID | 31997696 |
Filed Date | 2017-03-09 |
United States Patent
Application |
20170066975 |
Kind Code |
A9 |
Nguyen; Tran M. ; et
al. |
March 9, 2017 |
ADDITIVES TO ENHANCE METAL AND AMINE REMOVAL IN REFINERY DESALTING
PROCESSES
Abstract
It has been discovered that metals and/or amines can be removed
or transferred from a hydrocarbon phase to a water phase in an
emulsion breaking process by using a composition that contains
water-soluble hydroxyacids. Suitable water-soluble hydroxyacids
include, but are not necessarily limited to glycolic acid, gluconic
acid, C.sub.2-C.sub.4 alpha-hydroxy acids, poly-hydroxy carboxylic
acids, thioglycolic acid, chloroacetic acid, polymeric forms of the
above hydroxyacids, poly-glycolic esters, glycolate ethers, and
ammonium salt and alkali metal salts of these hydroxyacids, and
mixtures thereof. The composition may also include at least one
mineral acid to reduce the pH of the desalter wash water. A solvent
may be optionally included in the composition. The invention
permits transfer of metals and/or amines into the aqueous phase
with little or no hydrocarbon phase undercarry into the aqueous
phase. The composition is particularly useful in treating crude oil
emulsions, and in removing calcium and other metals therefrom.
Inventors: |
Nguyen; Tran M.; (Houston,
TX) ; Kremer; Lawrence N.; (The Woodlands, TX)
; Weers; Jerry J.; (Richmond, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Baker Petrolite LLC |
Sugar Land |
TX |
US |
|
|
Assignee: |
Baker Petrolite LLC
Sugar Land
TX
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20160230101 A1 |
August 11, 2016 |
|
|
Family ID: |
31997696 |
Appl. No.: |
15/130450 |
Filed: |
April 15, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13008615 |
Jan 18, 2011 |
9434890 |
|
|
15130450 |
|
|
|
|
12390631 |
Feb 23, 2009 |
8372271 |
|
|
13008615 |
|
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|
|
10649921 |
Aug 27, 2003 |
7497943 |
|
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12390631 |
|
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|
60407139 |
Aug 30, 2002 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 31/08 20130101;
C10G 2300/44 20130101; C10G 2300/205 20130101; C10G 2300/202
20130101; C10G 2300/805 20130101; B01D 17/047 20130101; C10L
2290/545 20130101; B01D 17/0217 20130101; C10G 33/04 20130101; C10G
17/04 20130101; C10G 33/02 20130101; C10G 2300/80 20130101; B01D
17/0217 20130101; B01D 17/047 20130101 |
International
Class: |
C10G 17/04 20060101
C10G017/04; C10G 31/08 20060101 C10G031/08; C10G 33/02 20060101
C10G033/02 |
Claims
1. A method of transferring metals and amines from a crude oil
entering a refinery desalting process to an aqueous phase leaving
the refinery desalting process, the method comprising the steps of:
adding an effective amount of a hydroxyacid composition to a wash
water entering the refinery desalting process to transfer metals
and amines from the crude oil to the aqueous phase, the hydroxyacid
composition comprising at least one water-soluble hydroxyacid
selected from the group consisting of glycolic acid, gluconic acid,
C.sub.2-C.sub.4 alpha-hydroxy acids, malic acid, lactic acid,
poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic
acid, polymeric forms of the above hydroxyacids, poly-glycolic
esters, glycolate ethers, and ammonium salt and alkali metal salts
of these hydroxyacids, and mixtures thereof; lowering the pH of the
wash water to below 5, before, during and/or after adding the
hydroxyacid composition to the wash water; adding the wash water to
the crude oil to create a water-in-oil emulsion by dispersing the
wash water into the crude oil using a mixing valve, where
dispersing the wash water into the crude oil creates water droplets
dispersed throughout the crude oil; and resolving the water-in-oil
emulsion using electrostatic coalescence to create the aqueous
phase and a desalted crude oil ready for further processing that
leave the refinery desalting process, where the water droplets
throughout the crude oil coalesce into increasingly larger droplets
and at least a portion of the metals and amines are transferred
from the crude oil in the water-in-oil emulsion to the aqueous
phase.
2. The method of claim 1, where the effective amount of the
hydroxyacid composition is added to the wash water in water.
3. The method of claim 1, where the effective amount of the
hydroxyacid composition is added to the wash water in a
solvent.
4. The method of claim 1, where the pH of the wash water is lowered
to below 4 before, during and/or after adding the hydroxyacid
composition to the wash water.
5. The method of claim 1, where the effective amount of the
hydroxyacid composition is present in the water-in-oil emulsion in
an amount ranging from 1 to 2000 ppm-w.
6. The method of claim 1 where the hydroxyacid composition further
comprises at least one additional component selected from the group
consisting of a water or alcohol solvent, a corrosion inhibitor, a
demulsifier, a scale inhibitor, metal chelants, wetting agents and
mixtures thereof.
7. A method of transferring metals and amines from a crude oil
entering a refinery desalting process to an aqueous phase leaving
the refinery desalting process, the method comprising the steps of:
adding an effective amount of a hydroxyacid composition to a wash
water entering the refinery desalting process to transfer metals
and amines from the crude oil to the aqueous phase, the hydroxyacid
composition comprising at least one water-soluble hydroxyacid
selected from the group consisting of glycolic acid, gluconic acid,
C.sub.2-C.sub.4 alpha-hydroxy acids, malic acid, lactic acid,
poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic
acid, polymeric forms of the above hydroxyacids, poly-glycolic
esters, glycolate ethers, and ammonium salt and alkali metal salts
of these hydroxyacids, and mixtures thereof; lowering the pH of the
wash water to below 5, before, during and/or after adding the
hydroxyacid composition to the wash water; adding the wash water to
the crude oil to create a water-in-oil emulsion by dispersing about
5% wash water into the crude oil using a mixing valve, where
dispersing the wash water into the crude oil creates water droplets
dispersed throughout the crude oil; and resolving the water-in-oil
emulsion using electrostatic coalescence to create the aqueous
phase and a desalted crude oil ready for further processing that
leave the refinery desalting process, where the water droplets
throughout the crude oil coalesce into increasingly larger droplets
and at least a portion of the metals and amines are transferred
from the crude oil in the water-in-oil emulsion to the aqueous
phase.
8. The method of claim 7, where the effective amount of the
hydroxyacid composition is added to the wash water in water.
9. The method of claim 7, where the effective amount of the
hydroxyacid composition is added to the wash water in a
solvent.
10. The method of claim 7, where the pH of the wash water is
lowered to below 4 before, during and/or after adding the
hydroxyacid composition to the wash water.
11. The method of claim 7, where the effective amount of the
hydroxyacid composition is present in the water-in-oil emulsion in
an amount ranging from 1 to 2000 ppm-w.
