US008372271B2

(12) United States Patent
Nguyen et a].
(54) ADDITIVES TO ENHANCE METAL AND

(10) Patent No.:
(45) Date of Patent:
2,778,777 A

US 8,372,271 B2
*Feb. 12, 2013

1/1957 Powell

AMINE REMOVAL IN REFINERY
DESALTING PROCESSES ’ ’

2
3,167,500 A

lsiteclman
1/1965 P
as am

(75) Inventors: Tran M. Nguyen, Sugar Land, TX (U S);
Lawrence N. Kremer, Sugar Land, TX Jerry J‘ Wee“, Rlchmond’ TX

C t. ayn;

( on mue ) FOREIGN PATENT DOCUMENTS

(73) ( * ) Assignee: Notice: gikgslalughes Subject to any disclaimer, Incorporated, the term Houston, of this
patent is extended or adjusted under 35

(Commued)
OTHER PUBLICATIONS
PCT International Search Report for International Application No.

USC 154(b) by 848 days.
This

atem is Sub-em to a terminal dis_

clailnlér~
(21) Appl. No.: 12/390,631
_

J

PCT/US02/27116, Dec. 23, 2003.
( on “we )
Primary Examiner * Walter D Gri?in

C

t'

d

(22)

Flled'

Feb‘ 23’ 2009

Assistant Examiner * Renee E Robinson

(65)

Prior Publication Data
US 2009/0152164 A1
_ _ _ _ _

gc4) Attorney, Agent, or Firm * Mossman Kumar & Tyler
57 ABSTRACT
) _ _

Jun. 18, 2009
(
It has been discovered that metals and/or amines can be

Related US. Application Data

(62)

DlVlSlOn of aPPhCaUOn NO- 10/649921, ?led on Aug-

removed or transferred from a hydrocarbon phase to a Water

27, 2003, HOW Pat- N0~ 7,497,943

phase in an emulsion breaking process by using a composi

(60) Provisional application NO 60/407,1397 ?led on Aug
30 2002' ’

tion that contains Water-soluble hydroxyacids. Suitable
Water-soluble hydroxyacids mclude, but are not necessarily limited to glycolic acid, gluconic acid, C2-C4 alpha-hydroxy

(51) Int_ CL C10G 17/04

(200601)
208/252 25 4 R

acids, poly-hydroxy carboxylic acids, thioglycolic acid, chlo roacetic acid, polymeric forms of the above hydroxyacids,
P°1Y-g1Y°_°11° esters’ glycolate “hers, an‘? ammonntm Salt and alkah metal “1159f these hYdFOX-‘YZ‘CIdS’ and 1mm?“
thereof. The composition may also mclude at least one min

(52) us. Cl. ............... .. 208/252; 208/251 R; 208/254 R (58) Field of Classi?cation Search ............ .. 208/251 R,
See application ?le for Complete Search histor;
'

eral acid to reduce the pH of the desalter Wash Water. A
solvent may be optionally included in the composition. The
invention p ermits transfer of metals and/or amines into the

(56)

References Cited

U.S. PATENT DOCUMENTS
2,175,095 A 2,355,077 A 10/1939 Stoesser 8/1944 Johnson

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.

2,744,853 A
2,767,123 A

5/1956 Kavanagh etal.
10/1956 Hickoketal.

15 Claims, 1 Drawing Sheet
Amine/Ammonia Partitioning Across Desalters
As a Function of pH

CDPB% otaaeIrsAtuidoenig

11/1994 Bellos et 31. 2005.” EXCALIBUR brochure.876 4.439.627 A 5. 8/1979 Cheng et a1~ 9/1979 Street.. Jr. PATENT DOCUMENTS 5.957 A 5. Marcel Dekker. Czech Republ1c. 3/1995 Brown et al.778. Plaintiff’ s First Amended Complaint andApplication for Preliminary Injunction‘ Defendant Nalco company’s Response to Plaintiff’ s Application for P 1I - Bellos et al. Nov. Inc. et a1.164. “Remove Metals. et al.590 A 4.364.185 4.389.com.eptq.243 A 3.395. 10/1988 gramblick et al' eyno S J. Reynolds 011501 Reynolds et al. 2005.938.592 A 10/1988 Reynolds J.214 A 4.167. tiff’ s Application for Preliminary Injunction. Norman Duke Siskin et al. Weers et al.410 4. Jr.865 4.988.223 A 9/1994 siefert et 31. 3rd Edition.345 4. et al.587.992 A 5 078 858 A 1/1992 Hart et al ‘1 fe ‘.582.591 A lg.432. Weers. 3.005 ’ . Gary.. Improve Margins. pp. Chapter 4.104. 1994.847 A 5.433 4992210 A A A A A 12/ 1988 Reynolds 4/ 1989 8/1989 7/ 1990 1/1991 2/1991 11/1991 leum Technology Quarterly. 2004 _ _ >9 . 6/ 1997 Bellos et al. 6/1971 Meadow et al. Prague.853.346. Q3.818. Plaintiff’ s Answer to Defendant’s Second Amended Counterclaims. “A New Metals Removal Process for Doba Crude 011. ERTC 9th Annual Meetlng. 5. J.657 4.664 A 3.532 A 5.778.176. 39-69.372.174.J. g’ggg’égg 2 6’133’205 A ’ ’ ggggg 100000 Jones 31' 4.” Petro 4. 10/1988 Reynolds et al‘ Reynolds 4.US 8. * cited by examiner .342.2829 59 A 4/l992 Mccu?lough' 5 / 1992 Naeger et a1‘ 12/1992 McCullough 1/1993 Kremer 2/1994 Roling et a1.062.276. avilalbe from www. RU W0 W0 FOREIGN PATENT DOCUMENTS 1666520 A1 0052114 A1 WO 01/40410 * A A A A A 8/1989 9/2000 7/2001 OTHER PUBLICATIONS 2 4. Nalco Company’s Second AmendedAnswer to First Amended Com Plalnt Amended Memorandum Opinion and Order for Injunctive Relief.. 5’080’779 A V1992 Awbre e't a1 Pla1nt1ff’ s Reply to Defendant Nalco Company’s Response to Pla1n 5. Naeger et 31' McCullough 5.789.463 A 4. 15.536 A 5.322. Petroleum Re?ning: Technology and Economics. 6/1981 8/1982 2/1984 3/1984 5/ 1986 Martin Blair. Crude Distillation.449. NewYork.489 A 5/1967 Paterson et al.637.472 A 4. H.109 4.578 A 5:1 143566 A 5. “Calc1um Removal from H1gh TAN Crudes.592 A 12/1998 Bellos et a1. Baker Petrolite. Jr.271 B2 Page 2 US. 2/ 1995 Crump et al.853.m‘nary nluncnon' .594 A 5.778. 6/1969 Strong.

.

