EP1165723A1

EP1165723A1 - Metal phase transfer additive composition and method

Info

Publication number: EP1165723A1
Application number: EP00913766A
Authority: EP
Inventors: Tran Minh Nguyen; Lawrence N. Kremer
Original assignee: Baker Hughes Inc
Current assignee: Baker Hughes Holdings LLC
Priority date: 1999-03-05
Filing date: 2000-03-03
Publication date: 2002-01-02
Also published as: WO2000052114A1; AU3514600A

Abstract

It has been discovered that metal-containing components can be transferred from a hydrocarbon phase to a water phase in an emulsion breaking process by using a composition which is a blend of polymers. The composition includes at least one diepoxide polymer, at least one polyol; and preferably at least one aromatic sulfonic acid. An aromatic solvent may be optionally included in the composition. The invention permits transfer of metal-containing components 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 iron-containing components therefrom.

Description

METAL PHASE TRANSFER ADDITIVE COMPOSITION AND METHOD

Field of the Invention 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 metal-containing components to an aqueous phase in an emulsion breaking process

Background of the Invention 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 • Brine contamination in the crude oil as a result of the brine associated with the oil in the ground,

• Minerals, clay, silt, and sand from the formation around the oil well bore, and

• Iron sulfides and iron oxides resulting from pipeline and vessel corrosion during production, transport, and storage

Desalting is necessary prior to further processing to remove these salts and other inorganic materials which would otherwise cause fouling in downstream heat exchanger equipment and/or form corrosive salts detrimental to crude oil processing equipment 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

• Reduced crude unit corrosion

• Reduced crude preheat system fouling

• Reduced potential for distillation column damage • Reduced energy costs • Reduced downstream process and product contamination. Desalting is the resolution of the natural emulsion of water which 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 which 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.

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 electrostatic coalescence. These additives effectively allow small water droplets to more easily coalesce by lowering the oil/water interfacial tension.

Crude oil which contains a high percent of paniculate 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 which 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.

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. Some of the metals, including iron, 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.

Several treatment approaches have been made to reduce total iron levels and these all center on the removal of iron at the desalter unit.

It would thus be desirable to develop a composition and method employing it which would cause most or all of the metal-containing components 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.

Summary of the Invention Accordingly, it is an object of the present invention to provide a composition and method of using it which would transfer a large part of the metal-containing components in the crude oil to the aqueous phase in a desalter operation.

It is another object of the present invention to provide a composition and method for transferring metal-containing components from a hydrocarbon into an aqueous phase in an emulsion breaking operation without causing oil undercarry into the aqueous phase.

Yet another object of the invention is to provide a method and composition to transfer metal-containing components out of a hydrocarbon phase without the use of nonyl phenol resins. In carrying out these and other objects of the invention, there is provided, in one form, a method of transferring metal-containing components from a hydrocarbon phase to a water phase by adding to an emulsion of hydrocarbon and water an effective amount of a composition. The composition includes at least two of the following components: a diepoxide polymer; a polyol; and an acid selected from the group of sulfonic acids and carboxylic acids An aromatic solvent may also be present

Detailed Description of the Invention It has been discovered that application to the crude oil of a blend of polymers

(surfactants) helps ensure the metal-containing components will largely transfer to the aqueous phase when the emulsion is broken, without causing oil undercarry More particularly, in one embodiment, the blend includes high molecular weight polyglycol and polymerized polyols from diepoxide, additionally with the presence of a small amount of an aromatic sulfonic acid In another embodiment, the blend contains at least two of these three components a diepoxide polymer, a polyol, and an acid The acid may be a sulfonic acid and/or a carboxylic acid Some prior methods teach removing iron from the crude oil, but the problem of oil undercarry in the discharge water usually results The composition and method of this invention enables rapid penetration through the oil layer around a droplet or particle This penetration is vividly demonstrated by rapid visual indication of the emulsion breaking

The composition and method of the invention will be valuable to produce high quality (i.e., high purity) coke from crude which may originally contain high concentrations of metals and solids, in particular, iron-based solids Further, the invention advances the technology by removing inorganic material, such as iron, from the crude oil without discharging any oil or emulsion to the waste treatment plant