12. The method of claim 7 where the hydroxyacid composition further
comprises at least one additional component selected from the group
consisting of a water or alcohol solvent, a corrosion inhibitor, a
demulsifier, a scale inhibitor, metal chelants, wetting agents and
mixtures thereof.
13. A method of transferring amines from a crude oil entering a
refinery desalting process to an aqueous phase leaving the refinery
desalting process, the method comprising the steps of: adding an
effective amount of a hydroxyacid composition to a wash water
entering the refinery desalting process to transfer amines from the
crude oil to the aqueous phase, the hydroxyacid composition
comprising at least one water-soluble hydroxyacid selected from the
group consisting of glycolic acid, gluconic acid, C.sub.2-C.sub.4
alpha-hydroxy acids, malic acid, lactic acid, poly-hydroxy
carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric
forms of the above hydroxyacids, poly-glycolic esters, glycolate
ethers, and ammonium salt and alkali metal salts of these
hydroxyacids, and mixtures thereof; lowering the pH of the wash
water to below 5, before, during and/or after adding the
hydroxyacid composition to the wash water; adding the wash water to
the crude oil to create a water-in-oil emulsion by dispersing the
wash water into the crude oil using a mixing valve, where
dispersing the wash water into the crude oil creates water droplets
dispersed throughout the crude oil; and resolving the water-in-oil
emulsion using electrostatic coalescence to create the aqueous
phase and a desalted crude oil ready for further processing that
leave the refinery desalting process, where the water droplets
throughout the crude oil coalesce into increasingly larger droplets
and at least a portion of the amines are transferred from the crude
oil in the water-in-oil emulsion to the aqueous phase.
14. The method of claim 13, where the effective amount of the
hydroxyacid composition is added to the wash water in water.
15. The method of claim 13, where the effective amount of the
hydroxyacid composition is added to the wash water in a
solvent.
16. The method of claim 13, where the pH of the wash water is
lowered to below 4 before, during and/or after adding the
hydroxyacid composition to the wash water.
17. The method of claim 13, where the effective amount of the
hydroxyacid composition is present in the water-in-oil emulsion in
an amount ranging from 1 to 2000 ppm-w.
18. The method of claim 15 where the hydroxyacid composition
further comprises at least one additional component selected from
the group consisting of a water or alcohol solvent, a corrosion
inhibitor, a demulsifier, a scale inhibitor, metal chelants,
wetting agents and mixtures thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent
application Ser. No. 10/649,921 filed on Aug. 27, 2003, now U.S.
Pat. No. 7,497,943 on Mar. 3, 2009, which in turn claims the
benefit of U.S. Provisional Application No. 60/407,139 filed Aug.
30, 2002.
FIELD OF THE INVENTION
[0002] The present invention relates to methods and compositions
for separating emulsions of hydrocarbons and water, and more
particularly relates, in one embodiment, to methods and
compositions for transferring metals and/or amines to an aqueous
phase in an emulsion breaking process.
BACKGROUND OF THE INVENTION
[0003] In an oil refinery, the desalting of crude oil has been
practiced for many years. The crude is usually contaminated from
several sources, including, but not necessarily limited to: [0004]
Brine contamination in the crude oil as a result of the brine
associated with the oil in the ground; [0005] Minerals, clay, silt,
and sand from the formation around the oil well bore; [0006] Metals
including calcium, zinc, silicon, nickel, sodium, potassium, etc.;
[0007] Nitrogen-containing compounds such as amines used to scrub
H.sub.2S from refinery gas streams in amine units, or from amines
used as neutralizers in crude unit overhead systems, and also from
H.sub.2S scavengers used in the oilfield; and [0008] Iron sulfides
and iron oxides resulting from pipeline and vessel corrosion during
production, transport, and storage.
[0009] Desalting is necessary prior to further processing to remove
these salts and other inorganic materials that would otherwise
cause fouling and deposits in downstream heat exchanger equipment
and/or form corrosive salts detrimental to crude oil processing
equipment. Further, these metals can act as poisons for the
catalysts used in downstream refinery units. Effective crude oil
desalting can help minimize the effects of these contaminants on
the crude unit and downstream operations. Proper desalter
operations provide the following benefits to the refiner: [0010]
Reduced crude unit corrosion. [0011] Reduced crude preheat system
fouling. [0012] Reduced potential for distillation column damage.
[0013] Reduced energy costs. [0014] Reduced downstream process and
product contamination.
[0015] Desalting is the resolution of the natural emulsion of water
that accompanies the crude oil by creating another emulsion in
which about 5 percent relative wash water is dispersed into the oil
using a mix valve. The emulsion mix is directed into a desalter
vessel containing a parallel series of electrically charged plates.
Under this arrangement, the oil and water emulsion is exposed to
the applied electrical field. An induced dipole is formed on each
water droplet within the emulsion that causes electrostatic
attraction and coalescence of the water droplets into larger and
larger droplets. Eventually, the emulsion resolves into two
separate phases--the oil phase (top layer) and the water phase
(bottom layer). The streams of desalted crude oil and effluent
water are separately discharged from the desalter.
[0016] The entire desalting process is a continuous flow procedure
as opposed to a batch process. Normally, chemical additives are
injected before the mix valve to help resolve the oil/water
emulsion in addition to the use of electrostatic coalescence. These
additives effectively allow small water droplets to more easily
coalesce by lowering the oil/water interfacial tension.
[0017] Crude oil that contains a high percent of particulate solids
can complicate the desalting process. The particulate solids, by
nature, would prefer to transfer to the water phase. However, much
of the solids in a crude oil from a field exists in tight
water-in-oil emulsions. That is, oil-wetted solids in high
concentration in the crude may help form tight oil and water
emulsions that are difficult to resolve. These tight emulsions are
often referred to as "rag" and may exist as a layer between the
separated oil and water phases. The rag layer inside the desalter
vessel may grow to such an extent that some of it will be
inadvertently discharged with the water phase. This is a problem
for the waste water treatment plant since the rag layer still
contains a high percentage of unresolved emulsified oil.
[0018] As mentioned, much of the solids encountered during crude
oil desalting consists of iron, most commonly as particulate iron
such as iron oxide, iron sulfide, etc. Other metals that are
desirably removed include, but are not necessarily limited to,
calcium, zinc, silicon, nickel, sodium, potassium, and the like,
and typically a number of these metals are present. Some of the
metals may be present in a soluble form. The metals may be present
in inorganic or organic forms. In addition to complicating the
desalter operation, iron and other metals are of particular concern
to further downstream processing. This includes the coking
operation since iron and other metals remaining in the processed
hydrocarbon yields a lower grade of coke. Removing the metals from
the crude oil early in the hydrocarbon processing stages is desired
to eventually yield high quality coke as well as to limit corrosion
and fouling processing problems.
[0019] Several treatment approaches have been made to reduce total
metal levels and these all center on the removal of metals at the
desalter unit. Normally, the desalter only removes water soluble
inorganic salts such as sodium or potassium chlorides. Some crude
oils contain water insoluble metal organic acid salts such as
calcium naphthenante and iron naphthenate, which are soluble or
dispersed as fine particulate matter in the oil but not in
water.