Reduced energy costs. Proper desalter operations provide the fol loWing bene?ts to the re?ner: Reduced crude unit corrosion. 3.921 ?ledAug.497. 30 associated With the oil in the ground. but these materials have come under suspicion as possible hormonal mimics and are ineffective by themselves of removing metals such as calcium or iron. nickel. TECHNICAL FIELD tight Water-in-oil emulsions. HoW ever. This includes the coking operation since iron and other metals remaining in the processed hydrocarbon yields a loWer grade of coke. calcium. potassium. 40 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. 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. in one embodiment. Removing the metals from the crude oil early in the hydrocarbon processing stages is desired to even tually yield high quality coke as Well as to limit corrosion and ?eld. Under this arrangement. 30. by nature. fouling processing problems. Zinc. potassium. oil-Wetted solids in high concentration in the crude may help form tight oil and Water emulsions that are dif?cult to resolve. In Metals including calcium. silicon. Reduced potential for distillation column damage.271 B2 1 ADDITIVES TO ENHANCE METAL AND AMINE REMOVAL IN REFINERY DESALTING PROCESSES CROSS-REFERENCE TO RELATED APPLICATIONS 2 (top layer) and the Water phase (bottom layer). Effective crude oil desalting can help minimiZe the effects of these contaminants on the crude unit and doWn Several treatment approaches have been made to reduce total metal levels and these all center on the removal of metals at the desalter unit. or from amines used as neutraliZers in crude unit overhead 35 addition to complicating the desalter operation. The streams of desalted crude oil and e?luent Water are separately dis charged from the desalter. patent application Ser. Would prefer to transfer to the Water phase. 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 Water droplets into larger and larger droplets. With little or no oil carryunder in the Reduced crude preheat system fouling. issued as US. and also from H2S scavengers used in the oil cessing. and more particularly relates. As mentioned. including. The rag layer inside the desalter vessel may groW to such an extent that some of it Will In an oil re?nery. This is a problem for the Waste Water treatment plant since the rag layer still contains a high percentage of unresolved emulsi?ed oil. Desalting is the resolution of the natural emulsion of Water SUMMARY 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. Nitrogen-containing compounds such as amines used to scrub H2S from re?nery gas streams in amine units. Pat.943 on Mar. This application is a divisional application of US. 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. Normally. 2009. Further. 55 aqueous phase. the emulsion resolves into tWo separate phasesithe oil phase emulsion breaking operation Without causing oil undercarry into the aqueous phase. The metals may be present in inorganic or organic forms. It Would thus be desirable to develop a composition and 50 stream operations. much of the solids in a crude oil from a ?eld exists in the bene?t of US.372. to methods and compositions for transferring metals and/ or amines to an aqueous phase in an emulsion breaking process. and stor age. An induced dipole is formed on each Water droplet Within the emulsion that causes electrostatic attraction and coalescence of the 65 Accordingly. 2003. That is. the oil and Water emulsion is exposed to the applied electrical ?eld.US 8. and the like. 27. but are not necessarily limited to. etc. Which are soluble or dispersed as ?ne particulate matter in the oil but not in Water. Other metals that are desirably removed include. The entire desalting process is a continuous ?oW procedure as opposed to a batch process. No. the desalting of crude oil has been prac ticed for many years. the desalter only removes Water soluble inorganic salts such as sodium or potassium chlo 45 rides. The particulate solids. Crude oil that contains a high percent of particulate solids can complicate the desalting process. iron sul?de.. silicon. iron and other metals are of particular concern to further doWnstream pro systems. Provisional Application No. sodium. Eventually. but not necessarily limited to: Brine contamination in the crude oil as a result of the brine 25 be inadvertently discharged With the Water phase. 10/649. silt. Zinc. Some of the metals may be present in a soluble form. sodium. and Iron sul?des and iron oxides resulting from pipeline and vessel corrosion during production. most commonly as par ticulate iron such as iron oxide. No.139 ?led Aug. 2002. much of the solids encountered during crude oil desalting consists of iron. Normally. . Reduced doWnstream process and product contamination. clay. BACKGROUND 20 the separated oil and Water phases. and sand from the formation around the oil Well bore. and typically a number of these metals are present. 7. nickel. 60/407. Which in turn claims These additives effectively alloW small Water droplets to more easily coalesce by loWering the oil/Water interfacial tension. The crude is usually contaminated from several sources. These tight emulsions are often referred to as “rag” and may exist as a layer betWeen The present invention relates to methods and compositions for separating emulsions of hydrocarbons and Water. transport. The emulsion mix is directed into a 60 desalter vessel containing a parallel series of electrically charged plates. etc. chemical additives are injected before the mix valve to help resolve the oil/Water emulsion in addition to the use of electrostatic coalescence. Nonyl phenol resins have been used as desalt ing additives in the past. these metals can act as poisons for the catalysts used in doWnstream re?nery units. Minerals. Some crude oils contain Water insoluble metal organic acid salts such as calcium naphthenante and iron naphthenate.

Water. and mixtures thereof. BRIEF DESCRIPTION OF THE DRAWING 40 The FIGURE is a graph of various amines and ammonia partitioning across desalters as a function of pH. and a mineral acid. The alpha substituent on the Cl-C4 alpha-hydroxy acids may be any C l-C4 straight or branched alkyl group. By “removing” the metals and/or amines from the hydrocarbon or crude is meant any and all partitioning. This improves distri bution of the acid in the oil although addition to the aqueous 65 . 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 monoethanolamine (MEA). In another non-limiting embodiment of the invention. transferring.271 B2 3 In carrying out these and other objects of the invention. N-ethyl morpholine (EMO). including the salts thereof). DETAILED DESCRIPTION 45 In one preferred. polymeric forms of the above hydroxyacids.. N-methylethanolamine. Where at least a portion of the metals and/ or amines have been transferred to In this invention. polymeric forms of the above hydroxyacids. but are not necessarily limited to. there is provided a composition for transferring metals and/or amines from a hydrocarbon phase to a Water phase that poisons for catalysts used in ?uid catalytic cracking units (FCCUs) doWnstream. C2-C4 alpha-hydroxy acids. Wetting agents and mixtures thereof. iron. poly-glycolic esters. including the salts thereof) and at least one additional com ponent that may be a hydrocarbon solvent. but are not necessarily limited to. 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. soluble and Will not partition as much into the crude oil. The Water-soluble 4 phase should not be vieWed as a requirement for the compo sition of the invention to Work. Hydroxy acids are de?ned herein as not including or exclusive of acetic acid. The Water.e. the metals include. N-me thyldiethanolamine and combinations thereof. This is accomplished by converting the Water insoluble salt such as calcium naphthenate into a Water silicon. silicon. N-methyl morpholine. the alpha substituent may be C2-C4 straight or branched alkyl group and lactic acid is not included. the glycolic acid is typically added to the Wash Water in the desalter. In particular. trietha 25 nolamine (TEA). The glycolate ethers may have the formula: 60 rating. IIB and IVA of the Periodic Table (CAS ver sion). nickel and vanadium are knoWn 20 soluble salt such as calcium glycolate. including iron-based solids. While thioglycolic acid and chloroacetic acid are not strictly speak acid (hydroxyacetic acid) and other Water-soluble hydroxy acids to a crude oil can signi?cantly reduce the amount of calcium and other metals and/ or amines in the hydrocarbon When it is run through a desalter in a re?nery. The removal 55 acids. metal chelants. C l-C4 alpha-hydroxy acids. removing. The addition of glycolic acid in levels of up to a 5:1 ratio With calcium.US 8. the invention advances the technology by removing inorganic material from the crude oil Without dis charging any oil or emulsion to the Waste treatment plant. The levels of metals other than calcium such as iron. Acetic acid has sometimes been used to remove metals tor.soluble hydroxy acids are much more Water Water phase comprising a Water-soluble hydroxyacid (as de?ned above. VB. a corrosion inhibi In one embodiment of the invention. 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. of one or more metal from the hydrocarbon or crude to any extent. the Water-soluble hydroxyacid is selected from the The inventors have discovered that the addition of glycolic group consisting of glycolic acid. sepa (CHOH)4COOH. but it has a high oil solubility and tends to stay With 35 the hydrocarbon coming from the desalter. high purity) coke from crude that may originally have contained high concentrations of metals and/or amines and solids. sodium. dividing. a scale inhibitor. they are de?ned as hydroxy oil containing higher than normal amounts of calcium and found minimal calcium removal. N-methyl ethanolamine. in one form. including the salts thereof). iron sul?de. and mixtures thereof.N-dimethyl ethanolamine (DMEA). poly-glycolic esters. glycolate ethers. nickel. In still another non-limiting embodiment of the invention. glyco late ethers. nickel. sequestering. 0 Being an aqueous additive. and combina tions thereof.372. In another non-limiting embodiment. the aqueous phase. Gluconic acid. The emulsion is then resolved into hydrocarbon phase and an aqueous phase. thioglycolic acid. there is provided a treated hydrocarbon emulsion that includes hydrocarbon. and ammonium salt and alkali metal salts of these hydroxy acids. morpholine. it Will be understood that the metals include. sodium and potassium are also reduced. methoxypropylamine (MOPA). 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. The acidity of the acetic acid can then cause corrosion problems in the crude unit. N. In one non-limiting embodiment of the invention. a demulsi?er. The composition and method of the invention Will be valu able to produce high quality (i. The amines removed in accordance With the method of this invention may include. IIA. Zinc. hydroxyacid may be glycolic acid. 30 includes a Water-soluble hydroxyacid (as de?ned above. Zinc. ethylenediamine (EDA). vanadium. is a speci?c. and a composition for transfer ring metals and/or amines from a hydrocarbon phase to a as Well. those of Groups IA. Further. includes a Water-soluble hydroxyacid (as de?ned above. poly-hydroxy carboxylic acids. gluconic acid. chloroace tic acid. The inventors have compared the “normal” desalting on a reference crude 50 ing hydroxyacids. thus reducing doWnstream concerns. results in much loWer metals and/or amine content of the desalted oil. but are not necessarily limited to calcium. chloroacetic acid. potassium. they are functional equivalents thereof. there is provided. etc. non-limiting embodiment of the inven tion. the composition of the invention includes a Water-soluble hydroxy acid. For the purposes of this invention. non-limiting embodiment of the invention. is a non-limiting but preferred polymer of glycolic acid. CH2OH of particulate iron in the form of iron oxide. VIII. poly-hydroxy carboxylic acids. diethanolamine (DEA). thioglycolic acid. eliminating.