In this invention, it will be understood that the term "metal-containing component" includes, but is not necessarily limited to, inorganic species, such as elemental metal, metal oxides, e.g. iron oxides, but also organic metal-containing species, such as iron porphyrin, naphthenate salts of iron, and any other metal- containing material, compound or chemical These metal-containing components may be in particulate or solid form, or in solubilized form It will be further understood that while iron is often mentioned as the metal element removed by the compositions and methods of this invention, that the invention is not limited to iron removal, but is expected to be useful to remove other metals, such as nickel and vanadium, in a further non-limiting embodiment Nickel and vanadium are known poisons for catalysts used in fluid catalytic cracking units (FCCUs) downstream

In one embodiment of the invention, the composition of the invention is a blend of at least two of a diepoxide polymer, a polyol, and an acid In one preferred embodiment of the invention, the diepoxide polymer is one of the components In an alternate embodiment of the invention, the composition is a diepoxide polymer and a polyol, in the absence of a sulfonic acid and/or a carboxylic acid In one preferred embodiment of the invention, all three are employed In another, non-limiting embodiment, the proportion of these three components may be diepoxide polymer in the range of from about 5 to about 99 8 wt %, a polyol in the range of from about 0 1 to about 75 wt %, and an aromatic sulfonic acid in the range of from about 0 1 to about 20 wt % In a non-limiting, preferred embodiment of the invention, the proportion of these three components may be diepoxide polymer in the range of from about 10 to about 85 wt %, a polyol in the range of from about 1 to about 60 wt %, and an aromatic sulfonic acid in the range of from about 0 1 to about 15 wt % In embodiments where no acid is used, the proportions of diepoxide polymer and polyol are the same as given above

In still another embodiment of the invention, the composition has an absence of ammonium ion and/or an absence of an alkoxylated formaldehyde resin

By the term "diepoxide polymer" is meant any diepoxide reaction product with a polyol It will be appreciated that the recitation of "a diepoxide polymer" includes the possibility of more than one diepoxide polymer The diepoxide polymer may have a molecular weight in the range from about 15,000 to about 30,000 It will be understood that all molecular weights expressed herein are number average molecular weights Preferably, the diepoxide polymer may have a molecular weight in the range from about 20,000 to about 25,000 In one non-limiting embodiment of the invention, the diepoxide polymers are reaction products of polyols with glycidyl ethers from a compound containing at least one phenolic group Non-limiting examples of suitable diepoxide polymer include, but are not necessarily limited to, reaction products of bisphenol-A diglycidyl ethers or copolymers of bisphenol-A and epichlorohydrin or Epon 828 with polyols, and the like The polyols may be made by alkoxylating initiators with alkoxides such as ethylene oxide (EO), propylene oxide (PO), butylene oxide and mixtures thereof Suitable initiators or starting materials for the polyols include, but are not necessarily limited to, glycerine, trimethylolpropane (TMP), ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and other glycols, pentaerythritol, sugars and sugar derivatives such as sorbitol or sorbate, amines such as diethylenetriamine, triethylenepentamine, polyethylene(imine) and polyallylamine, and the like Specific, non-limiting examples of suitable diepoxide polymers include, but are not necessarily limited to, EPON 828 reaction products with polypropylene glycol (PPG)

The polyol may have a molecular weight in the range from about 10,000 to about 60,000 Preferably, the polyol may have a molecular weight in the range from about 11,000 to about 28,000 It will be appreciated that the recitation of "a polyol" includes the possibility of more than one polyol Specific, non-limiting examples of suitable polyols include, but are not necessarily limited to, those polyols discussed above with respect to the diepoxide polymers

It will be appreciated that the recitation of "an acid" includes the possibility of more than one sulfonic and/or carboxylic acid Specific, non-limiting examples of suitable diepoxide polymers include, but are not necessarily limited to, dodecyl benzene sulfonic acid (DDBSA), naphthalene sulfonic acid, dialkylbenzene sulfonic acid, isopropyl sulfonic acid (IPSA), alkylsulfonic acids such as decanesulfonic acid, carboxylic acids such as citric acid and erythorbic acid (rf-erythro-ascorbic acid, isoascorbic acid), and the like It will be appreciated that the term "carboxylic acid" also encompasses dicarboxylic acids herein