[0020] It would thus be desirable to develop a composition and
method employing it that would cause most or all of the metals in
the crude oil to transfer from the oil phase in a desalter
operation, with little or no oil carryunder in the aqueous phase.
Nonyl phenol resins have been used as desalting additives in the
past, but these materials have come under suspicion as possible
hormonal mimics and are ineffective by themselves of removing
metals such as calcium or iron.
SUMMARY OF THE INVENTION
[0021] Accordingly, it is an object of the present invention to
provide a composition and method of using it that would transfer a
large part of the metals and/or amines in the crude oil to the
aqueous phase in a desalter operation.
[0022] It is another object of the present invention to provide a
composition and method for transferring metals and/or amines from a
hydrocarbon into an aqueous phase in an emulsion breaking operation
without causing oil undercarry into the aqueous phase.
[0023] In carrying out these and other objects of the invention,
there is provided, in one form, a method of transferring metals
and/or amines from a hydrocarbon phase to a water phase involving
adding to an emulsion of hydrocarbon and water, an effective amount
of a composition to transfer metals and/or amines from a
hydrocarbon phase to a water phase containing at least one
water-soluble hydroxyacid. The water-soluble hydroxyacid may be
glycolic acid, gluconic acid, C.sub.2-C.sub.4 alpha-hydroxy acids,
poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic
acid, polymeric forms of the above hydroxyacids, poly-glycolic
esters, glycolate ethers, and ammonium salt and alkali metal salts
of these hydroxyacids, and mixtures thereof. The emulsion is then
resolved into hydrocarbon phase and an aqueous phase, where at
least a portion of the metals and/or amines have been transferred
to the aqueous phase. This is accomplished by converting the water
insoluble salt such as calcium naphthenate into a water soluble
salt such as calcium glycolate.
[0024] In another non-limiting embodiment of the invention, there
is provided a composition for transferring metals and/or amines
from a hydrocarbon phase to a water phase that includes a
water-soluble hydroxyacid (as defined above, including the salts
thereof), and a mineral acid.
[0025] There is provided in another non-limiting embodiment of the
invention a composition for transferring metals and/or amines from
a hydrocarbon phase to a water phase that includes a water-soluble
hydroxyacid (as defined above, including the salts thereof) and at
least one additional component that may be a hydrocarbon solvent, a
corrosion inhibitor, a demulsifier, a scale inhibitor, metal
chelants, wetting agents and mixtures thereof.
[0026] In still another non-limiting embodiment of the invention,
there is provided a treated hydrocarbon emulsion that includes
hydrocarbon, water, and a composition for transferring metals
and/or amines from a hydrocarbon phase to a water phase comprising
a water-soluble hydroxyacid (as defined above, including the salts
thereof).
BRIEF DESCRIPTION OF THE DRAWING
[0027] The FIGURE is a graph of various amines and ammonia
partitioning across desalters as a function of pH.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The inventors have discovered that the addition of glycolic
acid (hydroxyacetic acid) and other water-soluble hydroxyacids to a
crude oil can significantly reduce the amount of calcium and other
metals and/or amines in the hydrocarbon when it is run through a
desalter in a refinery. The inventors have compared the "normal"
desalting on a reference crude oil containing higher than normal
amounts of calcium and found minimal calcium removal. The addition
of glycolic acid in levels of up to a 5:1 ratio with calcium,
results in much lower metals and/or amine content of the desalted
oil. The levels of metals other than calcium such as iron, zinc,
silicon, nickel, sodium and potassium are also reduced. The removal
of particulate iron in the form of iron oxide, iron sulfide, etc.
is a specific, non-limiting embodiment of the invention. By
"removing" the metals and/or amines from the hydrocarbon or crude
is meant any and all partitioning, sequestering, separating,
transferring, eliminating, dividing, removing, of one or more metal
from the hydrocarbon or crude to any extent.
[0029] Being an aqueous additive, the glycolic acid is typically
added to the wash water in the desalter. This improves distribution
of the acid in the oil although addition to the aqueous phase
should not be viewed as a requirement for the composition of the
invention to work.
[0030] The composition and method of the invention will be valuable
to produce high quality (i.e., high purity) coke from crude that
may originally have contained high concentrations of metals and/or
amines and solids, including iron-based solids. Further, the
invention advances the technology by removing inorganic material
from the crude oil without discharging any oil or emulsion to the
waste treatment plant.
[0031] In this invention, it will be understood that the metals
include, but are not necessarily limited to, those of Groups IA,
IIA, VB, VIII, IIB and IVA of the Periodic Table (CAS version). In
another non-limiting embodiment, the metals include, but are not
necessarily limited to calcium, iron, zinc, silicon, nickel,
sodium, potassium, vanadium, and combinations thereof. In
particular, nickel and vanadium are known poisons for catalysts
used in fluid catalytic cracking units (FCCUs) downstream.
[0032] The amines removed in accordance with the method of this
invention may include, but are not necessarily limited to,
monoethanolamine (MEA); diethanolamine (DEA); triethanolamine
(TEA); N-methylethanolamine; N,N-dimethylethanolamine (DMEA);
morpholine; N-methyl morpholine; ethylenediamine (EDA);
methoxypropylamine (MOPA); N-ethyl morpholine (EMO); N-methyl
ethanolamine, N-methyldiethanolamine and combinations thereof.
[0033] In one embodiment of the invention, the composition of the
invention includes a water-soluble hydroxy acid. Hydroxy acids are
defined herein as not including or exclusive of acetic acid. Acetic
acid has sometimes been used to remove metals as well, but it has a
high oil solubility and tends to stay with the hydrocarbon coming
from the desalter. The acidity of the acetic acid can then cause
corrosion problems in the crude unit. The water-soluble hydroxy
acids are much more water-soluble and will not partition as much
into the crude oil, thus reducing downstream concerns. They are
also less volatile and do not distill into the crude unit overhead
system where they can increase corrosion rates when combined with
the water usually present at this location.
[0034] In one preferred, non-limiting embodiment of the invention,
the water-soluble hydroxyacid is selected from the group consisting
of glycolic acid, C.sub.1-C.sub.4 alpha-hydroxy acids, poly-hydroxy
carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric
forms of the above hydroxyacids, glycolate ethers, poly-glycolic
esters, and mixtures thereof. While thioglycolic acid and
chloroacetic acid are not strictly speaking hydroxyacids, they are
functional equivalents thereof. For the purposes of this invention,
they are defined as hydroxyacids. The alpha substituent on the
C.sub.1-C.sub.4 alpha-hydroxy acids may be any C.sub.1-C.sub.4
straight or branched alkyl group. In one non-limiting embodiment of
the invention, the alpha substituent may be C.sub.2-C.sub.4
straight or branched alkyl group and lactic acid is not included.