mineral acids may be used since metal removal is best accomplished at an acidic pH. As noted. phthalic and benZoic anhydrides. particularly glycolic acid or gluconic acid. particularly acetic. the concentration of metal species and amine to be removed. In yet another non-limiting embodiment of the invention. preferably 20% or less . % Water-soluble hydroxyacid. In one non combinations of Water-soluble hydroxyacids. phosphoric acid. 25% or less metal and/or amine is present in the hydrocarbon phase after desalting. % mineral acid. The additive blend of this invention is injected into the Wash Water before the mix valve in neat form or diluted With Water. and from about 1 to about 20 Wt. % mineral acid. Since many undesirable species are affected. In one non limiting embodiment of the invention. glycolic acid and gluconic acid may be used to remove cal cium and amines. malic acid. or greater than stoichiometric. more preferably from about 10 to about 500 ppm-W and Will depend on the concentration of sarily limited to. in one non-limiting theory of the invention. the desalting conditions (temperature. although in some situations it may be necessary or desirable to adjust the pH to achieve the desired contaminant transfer or separation. the amount of Water soluble hydroxyacid is stoichiometric With the amount of metals and/or amines present. 0 O Where n is as above. but not neces dif?cult to predict in advance since it depends on multiple. in one embodiment of the invention. alcohol or similar solvent suitable to keep all additive components in solution. sulfuric acid. and thioglycolic acid may be used for iron 35 removal. the temperature and pressure conditions of formula: method. butyric. the compo sition of the crude. It is most preferred. It is also most preferred. interrelated factors including. but not limited to. the more of the reactive acid that must be added. nitric acid. the mineral acid is optional and may be omitted. that in the practice of this invention all of the metals and/or amines transfer to the 65 desired proportions of the hydroxyacid and/or the mineral acid Will be dif?cult to predict in advance. the nature of the hydrocarbon. In yet another non-lim iting embodiment of the invention. Metal chelants are compounds that complex With metals to form chelates. hydrocarbon sol vents. preferably from about 1 to about 100 Wt. such as calcium. As noted beloW. 50 to. A slight excess of the acid Will ensure that the reaction goes to completion. of course. potassium hydroxyide. Suitable mineral acids for use in conjunction With the Water-soluble hydroxy acids of this invention include. and most preferably from about 25 to about 85 Wt.) of these hydroxyacids alone or in combination With the other Water-soluble hydroxyacids men tioned. effective or some of the metals and/or amines may be transferred from the oil phase into the rag. While it is preferred that all of the metals and/or amines transfer to the aqueous phase. Thioglycolic acid and the ethers of etc. the more of a species. and the like.US 8. In another non-limiting embodiment the Water-soluble 25 hydroxyacids do not include citric acid. The concentration of the additive blend composition of this invention to be used in the crude oil to be effective is very ing units. from crude oil or another hydrocarbon phase. propionic. the composition may comprise doWn to about 1 Wt. for the purposes of non-limiting illustration. preferably from about 20 to about 10 Wt. In general. The amount of solvent used may range from about 10 to about 95 Wt. there is to be removed. hydrochloric acid. demulsi?ers. it may be necessary or preferred to loWer the pH of the Wash Water to 5 or beloW. alternatively to 4 or beloW. and possibly increased Water solubility. in order to give some sense of the proportions that may be used. tartaric acid. pressure. valeric. of course. that in the practice of this invention there be no oil carryunder in the aqueous phase. It is expected that the Water-soluble hydroxyacids Will be used together With other additives including. The organic hydroxy acid reacts stoichiometrically With the organo metal and/or amine spe cies to be removed. corrosion inhibitors. the particular hydroxyacid and mineral acid used.372. a suc cessful metal removal process may require more reactive acid on a stoichiometric basis than Would be indicated by the glycolic acid may have the added bene?ts of a higher boiling point. Further. the amount of mineral acid used may be su?icient to loWer the pH of the Wash Water to 6 or beloW. stearic. %. A higher boil ing point means the additive Will not distill into the distillate fractions in the crude unit and cause corrosion or product quality concerns. % mineral acid. in some embodiments of the 55 invention. It Will be appreciated that the necessary. The use of 40 metal species to be removed. Nevertheless. % Water-soluble hydroxyacid. the method of this inven For economic reasons the re?nery may chose to leave some of tion is practiced in a re?nery desalting process that involves Washing the crude emulsion With Wash Water. the How rate of the crude and its residence time in the desalter. 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. phosphorous acid. and mixtures thereof. scale inhibitors. Such salts Would be formed in the desalter Wash Water as the system’s pH Was adjusted With pH adjusters such as 20 sodium hydroxide. pH adjusters. the de?nition of Water-soluble hydroxyacids includes ammonium salt and alkali metal salts (eg sodium and potassium salts. etc. The the metal and/or amine species in the crude at an acceptably loW level of contamination of hydrocarbon. It may therefore be insuf?cient to only just add enough acid to get the pH beloW 6. % Water-soluble hydroxyacid. Nevertheless. the de?nition of Water soluble hydroxyacids does not include organic acid anhy 30 drides. ammonia. and that at least oil carryunder is minimiZed. 60 Water-soluble hydroxyacids (and salts thereof) are expected to be useful over a Wide pH range. aqueous phase. in a commercial process. and up to about 20 Wt.271 B2 5 Where n ranges from 1-10.). among others. in one non-limiting embodiment of the invention. In some non-limiting embodi ments of the invention. but not necessarily limited to. and lactic acid. and mineral acids may give the best economics in a commercial application. but are not necessarily limited 45 limiting embodiment of the invention. and from about 15 to about 75 Wt. %. The glycolate esters may have a 6 including. etc. In particular. In particular. since these pro portions or dosages are dependent upon a number of factors. 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 process concentration of only the target species. In those cases the treatment level of the hydroxy acids can be correspondingly reduced. This proportion of metals and/or amines is then removed When the rag is cleaned out. mandelic acid. based on the total composition. and mixtures thereof. metal chelants. In another non-limiting embodiment of the invention. Thus an equivalent amount of organic hydroxy acid must be added compared to the concentration of metal species to be removed.