The additive blend of this invention is injected into the flowing crude oil before the mix valve in neat form or diluted in a suitable aromatic solvent at a rate to provide effective oil/water separation Specific, non-limiting examples of suitable aromatic solvents include, but are not necessarily limited to, heavy aromatic solvent, ethyl benzene, xylene, toluene, heavy aromatic naphthalene such as Panasol AN-3N, FAS 150, EXXON 150, and the like The amount of solvent used may range from about 10 to about 95 wt %, based on the total blend with the other three components, preferably from about 20 to about 10 wt %

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 blend that may be used in the crude (not including any aromatic solvent) may range from 1 to 500 ppm- w A preferable concentration will range from 10 to 100 ppm-w

It is most preferred, of course, that in the practice of this invention there be no oil carryunder in the aqueous phase is minimized Further, while it is preferred that all of the metal-containing components transfer to the aqueous phase, in one non-limiting theory of the invention, some of the metals may be transferred from the oil phase into the rag This proportion of metals is then removed when the rag is cleaned out

It is also most preferred, of course, that in the practice of this invention all of the metal-containing components transfer to the aqueous phase In another non- limiting embodiment of the invention, 25% or less metal-containing component is present in the hydrocarbon phase after desalting, preferably 20% or less metal- containing component remains, most preferably only 10% or less remains

The invention will be illustrated further with reference to the following Examples, which are not intended to limit the invention, but instead illuminate it further

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 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 Add the required percentage of wash water to the blender to bring the total volume up to 800, 600 or 400 ml Mix at 50% speed (on the Nariac) for 30 seconds The speed can be reduced if the DP on the mix valve is low Pour the mixture into the EDDA tubes to just below the 100 ml line Place the tubes in the EDDA heating block that is at the desired test temperature (99°C) Add the desired quantity of demulsifier, in ppm, to each tube With every test, a blank must be run for comparison purposes Place the screw top electrode in the tubes and allow the samples to heat for approximately 15 minutes Tighten the caps and shake each tube 100-200 times and place back in the heating block to reheat for five minutes 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 Set the time for five minutes and run at 1500-3000 volts, depending on the test requirements 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 Repeat steps 9, 10, and 11 until the desired total residence time is achieved Determine the best candidates and run a dehydration test on those samples a) Fill the desired number of 12 5 ml centrifuge tubes to the 50% mark with xylene 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 c) Centrifuge the tubes at 2000 rpm for 4 minutes d) Check for the quantity of water, emulsion, and solids that are present in the bottom of the tube and record

Total Iron Test from Crude Oil Equipment

Analytical balance (0 0000 gr readout) Muffle furnace capable of reaching 600°C Ceramic crucible and crucible lids Platinum-tipped crucible tong Extreme temperature gloves (Zetex gloves, asbestos replacement)

Reagents

10% (w) solution of hydrochloric acid Deionized water

Procedure

1 Using a glass syringe and cannula (long, wide bore needle), withdraw a 10 ml aliquot from the EDDA desalted crude oil Abstract the oil at a level in the EDDA tube which is at 70 ml below the surface of the oil 2 Eject the 10 ml aliquot oil sample into a preweighed (nearest 0 0001 g) ceramic crucible

3 Place the crucible with the sample into a muffle furnace and ash the sample starting at room temperature and rising to 550°C, then hold for 5 to 6 hours

4 Remove the crucible from the oven and place in a desiccator to cool for 1 hour 5 After cooling, reweigh the crucible and ash Subtract the crucible's original weight to obtain the weight of the ash