Gluconic acid, CH.sub.2OH(CHOH).sub.4COOH, is a non-limiting but
preferred polymer of glycolic acid. The glycolate ethers may have
the formula:
##STR00001##
[0035] where n ranges from 1-10. The glycolate esters may have a
formula:
##STR00002##
[0036] where n is as above. Thioglycolic acid and the ethers of
glycolic acid may have the added benefits of a higher boiling
point, and possibly increased water solubility. A higher boiling
point means the additive will not distill into the distillate
fractions in the crude unit and cause corrosion or product quality
concerns. The higher water solubility also favors removal of the
additive from the crude in the desalter and reduces the amount that
may reach the downstream processing units.
[0037] In particular, the definition of water-soluble hydroxyacids
includes ammonium salt and alkali metal salts (e.g. sodium and
potassium salts, etc.) of these hydroxyacids alone or in
combination with the other water-soluble hydroxyacids mentioned.
Such salts would be formed in the desalter wash water as the
system's pH was adjusted with pH adjusters such as sodium
hydroxide, potassium hydroxide, ammonia, and the like.
[0038] In another non-limiting embodiment the water-soluble
hydroxyacids do not include citric acid, malic acid, tartaric acid,
mandelic acid, and lactic acid. In yet another non-limiting
embodiment of the invention, the definition of water-soluble
hydroxyacids does not include organic acid anhydrides, particularly
acetic, propionic, butyric, valeric, stearic, phthalic and benzoic
anhydrides.
[0039] In yet another non-limiting embodiment of the invention,
glycolic acid and gluconic acid may be used to remove calcium and
amines, and thioglycolic acid may be used for iron removal, from
crude oil or another hydrocarbon phase.
[0040] It is expected that the water-soluble hydroxyacids will be
used together with other additives including, but not necessarily
limited to, corrosion inhibitors, demulsifiers, pH adjusters, metal
chelants, scale inhibitors, hydrocarbon solvents, and mixtures
thereof, in a commercial process. Metal chelants are compounds that
complex with metals to form chelates. In particular, mineral acids
may be used since metal removal is best accomplished at an acidic
pH. The use of combinations of water-soluble hydroxyacids,
particularly glycolic acid or gluconic acid, and mineral acids may
give the best economics in a commercial application. Suitable
mineral acids for use in conjunction with the water-soluble
hydroxyacids of this invention include, but are not necessarily
limited to, sulfuric acid, hydrochloric acid, phosphoric acid,
nitric acid, phosphorous acid, and mixtures thereof. As noted, in
one embodiment of the invention, the method of this invention is
practiced in a refinery desalting process that involves washing the
crude emulsion with wash water. In one non-limiting embodiment of
the invention, the amount of mineral acid used may be sufficient to
lower the pH of the wash water to 6 or below. As noted below, in
some embodiments of the invention, it may be necessary or preferred
to lower the pH of the wash water to 5 or below, alternatively to 4
or below. The water-soluble hydroxyacids (and salts thereof) are
expected to be useful over a wide pH range, although in some
situations it may be necessary or desirable to adjust the pH to
achieve the desired contaminant transfer or separation.
[0041] It will be appreciated that the necessary, effective or
desired proportions of the hydroxyacid and/or the mineral acid will
be difficult to predict in advance, since these proportions or
dosages are dependent upon a number of factors, including, but not
necessarily limited to, the nature of the hydrocarbon, the
concentration of metal species and amine to be removed, the
temperature and pressure conditions of method, the particular
hydroxyacid and mineral acid used, etc. In general, the more of a
species, such as calcium, there is to be removed, the more of the
reactive acid that must be added. Since many undesirable species
are affected, a successful metal removal process may require more
reactive acid on a stoichiometric basis than would be indicated by
the concentration of only the target species. It may therefore be
insufficient to only just add enough acid to get the pH below 6.
Nevertheless, in order to give some sense of the proportions that
may be used, in one non-limiting embodiment of the invention, the
composition may comprise down to about 1 wt. % water-soluble
hydroxyacid; and up to about 20 wt. % mineral acid, preferably from
about 1 to about 100 wt. % water-soluble hydroxyacid; and from
about 1 to about 20 wt. % mineral acid, and most preferably from
about 25 to about 85 wt. % water-soluble hydroxyacid; and from
about 15 to about 75 wt. % mineral acid. In some non-limiting
embodiments of the invention, the mineral acid is optional and may
be omitted.
[0042] The additive blend of this invention is injected into the
wash water before the mix valve in neat form or diluted with water,
alcohol or similar solvent suitable to keep all additive components
in solution. The amount of solvent used may range from about 10 to
about 95 wt. %, based on the total composition, preferably from
about 20 to about 10 wt. %.
[0043] The concentration of the additive blend composition of this
invention to be used in the crude oil to be effective is very
difficult to predict in advance since it depends on multiple,
interrelated factors including, but not limited to, the composition
of the crude, the desalting conditions (temperature, pressure,
etc.), the flow rate of the crude and its residence time in the
desalter, among others. Nevertheless, for the purposes of
non-limiting illustration, the proportion of the active
water-soluble hydroxyacid that may be used in the crude (not
including any solvent or mineral acid) may range from about 1 to
about 2000 ppm-w, more preferably from about 10 to about 500 ppm-w
and will depend on the concentration of metal species to be
removed. The organic hydroxy acid reacts stoichiometrically with
the organo metal and/or amine species to be removed. Thus an
equivalent amount of organic hydroxy acid must be added compared to
the concentration of metal species to be removed. A slight excess
of the acid will ensure that the reaction goes to completion. In
one non-limiting embodiment of the invention, the amount of
water-soluble hydroxyacid is stoichiometric with the amount of
metals and/or amines present, or greater than stoichiometric. For
economic reasons the refinery may chose to leave some of the metal
and/or amine species in the crude at an acceptably low level of
contamination of hydrocarbon. In those cases the treatment level of
the hydroxy acids can be correspondingly reduced.
[0044] It is most preferred, of course, that in the practice of
this invention there be no oil carryunder in the aqueous phase, and
that at least oil carryunder is minimized. Further, while it is
preferred that all of the metals and/or amines transfer to the
aqueous phase, in one non-limiting theory of the invention, some of
the metals and/or amines may be transferred from the oil phase into
the rag. This proportion of metals and/or amines is then removed
when the rag is cleaned out.
[0045] It is also most preferred, of course, that in the practice
of this invention all of the metals and/or amines transfer to the
aqueous phase. In another non-limiting embodiment of the invention,
25% or less metal and/or amine is present in the hydrocarbon phase
after desalting, preferably 20% or less metal and/or amine remains,
most preferably only 10% or less remains. In some cases the
refinery may chose to leave higher percentages of metal and/or
amine contaminants in the crude if the detrimental effects are
judged to be economically acceptable.
[0046] The invention will be illustrated further with reference to
the following
[0047] Examples, which are not intended to limit the invention, but
instead illuminate it further.