. 1 Calcium 2 " 3 Iron 4 " A B 60 60 14 26 15 27 113 8 20 5 Zinc 6 " A B 35 35 6 17 4 16 163 34 3. 20% acrylic acid polymer scale 65 inhibitor (Which alone is designated S11). 1 1 . AddiEx. c) Centrifuge the tubes at 2000 rpm for 4 minutes. 30% Water Additive D 75% Additive C.5 ml centrifuge tubes to the 50% mark With xylene. ppm Emulsion 58 Top Phase. dilution. Place the tubes in the EDDA heating block that is at the 9 Nickel 10 " A B 8 8 9 9 9 10 <2 <2 25 11 Sodium 12 " A B 97 97 9 13 10 12 416 404 desired test temperature (99° C. isopropyl alcohol and Water. The inventive method Was particularly effective on the high content metals such as calcium and After completing the EDDA test. 600 or 400 ml. and analyZed by ion chromatography for other contaminants such as amine salts. The invention Will be illustrated further With reference to the following Examples. 35 TABLE II Sample B — 20% High Calcium Crude Blend Desalted Crude Oil depending on the test requirements.). Metal Additive A B Desalted Crude Oil* RaW Crude Oil. Add the desired quantity of demulsi?er.US 8. 12.271 B2 7 metal and/or amine remains.At the end of the ?ve minutes. Which are not intended to limit the invention. a dinonyl phenol/ethylene oxide oxyalkylate (co-solvent). Pour the mixture into the EDDA tubes to just beloW the 100 ml line. Interface = 20 mL oil sample taken near oil/Water interface present in EDDA test tube. The tWo samples (top cut and bottom cut) are each analyZed for calcium concentration by Whatever appropriate method (Wet ash or microWave digestion. but instead illuminate it further. AA or ICP analysis). 7. 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. acceptable.6 19 Zinc 20 " A B Emulsion 6 Emulsion 5 Emulsion 22 Emulsion 32 21 Silicon 45 22 " A B Emulsion <2 Emulsion 11 Emulsion 20 Emulsion 2 a) Fill the desired number of 12. Place the screW top electrode in the tubes and alloW the 30 13 Potassium 14 " A B 789 789 31 34 32 32 4030 3900 *Top Phase = 20 mL sample taken at 75 mL mark of 1 00 mL EDDA test tube. 10.8 ml of dehydrated crude sample from the desired level in the tube and mix in With 23 Nickel 24 " A B Emulsion 2 Emulsion 3 Emulsion 3 Emulsion <2 25 Sodium 26 " A B Emulsion 17 Emulsion 15 Emulsion 8 Emulsion 113 27 Potassium 50 28 " A B Emulsion 79 Emulsion 3 Emulsion 4 Emulsion 91 the xylene in the centrifuge tubes. In some cases the re?nery may chose to leave higher 8 The crude oil used Was from an African country that has a percentages of metal and/or amine contaminants in the crude if the detrimental effects are judged to be economically high calcium content. ANALYSIS FOR CALCIUM From the data presented above it may be seen that the Water-soluble hydroxyacid used (glycolic acid) effectively 55 removed or transferred a variety of metals from the oil phase to the Water phase.8% alkyl pyri dine quaternary ammonium salt corrosion inhibitor. 6. EDDA TEST METHOD Ex. pull the tubes out and check for the percent Water drop. 3. 2. Mix at 50% speed (on the Variac) for 30 seconds. ppm 1700 1210 . Additive BIA blend of glycolic acid. 8. phosphoric acid (pH adjuster). Make sure that there is good contact betWeen the cover and the electrode caps. The EDDA is a laboratory test device to simulate the desalting process. Metal 40 RaW Crude Oil.2% oxyalkylated alkyl phenol surfactant. Also check the quality of the interface and the quality of the Water and record it. TABLE I Sample A — 100% Crude The folloWing Electrostatic Desalting Dehydration Appa ratus (EDDA) Test Method Was employed to screen possible blend compositions. Add the required percentage of Wash Water to the blender to bring the total volume up to 800. A similar procedure Would be used to generate oil and Water samples that could be potassium. mo st preferably only 10% or less remains. and 11 until the desired total residence time is achieved. 13. The various components are de?ned as folloWs (all proportions are volume percents): Additive C 70% glycolic acid. 1. samples to heat for approximately 15 minutes. 10. Additive A:70% glycolic acid. ppm 31 76 Water Phase. ppm Emulsion 5 Water Phase. acidi ?cation. and solids that are present in the bottom of the tube and record. With every test. Place the electrode cover over the tubes and lock into place. 5.Add 800. in ppm. Abstract the oil at a level in the EDDA tube that is at 25 ml and 70 ml beloW the surface of the oil. Repeat steps 9. a blank must be run for comparison purposes. Set the time for ?ve minutes and run at 1500-3000 volts. ppm Emulsion 8 Interface. Determine the best candidates and run a dehydration test on those samples. The speed can be reduced if the AP on the mix valve is loW. emulsion. balance Water. a pyridine quaternary ammonium compound (corrosion inhibitor). d) Check for the quantity of Water. ppm 370 370 Top Phase.372. b) Use a glass syringe to pull 5. Tighten the caps and shake each tube 100-200 times and place back in the heating block to reheat for ?ve minutes. to WithdraW tWo 20 ml aliquots of the EDDA desalted crude oil. 9. ppm Emulsion 362 tive A B 15 Calcium 16 " 17 Iron 18 " A B Emulsion 10 Emulsion 2 Emulsion <2 Emulsion 3. to each tube. ppm 30 76 Interface. use a glass syringe and cannula (long. Tables III-VI provide additional data shoWing the transfer of various metals from a hydrocarbon phase to a Water phase 60 using the Water-soluble hydroxyacids of the invention. 7 Silicon 8 " A B 37 37 <2 <2 <2 2 6 7 4. Wide bore needle).