6 To the ash, add 1 ml of a 10% (w) solution of hydrochloric acid and wait 5 minutes to dissolve the ash

7 Dilute the solution with 24 ml of deionized water to the dissolved ash solution for a total of 25 ml and wait 2-3 minutes 8 Determine the iron concentration in the aqueous acid solution using a Chemetrics Total Iron procedure (Model FE-10, Kit K-6010) (CHEMet) a) Place the CHEMet' s tapered tip down in the bottom of the sample crucible cup Snap the tip by pressing the ampoule against the side of the sample cup The sample fluid will fill the ampoule and begin to mix with the reagent A small bubble of inert gas will remain in the ampoule to facilitate mixing b) Remove the fluid-filled CHEMet from the crucible cup Mix the contents by inverting it several times allowing the bubble to travel from end to end each time, until the solution is uniform in color c) Wipe all liquid from the exterior of the CHEMet and wait 2 minutes d) Use the appropriate comparator to determine the concentration of the iron in the aqueous sample

9 Convert the aqueous iron concentration to the iron concentration found in the oil sample, using the following conversion formula

where [Fe(_0Ii)] = iron concentration in oil, expressed as mg Fe/1

[Fe_(aq)] = iron concentration in ash's acidic aqueous solution, in mg Fe/1

N(aq) = volume of acidic acid solution in iron Chemetrics test, in ml V(oιi) = volume of oil ashed, in ml

Five gallons of crude oil and one gallon of wash water were received from a refinery in Oklahoma for this iron removal study The following formulations were prepared Components

A Propoxylated sorbitol 10.4 wt.%

B Resin esters 5.0

C 6.0 mole EO adduct nonyl phenol resin 4.6 FAS 150 Fina Aromatic Solvent 80.0

FeS₂ Components

A Propoxylated sorbitol 10.6 wt.%

D Resin esters 4.5 C 6.0 mole EO adduct nonyl phenol resin 3.0

FAS 150 81.9

FeS₃ Components

Water 78.0 wt.% Citric acid 2.0

Calfax 2A1 Sodium salt of naphthalene disulfate 12.5

Nonyl phenol with 9.5 mole ethylene oxide 81.9

FeS₄ Components

A Propoxylated sorbitol 10 wt.%

E Nonylphenol resin ethoxylated with 6 moles 16 of ethylene oxide

B Resin esters 4

F Amylphenol resin 4

FAS 150 66

RJ-1 Compi onents

G Diepoxide reaction product of EPON 828 with 22 wt.% polypropylene glycol H Polyglycol 8 DDBSA 0.5

FAS 150 69.5

RJ-2 Components J Diepoxide 22 wt.%

H Polyglycol 8

DDBSA 0.5

FAS 150 69.5

RJ-3 Components

K Diepoxide reaction product made with EPON 24.0 wt.% 828 and propylene oxide and ethylene oxide

H Polyglycol DDBSA 0.5 FAS 150 67.5

Other Compositions

PC- 18 Experimental demulsifier

FeS₂A Experimental demulsifier

BPR27141 Complex blend of resins

BPR27210 Complex blend of resins

98BH171 Complex blend of resins

Physical Pro perties

The physical properties of the two most promising blends were as shown below: FeS₄

Specific Gravity at 78°F (26°C) = 0.96 pH at 25°C, 10% in 50/50 water/IPA (isopropyl alcohol) = 9.47 Flash point, TCC = 145°F (63°C) RJ-1

Specific Gravity at 83 °F (28°C) - 0 95 pH at 25°C, 10% in 50/50 water/IPA = 7 60 Flash point, TCC = 149°F (65°C)

Examples 1 through 29 demonstrate the amount of iron left in the oil phase after the EDDA test using the indicated components In all Examples, 5% wash water was used, except for the Examples of Tables V and NIII, where 3% wash water was used The test temperature was 98°C (208°F) Ten ml aliquots were removed at each indicated time interval

TABLE I EDDA Test Results

Nol % water returned

Cone after indicated no of minutes

Ex_ Compound ppm 5 10 15 Fe. ppm

1 FeS₃ 20 0 2 2 2 4 0

2 FeS₂ 20 0 2 0 5 1 3 0

3 FeS₃/PC-18 12/3* 1 8 2 3 5 4 0

* Concentrations expressed as ratios are ppm of the first component ppm of the second component