[0048] The following Electrostatic Desalting Dehydration Apparatus
(EDDA) Test Method was employed to screen possible blend
compositions. The EDDA is a laboratory test device to simulate the
desalting process.
EDDA Test Method
[0049] 1. Add 800, 600 or 400 ml of crude oil to be tested minus
the percent of wash water (depending on the number of tubes the
EDDA will hold) to a Waring blender. [0050] 2. Add the required
percentage of wash water to the blender to bring the total volume
up to 800, 600 or 400 ml. 3. Mix at 50% speed (on the Variac) for
30 seconds. The speed can be reduced if the .DELTA.P on the mix
valve is low. [0051] 4. Pour the mixture into the EDDA tubes to
just below the 100 ml line. [0052] 5. Place the tubes in the EDDA
heating block that is at the desired test temperature (99.degree.
C.). [0053] 6. Add the desired quantity of demulsifier, in ppm, to
each tube. With every test, a blank must be run for comparison
purposes. [0054] 7. Place the screw top electrode in the tubes and
allow the samples to heat for approximately 15 minutes. [0055] 8.
Tighten the caps and shake each tube 100-200 times and place back
in the heating block to reheat for five minutes. [0056] 9. Place
the electrode cover over the tubes and lock into place. Make sure
that there is good contact between the cover and the electrode
caps. [0057] 10. Set the time for five minutes and run at 1500-3000
volts, depending on the test requirements. [0058] 11.At the end of
the five minutes, pull the tubes out and check for the percent
water drop. Also check the quality of the interface and the quality
of the water and record it. [0059] 12. Repeat steps 9, 10, and 11
until the desired total residence time is achieved. [0060] 13.
Determine the best candidates and run a dehydration test on those
samples.
[0061] a) Fill the desired number of 12.5 ml centrifuge tubes to
the 50% mark with xylene.
[0062] b) Use a glass syringe to pull 5.8 ml of dehydrated crude
sample from the desired level in the tube and mix in with the
xylene in the centrifuge tubes.
[0063] c) Centrifuge the tubes at 2000 rpm for 4 minutes.
[0064] d) Check for the quantity of water, emulsion, and solids
that are present in the bottom of the tube and record.
Analysis for Calcium
[0065] After completing the EDDA test, use a glass syringe and
cannula (long, wide bore needle), to withdraw two 20 ml aliquots of
the EDDA desalted crude oil. Abstract the oil at a level in the
EDDA tube that is at 25 ml and 70 ml below the surface of the oil.
The two samples (top cut and bottom cut) are each analyzed for
calcium concentration by whatever appropriate method (wet ash or
microwave digestion, acidification, dilution, AA or ICP analysis).
A similar procedure would be used to generate oil and water samples
that could be analyzed by ion chromatography for other contaminants
such as amine salts.
[0066] The crude oil used was from an African country that has a
high calcium content.
[0067] Additive A=70% glycolic acid, balance water.
[0068] Additive B=A blend of glycolic acid, phosphoric acid (pH
adjuster), a pyridine quaternary ammonium compound (corrosion
inhibitor), a dinonyl phenol/ethylene oxide oxyalkylate
(co-solvent), isopropyl alcohol and water.
TABLE-US-00001 TABLE I Sample A - 100% Crude Desalted Crude Oil*
Top Water Addi- Raw Crude Phase, Interface, Phase, Ex. Metal tive
Oil, ppm ppm ppm ppm 1 Calcium A 370 30 31 1700 2 '' B 370 76 76
1210 3 Iron A 60 14 15 113 4 '' B 60 26 27 8 5 Zinc A 35 6 4 163 6
'' B 35 17 16 34 7 Silicon A 37 <2 <2 6 8 '' B 37 <2 2 7 9
Nickel A 8 9 9 <2 10 '' B 8 9 10 <2 11 Sodium A 97 9 10 416
12 '' B 97 13 12 404 13 Potassium A 789 31 32 4030 14 '' B 789 34
32 3900 *Top Phase = 20 mL sample taken at 75 mL mark of 100 mL
EDDA test tube. Interface = 20 mL oil sample taken near oil/water
interface present in EDDA test tube.
TABLE-US-00002 TABLE II Sample B - 20% High Calcium Crude Blend
Desalted Crude Oil Top Water Addi- Raw Crude Phase, Interface,
Phase, Ex. Metal tive Oil, ppm ppm ppm ppm 15 Calcium A Emulsion
Emulsion Emulsion Emulsion 16 '' B 58 8 5 362 17 Iron A Emulsion
Emulsion Emulsion Emulsion 18 '' B 10 2 <2 3.6 19 Zinc A
Emulsion Emulsion Emulsion Emulsion 20 '' B 6 5 22 32 21 Silicon A
Emulsion Emulsion Emulsion Emulsion 22 '' B <2 11 20 2 23 Nickel
A Emulsion Emulsion Emulsion Emulsion 24 '' B 2 3 3 <2 25 Sodium
A Emulsion Emulsion Emulsion Emulsion 26 '' B 17 15 8 113 27
Potassium A Emulsion Emulsion Emulsion Emulsion 28 '' B 79 3 4
91
[0069] From the data presented above it may be seen that the
water-soluble hydroxyacid used (glycolic acid) effectively removed
or transferred a variety of metals from the oil phase to the water
phase. The inventive method was particularly effective on the high
content metals such as calcium and potassium.
[0070] Tables III-VI provide additional data showing the transfer
of various metals from a hydrocarbon phase to a water phase using
the water-soluble hydroxy-acids of the invention. The various
components are defined as follows (all proportions are volume
percents): [0071] Additive C 70% glycolic acid, 30% water [0072]
Additive D 75% Additive C, 20% acrylic acid polymer scale inhibitor
(which alone is designated SI1), 1.8% alkyl pyridine quaternary
ammonium salt corrosion inhibitor, and 3.2% oxyalkylated alkyl
phenol surfactant [0073] Additive E 72% phosphorous acid scale
control/pH adjuster compound, 14% oxyalkylated polyalkyleneamine,
and 14% S11. [0074] Additive F 10% oxalic acid, 20% thioglycolic
acid, 10% glycolic acid, 1.5% alkyl pyridine quaternary ammonium
salt corrosion inhibitor, and 58.5% water. [0075] DA through DF
designate Demulsifiers A through F, which are all various
oxyalkylated alkylphenol resin demulsifiers. When used together
with an additive of this invention, they may be abbreviated such as
DA/D which indicates Demulsifier A is used together with Additive D
in the ppm ratio given in the next column. [0076] SI2 Scale
Inhibitor 2 that contains diammonium ethylenediamine tetracetic
acid (EDTA). [0077] SI3 Scale Inhibitor 3 that contains an amine
phosphonate scale inhibitor. [0078] SRA1 Scale Removal Additive 1,
which is a blend of an alkyl pyridine quaternary ammonium salt
corrosion inhibitor (same as in Additive D) with phosphoric acid,
glycolic acid and a demulsifier.