0 1.1 14 2.6 7 10 0. they may be abbreviated such as DA/D Which indicates Demul. and 14% S11.0 6.3 1.5 0.0 10% D1 Wash Water Test Ex 29 Test Sample CrudeA Dose Additive C Metals Analysis Sb Top Oil Interface Water Top Oil Condition EDDA.8 24 1640 363 76 16 93. TABLE III EDDA Test Results.1 30 " lactic acid " Blank (in Water) none Interface Water Oil <1 5.6 8.271 B2 9 Additive E 72% phosphorous acid scale control/pH adjuster 10 S12 Scale Inhibitor 2 that contains diammonium ethylenedi compound.4 <1 30.5 0.372.2 <0.6 26 <0.5 443 2.2 3 9.8 93 0. and 58. " 10% D1 35 (in Water) " S12 2000 Interface Water Top Oil 2 8 6 88 80 3 33 10.0 2.2 8.3 2.1 5.0 34.9 <1 Ca 85 68 1560 37 Fe 51 40 2.0 39 10% D1 Wash Water EDDA. 10% amine tetracetic acid (EDTA)_ _ _ _ _ glycolic acid’ 15% alkyl pyridine quaternary ammonium 5 S13 Scale 1nh1b1tor 3 that contains an amine phosphonate salt corrosion inhibitor.0 35 .4 12.7 <0.1 0.4 33 34 EDDA.0 163. " SRAl 2000 Top Oil 15 3 8 2 5. " C 2000 5 19 <3 24 16 <0.5 0.0 2 7 45 91 13 00 9 Wash Water EDDA.5 4400 6. " Blank (in Water) none Interface Water Oil 8 1 13 17 4 91 79 5 6 3 62 58 22.US 8.0 3.5 11. 10% D1 Wash Water EDDA. 14% oxyalkylated polyalkyleneamine.0 8. 10% D1 Wash Water (in Water) Interface Water 5 11 84 4 58 9.7 <2 10% D1 WashWater (in Water) Blank SRAl None 2000 Oil Top Oil <0.1 <1 <1 <0.5 8. " Blank (in Water) none Interface Water Oil 15 440 97 60 41 90 789 4 281 53 8 370 51 60 39.0 3.5 33. " 10% D1 Wash Water 35 EDDA. 0 0.4 2. " S12 (in Water) 2000 Interface Water Top Oil 12 404 11 32 3900 14 21 76 1210 192 27 8 29 16 . (ppm) 1000 (in Water) 1000 Ba V Pb 8 8 0.5% Water.6 <2 2.1 <2 Zn 40.10 SRAl Scale Removal Additive 1. 6 10 32 . 0 12. 10% D1 Wash Water 38 EDDA.0 1.6 56.1 8 15 15 <0.0 30.2 32.0 0.5 2.3 7.1 <2 1.0 8.3 10 31 8. Which are all various oxyalkylated alkylphenol resin demulsi?ers.0 32.2 8.4 <0.1 6. Examples 29-40 Test Test Dose Metals Analysis Ex 29 Condition EDDA.7 30.5 1.8 86 33 34 EDDA.3 Mg <1 <1 21.4 2 .0 Wash Water EDDA.6 8 Mn 10 8 18.0 1. Which is a blend of an alkyl si?er A is used together With Additive D in the ppm ratio given in the next column.0 Si 1.0 7.0 8.9 30.2 6 6 29. Sample CrudeA Additive C (ppm) 1000 (in Water) 1000 Na Top Oil Interface Water Top Oil K 11.4 <0.4 9.0 38.0 10% D1 36 (in Water) " C 2000 Interface Water Top Oil 7 414 9 10 4000 31 20 191 95 9 30 28 82 14 2 .7 0.2 10% D1 Wash Water (in Water) Blank SRAl None 2000 Oil Top Oil 5 425 87 13 20 4670 919 34 <3 24 5. When used together With an additive of this invention. pyridine quaternary ammonium salt corrosion inhibitor (Same as inAdditiVe D) With Phosphoric acid.0 9.0 1.0 2 6 6 .0 Al 1. " acid Blank (in Water) none Interface Water Oil 1 388 164 6. 10% D1 37 (in Water) " S13 2000 Interface Water Top Oil 10 416 15 32 4030 60 22 31 1700 276 15 113 49 4.5 49 <2 <0.7 39 Cu <2 <2 <0.0 162. " C 2000 <0. glycolic acid and a demulsi?er.5 2 7.5 4170 765 <1 22.9 3.1 7 11 0. 10% D1 Wash Water EDDA.3 <0.1 14 20 <0.5 15. DA through DF designate Demulsi?ers A through E.6 30.0 1 64.3 <1 5. Scale inhibitor. 8 68.5 11.0 31. 20% thioglycolic acid.0 10% D1 Wash Water 32 EDDA.5 <1 P 8 8 <0.5 0.2 2.0 0.0 10% D1 Wash Water 40 EDDA.0 6.0 8.0 7.5 <1 32 10% D1 Wash Water EDDA.7 <1 2.0 Wash Water EDDA.8 0.4 30 " lactic 10% D1 Wash Water 31 EDDA.7 <0.5 2.0 17.1 4 37 1610 306 38 5.5 8.2 2. Additive F 10% oxalic acid.4 11 Ni 10. 10% D1 Wash Water EDDA.

10% DIWW EDDA.2 36.2 <3 <0. 10% DI W (ppm) 15 Ba 5 7 5 8 6 7 6 9 5 8 5 8 <3 2 <3 2 V <3 <0.0 <02 10. 10% DI W EDDA.2 14 <0.2 7 <0.2 14 <0.0 5 12 10% DI 37 (in Water) " SI3 2000 Interface Water Top Oil 31 86 4 82 57 13 9. 10% DIWW EDDA.4 17 <0.2 <1 <1 <1 <1 <0.0 54 " Blank none 10% DI WW Test EX 41 42 Test Sample Crude A " Dose Additive DA DB Metals Analysis Sb Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Oil Water Top Oil Water Top Oil Water Condition EDDA.2 43 44 45 46 " " " " DC DD DE Blank 15 15 15 None 47 48 Crude B " DA DB 15 15 <3 <02 <3 <02 <3 <02 <3 <02 <3 <02 <3 <02 <3 <02 <3 <02 . 10% DI W EDDA.0 Al 4.372. 10% DI W EDDA.0 <02 5.0 6.2 8 <0.2 6. 10% DI W EDDA. 10% DIWW EDDA. 10% DI W EDDA.0 8.2 38.2 <3 <0.0 2. 10% DI WW EDDA.0 <02 <3 <02 <3 <02 <3 <02 <3 <02 <3 <02 <3 <02 <3 43 " DC 15 44 45 46 " " " DD DE Blank 15 15 None 47 48 Crude B " DA DB 15 49 50 51 52 " " " " DC DD DE Blank 15 15 15 none <3 7 <3 6 <3 7 <3 6 46 140 <3 53 10% DIWW EDDA. " SRAI 2000 Top Oil 73 3.2 6.2 14 <0.0 9.2 2 5 124 22 <0.0 <0.2 Pb 27 <0.0 20 2 5 516 10% DI Wash Water TABLE IV EDDA Test Results.2 7 <0.1 <5 13 <5 32 <5 27 <5 23 <5 19 <5 <5 950 <5 882 <5 948 <5 954 <3 7 <5 Mg <3 17 <3 19 5 15 <3 17 3 16 <3 18 Ca 371 210 384 236 443 193 368 234 366 204 361 216 40 143 41 129 39 140 41 140 8 <0.2 60 <0.0 <02 4.2 <3 <0.2 6 <0.2 <3 <0.0 <02 10.2 6 <0.2 <3 <0.0 <0.4 20 <0. " Blank (in Water) none Interface Water Oil 5 13 8 95 48 13 13 10.2 6.0 2.0 <0.2 48 Fe 58 <0.2 6.0 <02 9.9 626 5 705 11 579 8 698 6 612 6 650 4 147 5 134 5 147 4 148 <5 943 5 K 17.2 <3 <0.2 6.2 88 <0. 10% DIWW EDDA.0 <0. " C 2000 Top Oil 94 9.2 Ni 10.0 <0.0 <02 1. Sample CrudeA " Additive DA DB (ppm) 15 Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water 6 146 Oil Na 5.2 <3 <0. 10% DI W EDDA.2 <3 <0.2 57 <0. 10% DIWW EDDA. Examples 41-54 Test Test Dose Metals Analysis EX 41 42 Condition EDDA.4 33 <0. 10% DI W EDDA.2 <3 <0.0 <02 41.2 <3 <0.0 2.US 8.2 14 <0.0 <0.0 <0.2 <3 <0.0 <02 4. 10% DIWW EDDA. 10% DI W EDDA.0 <02 11.0 <02 10. 10% DI Wash Water 38 EDDA. 10% DIWW EDDA. " Blank (in Water) none Interface Water Oil 59 12 37 3 .2 35 .0 <0.2 <3 <0.2 6.2 13 <0.4 22 <0.0 7 7 37 223 50 3 39 10% DI Wash Water EDDA.2 <3 <0. 10% DI W EDDA.2 7 <0.271 B2 11 TABLE III-continued EDDA Test Results.2 <3 <0.0 4 6 14 3 215 Wash Water EDDA.0 <0.4 21 <0. Crude C C 50 Water Top Oil Interface Water Oil 130 3 4 690 46 858 <1 <1 42 4 5 <1 <1 31 3 122 4 3 174 14 <0.2 54 <0.2 36.0 <0.2 <3 <0.0 1. Examples 29-40 36 EDDA.2 <3 Zn 36.2 <3 <0.2 6 Cu <3 <0. 10% DIWW EDDA.4 Mn 14 <0.2 55 <0.2 <1 1.2 35 .4 24 <0.0 <02 <3 <02 <3 <02 Si 13 10 9 10 55 8 8 9 66 8 8 9 6 2 6 2 P 4 <02 3 <02 3 <02 4 <02 <3 <02 3 <02 <3 <02 <3 <0.0 11 11 10% DI Wash Water 40 EDDA.2 <3 <0.2 <3 <0. 10% DI W EDDA.0 <0.4 33 <0.0 2.