TABLE II EDDA Test Results

Nol % water returned Cone after indicated no of minutes

Ex Compound ppm 5 10 15 Fe⁺⁺. ppm

4 FeS₂A 20 2 6 3 3 6 0

5 FeS₂/BPR27141 16/4 3 8 4 4 5 0 6 FeS₃/BPR27141 16/4 35 50

7 Blank 70

TABLE III EDDA Test Results

Vol % water returned

Cone after indicated no of minutes

E2 Compound ppm 5 10 15 Fe⁺⁺, ppm

8 Experimental 20 0 0 0 45 demulsifier

9 Experimental 20 0 0 0 45 demulsifier

10 BPR27210/BPR27141 16/3 07 15 17 50

TABLE IV

EDDA Test Results

Vol % water returned

Cone after indicated no of minutes

Ex Compound ppm 5 10 J Fe⁺⁺, ppm

11 FeS₄ 10 2 20 3 30

13 BPR27141/B 4/8 24 28 3 50 PR27210

TABLE V

EDDA Test Results

Vol % water returned

Cone after indicated no of minutes

Ex_ Compound ppm 5 10 15 18 Fe , ppm

14 FeS-JRJ-1 16/4 1.2 2 2 22 40 15 FeSι/RJ-2 16/4 0.5 1.5 1.9 2.0 6.0

16 FeSι/RJ-3 16/4 0.5 1.5 1.7 2.0 4.0

TABLE VI EDDA Test Results

Vol.% water returned

Cone. after indicated no. of minutes

Ex, Compound ppm 5 10 i-5 Fe ⁺⁺. ppm

17 98BH171/FeS 4/16 3.5 5 5 8.0

4

18 RJ-l/FeS₄ 4/16 2.0 4 4 4.0

19 RJ-2/FeS₄ 4/16 2 3.5 4 1.0

TABLE VII EDDA Test Results

Vol.%) water returned after indicated no. of minutes

Ex, Compound ppm 5 10 15 Fe . ppm

20 FeS-t/RJ-1 16/4 3 3.5 4 1.0

21 FeS_JRJ-2 16/4 2.6 3 3.8 2.0

22 FeS-JRJ-3 16/4 3 3.5 4 4.0

TABLE VIII EDDA Test Results

Vol.% water returned

Cone after indicated no. of minutes

Ex, Compound ppm 5 10 15 Fe , ppm

23 FeS-JRJ-1 16/4 0.5 0.9 1.5 2

24 FeS-JRJ-2 16/4 0.5 0.8 1.2 3

25 FeS RJ-3 16/4 0.5 0.9 1.5 4 T. ABLE IX

EDDA Test Results

Vol.% water returned

Cone. after indicated no. of minutes

Ex, Compound ppm 5 10 15 20 Fe ⁺⁺, PPm

26 FeS-JRJ-1 16/4 0.5 2 2.6 3 2

27 FeS.JRJ-1 16/6 1.0 2 2.8 3 1

28 FeS-JRJ-l 16/8 1.0 2 3 3.5 1

29 FeS-JRJ-1 16/10 1.5 2.6 3 3.5 1.5

It may be seen that the blend of FeSφ/RJ-1 gives the best results as shown by values of 1 and 2 ppm iron retained in Examples such as 20, 23, and 26 through 28. Because of the promise of RJ-1 in the laboratory tests, it was used alone in a field trial in Oklahoma. The iron measurements were made using an atomic adsorption method, and are shown in Tables X and XI for the indicated time periods.