TABLE-US-00003 [0078] TABLE III EDDA Test Results, Examples 29-40
Test Test Addi- Dose Metals Analysis Ex Condition Sample tive (ppm)
Na K Mg Ca Fe 29 EDDA. Crude A C 1000 Top Oil 2.3 11.5 <1 85 51
10% DI (in water) Interface 2.5 8.5 <1 68 40 Wash Water Water
443 4400 21.9 1560 2.7 30 EDDA. '' lactic 1000 Top Oil 2.4 6.3
<1 37 39 10% DI acid (in water) Interface 1 6.5 <1 37 38 Wash
Water Water 388 4170 22.1 1610 5.5 31 EDDA. '' Blank none Oil 164
765 4 306 49 10% DI Wash Water 32 EDDA. '' C 2000 5 19 <3 24 16
10% DI (in water) 5 20 <3 24 16 Wash Water 425 4670 24 1640 93.8
33 Blank None Oil 87 919 5.8 363 68.6 34 EDDA. '' SRA1 2000 Top Oil
13 34 76 26 10% DI (in water) Interface 12 32 76 27 Wash Water
Water 404 3900 21 1210 8 35 EDDA. '' SI2 2000 Top Oil 11 14 192 29
10% DI (in water) Interface 7 10 191 28 Wash Water Water 414 4000
20 959 82 36 EDDA. '' C 2000 Top Oil 9 31 30 14 10% DI (in water)
Interface 10 32 31 15 Wash Water Water 416 4030 22 1700 113 37
EDDA. '' SI3 2000 Top Oil 15 60 276 49 10% DI (in water) Interface
15 60 281 51 Wash Water Water 440 4190 538 38 EDDA. '' Blank none
Oil 97 789 4 370 60 10% DI Wash Water 39 EDDA. '' SRA1 2000 Top Oil
15 3 8 2 10% DI (in water) Interface 8 4 5 Wash Water Water 113 91
6 362 3.6 40 EDDA. '' Blank none Oil 17 79 58 10 10% DI Wash Water
Metals Analysis Ex Cu Zn Al Sb Ba V Pb Mn Ni Si P 29 <2 40.0 1.5
15 2.7 <1 8 10 10.0 1.3 8 <2 31.0 1.0 15 2.4 <1 8 8 8.0
<1 8 <0.1 3.7 0.3 <0.1 30.4 <0.1 0.6 18.2 0.2 5.5
<0.1 30 <2 30.0 1.2 14 2.4 <1 7 6 8.0 <1 7 <2 30.0
1.1 20 2.2 <1 10 6 8.0 <1 11 <0.1 9.9 0.5 <0.1 32.3
<0.1 0.6 29.4 0.3 5.3 0.1 31 <2 30.0 8.0 14 8.5 <1 8 11
7.0 10 8 32 <0.5 2.0 1.2 <0.5 0.7 <0.5 11.7 0.6 8.6 30.7
<2 <0.5 2.0 1.0 <0.5 0.7 <0.5 7.9 0.6 9.0 7.1 <2 0.2
162.0 1.5 0.4 33.8 0.2 3.1 56.4 1.0 5.5 2.2 33 <0.5 32.0 11.4
<0.5 8.4 <0.5 6.8 12.2 8.4 15.6 2.8 34 17.0 2 93 3 9.0 86
16.0 2 88 3 10.0 2 91 34.0 8 33 7 1300 35 7.0 6 80 12.0 45 9 2.0 5
84 9.0 2 6 164.0 11 4 58 6 36 6.0 94 9.0 5 4.0 86 9.0 4 163.0 2.0
31 4 57 6 3 37 38.0 5 82 13 9.0 14 215 39.0 5 95 13 10.0 7 223 13 7
50 38 35.0 8.0 8 48 13 8.0 37 3 39 5.0 73 3.0 11 11 22.0 59 3.0 20
5 32.0 12 2 516 40 6.0 37 2.0
TABLE-US-00004 TABLE IV EDDA Test Results, Examples 41-54 Test Test
Addi- Dose Metals Analysis Ex Condition Sample tive (ppm) Na K Mg
Ca Fe 41 EDDA. Crude A DA 15 Top Oil 5.9 17.1 <3 371 58 10% DI
WW Water 626 <5 17 210 <0.2 42 EDDA. '' DB 15 Top Oil 5 13
<3 384 60 10% DI WW Water 705 <5 19 236 <0.2 43 EDDA. ''
DC 15 Top Oil 11 32 5 443 88 10% DI WW Water 579 <5 15 193
<0.2 44 EDDA. '' DD 15 Top Oil 8 27 <3 368 57 10% DI WW Water
698 <5 17 234 <0.2 45 EDDA. '' DE 15 Top Oil 6 23 3 366 55
10% DI WW Water 612 <5 16 204 <0.2 46 EDDA. '' Blank None Oil
6 19 <3 361 54 10% DI WW Water 650 <5 18 216 <0.2 47 EDDA.