1 5.0 <0.2 6 33.0 <0.1 6. 4% D1 WW EDDA. 4% D1 WW EDDA.1 2 Zn 15.2 <3 <0.2 12 12 <1 11 21 0.1 15 . 4% D1 WW EDDA.0 <0.2 11 Ni 8. 4% D1 WW EDDA.0 <0.1 8 <0.2 34 0.0 6.6 5 13. 4% DIWW Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend DE/D DB/D Blank 25/50 25/50 None 62 63 64 65 DMD DE/D DB/D DF/D 40/50 40/50 40/50 40/50 3 <0.4 5 17.9 3 P 11 <01 <1 <01 6 <01 9 <01 <01 8 <01 9 <0.1 11 1 3. 4% D1 WW EDDA.0 59 60 61 EDDA.1 4 <0.2 10.0 <01 <01 2.6 8 1 8.6 9 0. 10% DIWW EDDA.0 Si 2 8.0 Al 4.2 3 3 2 4 10% D1 WW TABLE V EDDA Test Results. Examples 41-54 49 50 51 52 14 53 EDDA.1 <01 <01 59 60 61 EDDA.0 <0. 4% D1 WW EDDA.1 4 6.1 10 1. 4% D1 WW EDDA.1 14 <0.1 19.0 <0.0 <01 2.1 <01 6.2 11.0 <0.0 1.372. 4% D1 WW EDDA.5 5 17. 4% D1 WW EDDA.9 2 7.2 194 142 205 292 224 287 230 297 250 386 211 300 29 <0.0 <0.1 3 <0.1 <0.2 22 0. " " " " DC DD DE Blank 15 15 15 none Crude C C 50 54 " Blank none Top Oil Water Top Oil Water 6 146 Oil Water Top Oil Interface Water Oil <3 <0.1 12.4 8 <0.0 <0.3 5 18. 10% D1 W EDDA.1 14.2 0. 4% D1 WW EDDA.1 <0.0 <0.1 13. 4% D1 WW EDDA.2 10 3 <3 <0.3 33 Cu 3 <0.0 <0.5 <1 <1 <1 <1 <3 <0.2 6 3 3 3 2 4 <3 <0.1 4 <0.1 <1 <0.2 <1 <1 <1 <1 <0. 4% D1 WW EDDA.0 0.2 14.2 4 <0.271 B2 13 TABLE IV-continued EDDA Test Results. 4% D1 WW EDDA.1 2 8 <1 9.1 8.1 7 <0.1 6.0 <0.1 10 1. 4% DIWW EDDA.5 5 6. Examples 55-67 Test Test Dose Metals Analysis EX 55 56 57 58 Condition EDDA.8 5 13.0 4 3 3 3 <3 <0.4 <3 <0.1 5 3.0 0.2 32 0.1 11 1.1 2 <0.5 Test EX 55 56 57 58 Test Sample Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Dose Additive DMD DE/D DB/D DMD Metals Analysis Sb Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Oil Top Oil Water Top Oil Water Top Oil Water Top Oil Water Condition EDDA.1 10.0 <01 4.0 <1 6.7 8 33 5 33.2 36 0.0 <01 7.1 17.1 12 1.2 31 0.2 6. 4% D1 WW EDDA.2 4.0 <01 3.0 <0.1 12 1.0 <01 6.0 <0.0 <0.0 <0.2 1. 4% DIWW EDDA. 4% D1 WW (ppm) 15/50 15/50 15/50 25/50 Ba 5 17.2 26 0. 4% D1 WW EDDA.2 <3 1 <3 <0.0 <0.1 3 6. 4% D1 WW EDDA.2 <3 <3 <0.1 26 0.0 <01 3.2 30 0.1 15.6 10 1.1 28 0. 10% DIWW EDDA.1 15.4 21 <0. 4% D1 WW EDDA.1 3 7.US 8.2 23 0.1 <1 <0.2 <3 <0.0 <01 5. 10% D1 W EDDA.2 <3 <0.2 <3 <0.2 <3 1 <1 <1 2 <1 7 <0.0 <0.2 <1 <1 <1 <1 <3 1 <3 1 8 <0.1 4 <0.1 15.1 3. 10% D1 W EDDA. 4% D1 WW Sample Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Additive DMD DE/D DB/D DMD (ppm) 15/50 15/50 15/50 25/50 Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Oil Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Na 6 338 6 341 11 334 8 339 338 13 345 44 K 29 30 76 30 Mg 3 40 4 34 4 35 2 39 37 1 37 11 Ca 225 383 249 388 244 375 216 382 380 206 386 266 Fe 29 0.6 19 5 19 7 V Pb Mn 11 1.2 <3 <0.1 21.1 <0.0 0.1 5 <0.2 34 0.1 3 <0.4 5 13.1 <0.1 <0.2 <3 <0. 4% D1 WW Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend Crude D/G Blend DE/D DB/D Blank 25/50 25/50 None 33 930 62 63 64 65 66 67 DMD DE/D DB/D DF/D DD/D DC/D 40/50 40/50 40/50 40/50 40/50 40/50 30 155 6 341 8 336 8 352 8 344 7 352 20 25 26 43 67 33 4 18 4 39 4 34.2 7 <0.0 10. 4% D1 WW EDDA.8 14 114 15 180 18 180 18 187 .0 0.