TABLE X Example 30 — Field Trial of RJ-1 Alone

Resid Fe, (Feed to

Date Raw Crude Fe. ppm Desalter Effluent Fe, ppm Coker), ppm

11/28 19 15 90

11/29 16 14 79

11/30 18 16 76

12/1 * 19 37 173

12/2 19 11 49

12/3 - - -

12/4 17 13 49

* From 9:00 p.m. 11/30 to 5:00 a.m. 12/1, tank bottoms slop was being injected into the desalter which caused the high Fe values on this day. TABLE XI

Example 30 — Field Trial of RJ-1 Alone

Raw Crude Resid Fe, (Feed Comments

Date Time Fe. ppm to Coker , ppm

1/25 900 16 81

1/26 900 19 98

1/27 1700 20 54 Trial with RJ-1 starts

1/28 1500 19 67

1/29 800 22 74 Mud washed for 4+ hours

2/1 900 - 49

2/2 900 17 46

2/3 1300 15 66

2/4 900 17 50

2/5 800 19

2/5 1600 20 40 Rag sample = 680 ppm, Fe

2/8 1500 23 56

2/9 800 22 56

2/9 1400 21 52

2/10 800 18 63

2/11 900 17 42

2/11 1530 11 42

2/12 800 14 46

2/13 800 23 69

2/15 800 24 37

2/16 1000 16 38

2/17 900 15 41

2/18 900 16 65

2/19 900 23 80 Excessive mudwash before sample obtained 2/22 900 8 31

2/22 1600 12 33

2/23 900 11 22

In the foregoing specification, the invention has been described with reference to specific embodiments thereof, and has been demonstrated as effective in transferring metal-containing components, e.g. iron particulates, 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 polyols and diepoxide polymer reaction products, and combinations thereof, other than those specifically tried, falling within the claimed parameters, but not specifically identified or tried in a particular application to transfer metal-containing components into the aqueous phase, are within the scope of this invention. Likewise, aromatic sulfonic acids other than DDBSA are expected to be useful in various polymer blends not explicitly described herein. Similarly, it is expected that the inventive compositions will find utility as metal transfer compositions for other fluids besides crude oil emulsions.

Claims

We Claim

1 A method of transferring metal-containing components from a hydrocarbon phase to a water phase comprising adding to an emulsion of hydrocarbon and water, an effective amount of a composition to transfer metal-containing components from a hydrocarbon phase to a water phase comprising at least two of the following components a diepoxide polymer, a polyol, and an acid selected from the group consisting of sulfonic acids and carboxylic acids, and resolving the emulsion into hydrocarbon phase and an aqueous phase, where at least a portion of the metal-containing components are transferred to the aqueous phase

2 The method of claim 1 where in the adding of the composition, the composition comprises a diepoxide polymer and a polyol

3 The method of claim 1 where in the adding of the composition, the composition comprises a diepoxide polymer

4 The method of claim 1 where in the adding of the composition, the composition further comprises from about 5 to about 99 8 wt % diepoxide polymer, from about 0 1 to about 75 wt % polyol, and from about 0 1 to about 20 wt % acid

5 The method of claim 1 where in the adding of the composition, the diepoxide polymer has a molecular weight in the range from about 15,000 to about 30,000

6 The method of claim 1 where in the adding of the composition, the polyol has a molecular weight in the range from about 10,000 to about 60,000

7 The method of claim 1 where in the adding of the composition, the composition further comprises an aromatic solvent

8 The method of claim 7 where in the adding of the composition, the composition contains from about 10 to about 95 wt % aromatic solvent

9 The method of claim 1 where in the adding of the composition, the amount of the composition added to the emulsion is at least 1 ppm

10 A composition for transferring metal-containing components from a hydrocarbon phase to a water phase comprising at least two of the following components a diepoxide polymer, a polyol, and an acid selected from the group consisting of sulfonic acids and carboxylic acids

11 The composition of claim 10 where two of the components are a diepoxide polymer and a polyol

12 The composition of claim 10 where at least one of the components is a diepoxide polymer

13 The composition of claim 10 where the composition further comprises from about 5 to about 99.8 wt.% diepoxide polymer; from about 0.1 to about 75 wt.% polyol; and from about 0.1 to about 20 wt.% acid.

14. The composition of claim 10 where the diepoxide polymer has a molecular weight in the range from about 15,000 to about 30,000.

15. The composition of claim 10 where the polyol has a molecular weight in the range from about 10,000 to about 60,000.

16. The composition of claim 10 where the composition further comprises an aromatic solvent.

17. The composition of claim 16 where the composition contains from about 10 to about 95 wt.%) aromatic solvent.