Crude B DA 15 Top Oil 4 <5 <3 40 7 10% DI WW Water 147 950 7
143 <0.2 48 EDDA. '' DB 15 Top Oil 5 <5 <3 41 6 10% DI WW
Water 134 882 6 129 <0.2 49 EDDA. '' DC 15 Top Oil 5 <5 <3
39 7 10% DI WW Water 147 948 7 140 <0.2 50 EDDA. '' DD 15 Top
Oil 4 <5 <3 41 6 10% DI WW Water 148 954 6 140 <0.2 51
EDDA. '' DE 15 6 <5 <3 46 8 <3 10% DI WW 146 943 7 140
<0.2 <0.2 52 EDDA. '' Blank none Oil 5 <5 <3 48 6 10%
DI WW Water 130 858 5 122 <0.2 53 EDDA. Crude C C 50 Top Oil 3
<1 <1 4 2 10% DI WW Interface 4 <1 <1 3 5 Water 690 42
31 174 124 54 EDDA. '' Blank none Oil 46 4 3 14 22 10% DI WW Metals
Analysis Ex Cu Zn Al Sb Ba V Pb Mn Ni Si P 41 <3 36.0 4.0 <3
5 <3 27 14 10.0 13 4 <0.2 <0.2 <0.2 <0.2 7 <0.2
<0.4 <0.2 <0.2 10 <0.2 42 <3 36.0 5.0 <3 5 <3
22 14 10.0 9 3 <0.2 <0.2 <0.2 <0.2 8 <0.2 <0.4
<0.2 <0.2 10 <0.2 43 <3 38.0 41.0 <3 6 <3 33 14
11.0 55 3 <0.2 <0.2 <0.2 <0.2 7 <0.2 <0.4 <0.2
<0.2 8 <0.2 44 <3 36.0 4.0 <3 6 <3 33 14 10.0 8 4
<0.2 <0.2 <0.2 <0.2 9 <0.2 <0.4 <0.2 <0.2 9
<0.2 45 <3 35.0 4.0 <3 5 <3 21 14 10.0 66 <3 <0.2
<0.2 <0.2 <0.2 8 <0.2 <0.4 <0.2 <0.2 8 <0.2
46 <3 35.0 <3 <3 5 <3 20 13 9.0 8 3 <0.2 <0.2
<0.2 <0.2 8 <0.2 <0.4 <0.2 <0.2 9 <0.2 47
<3 6.0 <3 <3 <3 8 24 <3 <3 6 <3 <0.2
<0.2 <0.2 <0.2 2 <0.2 <0.4 <0.2 <0.2 2 <0.2
48 <3 6.0 <3 <3 <3 7 17 <3 <3 6 <3 <0.2
<0.2 <0.2 <0.2 2 <0.2 <0.4 <0.2 <0.2 2 <0.2
49 <3 6.0 <3 <3 <3 7 21 <3 <3 4 <3 <0.2
<0.2 <0.2 <0.2 1 <0.2 0.4 <0.2 <0.2 3 <0.2 50
<3 6.0 <3 <3 <3 7 21 <3 <3 3 <3 <0.2
<0.2 <0.2 <0.2 1 <0.2 <0.4 <0.2 <0.2 3 <0.2
51 6.0 <3 <3 <3 8 22 <3 <3 10 <3 <0.2 <0.2
<0.2 1 <0.2 0.4 <0.2 <0.2 3 <0.2 52 <3 6.0 <3
<3 <3 8 23 <3 <3 6 <3 <0.2 <0.2 <0.2
<0.2 1 <0.2 0.5 <0.2 <0.2 3 <0.2 53 <1 <1 1.0
<1 <1 12 <1 <1 6.0 3 3 <1 1.0 1.0 <1 <1 12
<1 <1 6.0 3 3 <1 6.0 2.0 <1 2 <1 <1 <1 <1 2
2 54 <1 2.0 2.0 <1 <1 11 <1 <1 6.0 4 4
TABLE-US-00005 TABLE V EDDA Test Results, Examples 55-67 Test Test
Addi- Dose Metals Analysis Ex Condition Sample tive (ppm) Na K Mg
Ca Fe 55 EDDA. Crude DA/D 15/50 Top Oil 6 29 3 225 29 4% DI WW D/G
Blend Water 338 40 383 0.2 56 EDDA. Crude DE/D 15/50 Top Oil 6 30 4
249 32 4% DI WW D/G Blend Water 341 34 388 0.2 57 EDDA. Crude DB/D
15/50 Top Oil 11 76 4 244 30 4% DI WW D/G Blend Water 334 35 375
0.1 58 EDDA. Crude DA/D 25/50 Top Oil 8 30 2 216 26 4% DI WW D/G
Blend Water 339 39 382 0.2 59 EDDA. Crude DE/D 25/50 Top Oil 4% DI
WW D/G Blend Water 338 37 380 0.2 60 EDDA. Crude DB/D 25/50 Top Oil
13 33 1 206 26 4% DI WW D/G Blend Water 345 37 386 0.3 61 EDDA.
Crude Blank None Oil 44 930 11 266 33 4% DI WW D/G Blend 62 EDDA.
Crude DA/D 40/50 Top Oil 30 20 4 194 29 4% DI WW D/G Blend Water
155 18 142 <0.1 63 EDDA. Crude DE/D 40/50 Top Oil 6 25 4 205 28
4% DI WW D/G Blend Water 341 39 292 0.2 64 EDDA. Crude DB/D 40/50
Top Oil 8 26 4 224 31 4% DI WW D/G Blend Water 336 34.2 287 0.2 65
EDDA. Crude DF/D 40/50 Top Oil 8 43 6 230 36 4% DI WW D/G Blend
Water 352 33.7 297 0.2 66 EDDA. Crude DD/D 40/50 Top Oil 8 67 8 250
34 4% DI WW D/G Blend Water 344 33 386 0.2 67 EDDA. Crude DC/D
40/50 Top Oil 7 33 5 211 34 4% DI WW D/G Blend Water 352 33.2 300
0.2 Metals Analysis Ex Cu Zn Al Sb Ba V Pb Mn Ni Si P 55 3 15.0 4.0
5 11 8.0 2 11 <0.1 <0.1 <0.1 <0.1 17.5 1.1 <0.1 8.1
<0.1 56 4 15.0 3.0 5 12 10.0 3 <1 <0.1 <0.1 <0.1
<0.1 17.4 1.1 <0.1 7.1 <0.1 57 5 14.0 2.0 5 12 8.0 2 6
<0.1 <0.1 <0.1 <0.1 17.3 1.1 <0.1 8 <0.1 58 7
15.0 3.0 5 11 7.0 <1 9 <0.1 <0.1 <0.1 <0.1 18.6 1.2
<0.1 9.6 <0.1 59 <0.1 <0.1 <0.1 <0.1 19 1.1
<0.1 8 <0.1 60 14 15.0 2.0 5 10 6.0 1 8 <0.1 <0.1
<0.1 <0.1 19 1.2 <0.1 8.9 <0.1 61 2 15.0 4.0 7 11 6.0 3
9 62 4 12.0 4.0 3 4 9 3.0 5 14 <0.1 <0.1 <0.1 <0.1 6.8
0.6 <0.1 3.5 114 63 3 13.0 5.0 2 5 10 3.0 5 15 <0.1 <0.1
<0.1 <0.1 13.6 1.1 <0.1 6.9 180 64 8 17.0 6.0 <1 5 10
5.0 2 18 <0.1 <0.1 0.2 <0.1 13.4 1.1 <0.1 7.1 180 65 4
19.0 11.0 <1 5 11 6.0 3 18 <0.1 <0.1 0.2 <0.1 13.6 1
<0.1 6.8 187 66 3 21.0 10.0 <1 6 12 8.0 4 27 <0.1 0.2 1.0
<0.1 13.4 1 <0.1 6.7 177 67 4 14.0 10.0 <1 5 10 4.0 4 14
<0.1 0.2 <0.5 <0.1 13.6 1.1 <0.1 6.7 183
TABLE-US-00006 TABLE VI EDDA Test Results, Examples 68-83 Test Test
Addi- Dose Metals Analysis Ex Condition Sample tive (ppm) Na K Mg
Ca Fe 68 EDDA. Crude E Blank None Oil 63 1590 12.2 475 23.8 7.5% DI
WW 69 EDDA. '' DA/E 30/70 Top Oil 6.1 20.5 7.8 482 25 7.5% DI WW
Water 212 2960 25 278 0.7 70 EDDA. '' DE/E 30/70 Top Oil 5.6 17.7
7.4 435 25.2 7.5% DI WW Water 215 2990 27 281 0.7 71 EDDA. '' DB/E