8 0.5 <0.0 2.4 27 7. 7.4 <0.1 <1 <0.1 <0.0% DI Wash W.5% DI WW EDDA.6 13. 7. acetic acid F Blank 1000 (in Water) 1000 (in Water) None Water Top Oil Water Oil Top Oil Water Top Oil Water 0.4 2.8 4.1 0.8 44.6 24.1 8.1 212 5.7 4.8 25 7.1 14.9 700 75 72.2 1.5% DI WW EDDA.1 0. Examples 68-83 Test Test Dose Metals Analysis EX 68 69 70 71 72 73 74 Condition EDDA.7 <0.4 <0.1 31.5 2.4 <0.2 7.6 V <0.4 38.3 1.6 28.4 <0.4 1.7 408 32.1 37.5 2.4 7.3 <0.6 12 1 10 1.1 0.1 15.1 1.9 Zn 13. 7.1 10.1 <0.3 7.4 <0.1 0.1 Test EX 68 69 70 71 72 73 74 Test Sample Crude E " " " " " " Dose Additive Blank DNE DE/E DB/E DF/E DD/E DC/E Metals Analysis Sb Oil Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Condition EDDA.4 <0.7 3280 1.6 <0.7 25. EDDA 5. 7.0% DI Wash W.3 24.1 <0.5% DI WW EDDA.3 4 0.2 29.6 0.4 <0. Examples 55-67 66 67 EDDA.6 +Other Crude 30/70 Re?nery acetic acid F 1000 (in Water) 1000 (in Water) .9 14.3 <0. 7.5 2.6 19.9 20.1 +Other Crude 30/70 Re?nery Blend " " acetic acid F lactic acid glycolic acid S11 Oxalic 1000 (in Water) 1000 (in Water) 1000 (in Water) 1000 (in Water) 1000 DI Wash W.0 0.0 <01 1.9 13.1 <0.4 <0.1 <0.8 1.6 Fe 23.3 4 <0.1 0.5 2.4 0.4 44.5 301 80 1.1 <0. 4% D1 WW 16 Crude D/G Blend DD/D DC/D 40/50 40/50 EDDA.4 <0. 7.6 7.5 5.7 1.5% DIWW EDDA.7 25.7 <0.6 0.8 25 0.US 8.2 0.7 24 0.2 0.9 3350 190 914 100 21.4 75 76 77 Crude G Crude F Blend E 78 79 80 81 82 DI Wash W.2 229 7 230 6 227 <0.4 Mn 10.5 <0.7 4.1 0.3 0. EDDA 5.8 0.4 <0.6 1.8 11.1 3.6 52.1 126 12.7 2970 20.4 20.4 <0.5 29.3 3.4 19.4 <01 <0.2 0.6 Water 132 3950 21.5% DI WW EDDA.4 <0.1 3.0% DI Wash W.1 <0.4 7. 7.1 <0.6 14.8 <0. 7.8 0.4 4. 4% D1 WW Crude D/G Blend Top Oil Water Top Oil Water <1 <0.9 15. EDDA 5.1 15.4 <0.2 25.5 3160 24.3 3.5 0.1 9. EDDA 5.1 14.1 14.1 8.2 7.3 11.3 11.8 <0.4 <0.0% D1 Wash W.2 Cu 0.6 2700 22.2 6.0% DI Wash W.9 44.2 5.1 4.3 2.7 <0.7 1.4 <0.7 2990 17.4 <0. 7.1 2.1 <0.2 <01 0. EDDA 5.4 4 7. EDDA 5.4 1.8 0.2 0.4 <0.9 56.0% acetic acid F Blank 1000 (in Water) 1000 (in Water) None Water Top Oil Water Oil 116 0.2 291 25.1 <0.7 1 29.6 <01 <0.5% DI WW EDDA 5.1 <0.6 3170 12.0% " (in Water) 1000 DI Wash W. EDDA 5.6 4.0% DI Wash W.4 <0. 7.1 <0.3 0. EDDA 5.7 <0.6 317 29.4 <0.1 0.1 <0.4 3.2 294 25.4 <0. EDDA 5.4 <0.0% Sample Crude E " " " " " " Additive Blank DNE DE/E DB/E DF/E DD/E DC/E (ppm) None 30/70 30/70 30/70 30/70 30/70 30/70 Na Oil Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil Water Top Oil K 1590 20.3 8.4 4.9 5.3 1.5% DI WW EDDA.5 Ca 475 482 278 435 281 420 283 485 298 415 301 398 293 22.6 Si 3.4 19.5 0.1 <0.6 24.9 1.4 <0.0 14.1 <0.372.4 <0.5 Water 121 Top Oil 2. 7.2 0.0 <0.2 19.6 Mg 12.7 25.1 84.6 28.1 0.9 2830 7.5 0.2 302 4.5% DI WW EDDA 5.1 3.0 0.5 0.0% DI Wash W.1 4 6.2 11.5% DI WW EDDA.8 0.1 0.0 <0.3 1.4 Water 124 Top Oil 2 Water 958 Top Oil 6.3 11.4 <0.9 48. 7.1 63 6.9 38.3 3 7.38 7.4 0.4 13.2 3020 19.4 0.5% DI WW EDDA.3 1.9 0.3 313 26.5 297 27. 7.8 9. EDDA 5.4 <0.1 <0.8 0.3 9.1 <0.1 <0.4 <0.4 <0.1 <0.5 0.4 <0.1 P 2.5% DI WW EDDA.5 0.6 2.4 11.0 <01 3.4 11.9 7.0 <0.4 <0.1 2.4 0.4 Pb <0.8 113 11 2430 7 2430 320 7.1 <0. 83 EDDA 5.2 <0.7 92.4 <0.9 0.3 11.3 10.4 6.6 Al 0.4 <0.9 26.4 <0.5 844 24.5 13.3 1.271 B2 15 TABLE V-continued EDDA Test Results.2 3170 25.0 <0.7 4 6.4 0.6 215 6 218 6.0% (ppm) None 30/70 30/70 30/70 30/70 30/70 30/70 Ba 11 9.2 0.2 1.3 0.4 <0.5% DI WW EDDA.9 14.2 1.5 11.4 75 76 77 Crude G Crude F Blend E 78 79 DI Wash W.7 27 177 14 183 TABLE VI EDDA Test Results.4 Water 146 Top Oil 3 Water 140 Top Oil 2.1 <0.7 14.4 <0.1 118 2 92.5 2960 17.6 0.2 <0.1 6 13.1 4.1 <0.6 3140 18. EDDA 5.4 <0.4 <01 2.6 1.5% DI WW EDDA.1 <0.1 0.6 11.2 0.1 <0.0% DI Wash W.3 2.4 2.9 0.4 <0.2 <0.4 <0.8 8.5 4. acid (in Water) Top Oil 1.2 <0.4 <0.1 0.2 <04 <0.4 <0.0% DI Wash W.1 43.4 <0.2 13.4 5 13.5% DI WW EDDA.5 0.5 96 1. 7.5 0.6 23.4 <0.3 1.0 0.6 4.1 1.0% DI Wash W.4 0.2 620 25.5 Ni 10.1 0.8 6.