30/70 Top Oil 6 17.2 7.7 420 24 7.5% DI WW Water 218 3020 25.9 283
0.6 72 EDDA. '' DF/E 30/70 Top Oil 6.2 19.6 7.5 485 24.8 7.5% DI WW
Water 229 3140 29.2 298 0.6 73 EDDA. '' DD/E 30/70 Top Oil 7 18.5
6.6 415 24.5 7.5% DI WW Water 230 3160 28.2 301 0.6 74 EDDA. ''
DC/E 30/70 Top Oil 6 24.6 7.6 398 23.4 7.5% DI WW Water 227 3170
28.1 293 0.7 75 EDDA 5.0% Crude G acetic 1000 Top Oil <0.4 12.6
2.5 22.6 25.2 DI Wash W. acid (in water) Water 116 2430 56.1 3350
72.1 76 EDDA 5.0% Crude F F 1000 Top Oil 0.8 7 3.9 190 31.8 DI Wash
W. (in water) Water 113 2430 48.3 914 4.6 77 EDDA 5.0% Blend E
Blank None Oil 11 320 3.3 100 11.3 DI Wash W. 78 EDDA 5.0% +Other
acetic 1000 Top Oil 1.4 7.7 1.2 21.5 3.5 DI Wash W. Crude acid (in
water) Water 146 3280 29.7 844 96 79 EDDA 5.0% 30/70 F 1000 Top Oil
3 1.2 1 24.7 1.1 DI Wash W. Refinery (in water) Water 140 3170 29.3
408 118 80 EDDA 5.0% Blend lactic 1000 Top Oil 2.5 25.6 1.3 32.2 2
DI Wash W. acid (in water) Water 121 2700 24.1 620 92.5 81 EDDA
5.0% '' glycolic 1000 Top Oil 2.4 22.9 1.2 25.9 2.7 DI Wash W. acid
(in water) Water 124 2830 25.2 700 92.2 82 EDDA 5.0% '' SI1 1000
Top Oil 2 7.9 1.9 75 11.1 DI Wash W. (in water) Water 958 3950 14.3
301 1.4 83 EDDA 5.0% '' Oxalic 1000 Top Oil 6.6 21.9 2.5 80 11.4 DI
Wash W. acid (in water) Water 132 2970 20.3 87.4 <0.1 Metals
Analysis Ex Cu Zn Al Sb Ba V Pb Mn Ni Si P 68 0.5 13.0 0.6 <0.4
11 <0.4 <0.4 10.4 10.6 3.9 2.9 69 0.8 14.5 2.1 <0.4 9.2
<0.4 <0.4 11.3 13.2 5.3 26.2 <0.1 0.1 4.0 <0.1 19.3
<0.4 <0.1 1.3 0.5 7.1 291 70 0.6 14.7 0.5 <0.4 9.4 <0.4
<0.4 11.6 13.6 2.4 25.5 <0.1 <0.1 0.1 <0.1 19.3 <0.4
<0.1 1.3 0.4 7.1 297 71 0.8 15.1 0.2 <0.4 8.6 <0.4 <0.4
11.3 13.8 3.4 27.2 <0.1 <0.1 <0.1 <0.1 19.8 <0.4
<0.1 1.3 0.7 7.5 294 72 0.8 14.7 0.6 <0.4 9.4 <0.4 <0.4
11.4 14.2 2.6 25.3 0.2 <0.1 <0.1 <0.1 19.8 <0.4 <0.1
1.3 0.9 7.3 313 73 0.4 14.5 <0.4 <0.4 8.9 <0.4 <0.4
11.3 13.6 3 26.6 <0.1 <0.1 <0.1 <0.1 20.1 <0.4
<0.1 1.3 0.6 7.4 317 74 <0.4 15.0 <0.4 <0.4 8.4 <0.4
<0.4 10.9 14.8 4 29.2 <0.1 <0.1 <0.1 <0.1 20.3
<0.1 <0.1 1.4 0.8 7.8 302 75 0.9 10.6 2.1 <0.4 0.6 <0.4
<0.4 2.5 11.6 1.1 4.2 0.5 43.9 <0.1 0.2 84.4 <0.1 0.2 126
0.5 5.4 0.3 76 0.7 15.2 3.0 <0.4 3.9 <0.4 <0.4 12.8 11.7
2.4 4 <0.1 0.7 <0.1 <0.1 44.5 <0.1 <0.1 6.4 <0.1
6.1 0.1 77 0.4 4.2 1.1 <0.4 2.5 <0.4 <0.4 4.1 3.5 0.7 1.5
78 <0.4 13.8 9.9 <0.4 0.9 <0.1 <0.4 <0.4 4.1 1.3 2.2
0.2 44.9 0.2 <0.1 14.8 <0.4 0.3 44.4 0.7 4 0.3 79 <0.4 0.6
1.0 <0.4 0.6 <0.1 <0.4 <0.4 4.0 <0.4 2.1 <0.1
52.4 2.2 <0.1 4.2 <0.4 <0.1 38.8 0.5 4.9 0.6 80 0.6 1.1
1.0 <0.4 0.9 <0.1 <0.4 1.2 3.9 1.8 2 0.3 37.2 0.7 0.1 10.3
<0.4 0.7 25.8 36.3 5 0.7 81 <0.4 0.9 1.5 <0.4 0.8 <0.1
<0.4 1.1 3.9 2.6 2.2 0.3 38.2 0.6 0.2 9.8 <0.4 0.9 27.6 30.7
4.2 0.6 82 0.5 5.0 1.1 <0.4 1.7 <0.1 <0.4 4.2 3.8 <0.4
1.9 0.3 0.6 0.3 <0.1 12.6 <0.4 <0.1 3.4 <0.1 5.4 0.1 83
0.5 4.7 1.0 <0.4 1.6 <0.1 <0.4 4.2 3.9 <0.4 2.3 <0.1
<0.1 <0.1 <0.1 5.2 <0.4 <0.1 0.7 <0.1 5
<0.1
[0079] The FIGURE presents a graph showing the partitioning across
desalters of various amines and ammonia as a function of pH. The
addition of water-soluble hydroxyacids of this invention such as
glycolic and gluconic acid to the desalter wash water at the use
rates specified herein will reduce the water's pH to the range of
about 3-6.5.
[0080] In the foregoing specification, the invention has been
described with reference to specific embodiments thereof, and has
been demonstrated as effective in transferring metals, e.g.
calcium, potassium, etc., and/or amines from crude oil to the
aqueous phase in bench scale desalting testing, as non-limiting
examples. However, it will be evident that various modifications
and changes can be made thereto without departing from the broader
spirit or scope of the invention as set forth in the appended
claims. Accordingly, the specification is to be regarded in an
illustrative rather than a restrictive sense. For example, specific
water-soluble hydroxyacids, and combinations thereof with other
mineral acids, other than those specifically exemplified or
mentioned, or in different proportions, falling within the claimed
parameters, but not specifically identified or tried in a
particular application to transfer metals and/or amines into the
aqueous phase, are within the scope of this invention. Similarly,
it is expected that the inventive compositions will find utility as
metal transfer compositions for other fluids besides crude oil
emulsions.
* * * * *