0% DI Wash W. EDDA 5. etc. it is expected that the inventive compositions Will ?nd utility as metal transfer compositions for other ?uids besides crude oil emulsions. a demulsi?er. e. the composition comprising: at least one Water-soluble corrosion inhibitor. malic acid. polymeric forms of the above hydroxyacids. during and/or after adding the composition. metal chelants. Where the Water soluble hydroxyacid comprises from about 1 to about 85 Wt. glycolate ethers. before.1 12.7 <0. thioglycolic acid. lactic acid.0% DI Wash W.6 1. and combinations thereof With other mineral acids.8 1.0% D1 Wash W.271 B2 17 TABLE VI-continued EDDA Test Results.US 8. and ammonium salt and alkali metal salts of these 45 hydrocarbon phase to a Water phase in a re?nery desalting process consisting of: adding to a Wash Water.9 5.4 <0. it Will be evident that various modi?cations and changes can be made thereto Without departing from the broader spirit or scope of the invention as alcohol solvent. Where at least a portion of the metals and/or amines are trans ferred to the aqueous phase.2 0.4 0. a scale inhibitor.3 0.4 0.4 <0. loWering the pH of the Wash Water to 6 or beloW. chloroacetic acid. and/ or amines from crude oil to the aqueous phase in bench scale desalting testing. poly-glycolic esters. potassium.4 3.3 <0.7 2.1 3.6 4.6 1. chloroacetic acid.1 5. Blend " " lactic acid glycolic acid S11 Oxalic 1000 (in Water) 1000 (in Water) 1000 (in Water) " 1000 acid (in Water) Top Oil Water Top Oil Water Top Oil Water Top Oil Water <0. citric acid. 5.3 3. an effective amount of a composi tion to transfer metals and/ or amines from a hydrocar bon phase to a Water phase. For example.4 <0. the composition comprising: 35 at least one Water-soluble corrosion inhibitor.9 <0. an effective amount of a composi tion to transfer metals and/or amines from a hydrocar hydroxyacids.5.8 9. C2-C4 alpha-hydroxy acids. 6. calcium. speci?c Water-soluble hydroxyacids. and mixtures composition.4 0. lactic 40 acid. and at least one Water-soluble hydroxyacid selected from the group consisting of glycolic acid. the invention has been described With reference to speci?c embodiments thereof. gluconic acid.7 <0.1 <0.1 0. adding the Wash Water to crude oil to create an emulsion. and ammonium salt and alkali metal salts of these hydroxyacids.4 <0.9 10.% of the composition and the composition fur ther comprises a Water or alcohol solvent. malic acid. the composition further comprises Water or 20 In the foregoing speci?cation. The method of claim 1 Where in the adding of the composition. but not speci?cally identi?ed or tried in a particular application to transfer metals and/or amines into the aqueous phase. 4. or in different proportions. The method of claim 1 Where in the adding of the sisting of glycolic acid.4 0.1 The FIGURE presents a graph showing the partitioning across desalters of various amines and ammonia as a function 3. 2. as non limiting examples.1 1. other than those speci?cally exempli?ed or mentioned. are Within the scope of this invention. malic acid. the speci?ca tion is to be regarded in an illustrative rather than a restrictive and mixtures thereof. poly-hy droxy carboxylic acids. polymeric forms of the above hydroxyacids. A method of transferring metals and/or amines from a sense. of pH. Wetting agents 25 set forth in the appended claims.7 <01 5 2 0. citric acid. glycolate ethers.372.1 <0. adding the Wash Water to crude oil to create an emulsion.1 2. thioglycolic acid.4 <0. thioglycolic acid. poly-glycolic esters.1 <0. at least one demulsi?er. gluconic acid. the Water-soluble hydroxyacid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm. What is claimed is: 1. However. 8. Examples 68-83 80 81 82 18 83 EDDA 5. C2-C4 alpha-hydroxy acids. The method of claim 1 Where the composition addition ally comprises at least one demulsi?er. falling Within the claimed parameters. gluconic acid.7 3.2 3. poly 65 glycolic esters.8 5 2. citric acid.2 25. chloroacetic acid.1 <0. A composition for transferring metals and/or amines from a hydrocarbon phase to a Water phase consisting of: Water. and mixtures thereof. A method of transferring metals and/or amines from a 30 hydrocarbon phase to a Water phase in a re?nery desalting process consisting of: adding to a Wash Water.4 0.8 1.4 4.6 <0.4 <0.2 <0. before.2 <0. and ammonium salt and alkali metal salts of these resolving the emulsion into hydrocarbon phase and an aqueous phase using electrostatic coalescence. and mixtures thereof. Similarly..g.2 <0. during and/or after adding the composition.4 <0. thereof. EDDA 5.1 27. Accordingly. lactic acid.% Water-soluble hydroxyacid. poly-hydroxy carboxylic acids.1 <0. and has been demonstrated as effective in transferring metals.0% DI Wash W. a Water-soluble hydroxyacid selected from the group con resolving the emulsion into hydrocarbon phase and an aqueous phase using electrostatic coalescence. The method of claim 1 Where the composition addition ally comprises at least one additional component selected from the group consisting of a Water or alcohol solvent. the composition further comprises doWn to about 1 Wt. The addition of Water-soluble hydroxyacids of this invention such as glycolic and gluconic acid to the desalter Wash Water at the use rates speci?ed herein Will reduce the Water’s pH to the range of about 3-6. C2-C4 alpha-hydroxy acids.9 0.4 <0. glycolate ethers.8 1. The method of claim 1 Where in the adding of the composition.9 30. 7. poly-hydroxy carboxylic acids. and 60 ferred to the aqueous phase. Where at least a portion of the metals and/or amines are trans hydroxyacids. and group consisting of glycolic acid.2 <0. bon phase to a Water phase. and at least one Water-soluble hydroxyacid selected from the loWering the pH of the Wash Water to 6 or beloW. polymeric forms of the above hydroxyacids.6 4.9 36.4 <0. . EDDA 5.

% Water soluble hydroxyacid. and mixtures thereof. 14. a composition for transferring metals and/or amines from a hydrocarbon phase to a Water phase comprising a Water soluble hydroxyacid selected from the group consisting of glycolic acid. metal chelants. The treated crude oil emulsion of claim 11 Where the at least one additional component is at least one demulsifer. poly-glycolic esters. C2-C4 alpha hydroxy acids. poly-hydroxy car 15. The composition of claim 8 Where the composition fur ther comprises doWn to about 1 Wt. A treated hydrocarbon crude oil emulsion consisting of: 12. The treated crude oil emulsion of claim 11 Where the Water-soluble hydroxyacid is present in the emulsion in an amount ranging from about 1 to about 2000 ppm. malic acid. The composition of claim 8 Where the Water-soluble hydroxyacid comprises from about 1 to about 85 Wt% of the scale inhibitor. crude oil. gluconic acid. a demulsi?er. chloroacetic acid. and ammonium salt and alkali metal salts of these hydroxyacids. 10. 9. .US 8. at least one Water-soluble corrosion inhibitor. thioglycolic acid. citric acid. lactic acid. Wetting agents and mix tures thereof. poly meric forms of the above hydroxyacids. 13. and at least one demulsi?er. and at least one additional component selected from the group consisting of a Water or alcohol solvent. The treated crude oil emulsion of claim 11 Where the composition further comprises doWn to about 1 Wt.372.271 B2 19 at least one Water-soluble corrosion inhibitor. The treated crude oil emulsion of claim 11 Where the crude oil contains more than 10 ppm iron or calcium. a Where the pH of the composition is 6 or below. glycolate ethers. composition. 11 . boxylic acids. 20 Wash Water Where the pH of the Wash Water is 6 or beloW.% Water-soluble hydroxy acid.