(19)
(11)EP 3 316 982 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
19.02.2020 Bulletin 2020/08

(21)Application number: 16738219.1

(22)Date of filing:  13.06.2016
(51)Int. Cl.: 
B01D 17/04  (2006.01)
C07C 47/127  (2006.01)
C10G 33/04  (2006.01)
C10G 31/08  (2006.01)
(86)International application number:
PCT/IB2016/053481
(87)International publication number:
WO 2017/001957 (05.01.2017 Gazette  2017/01)

(54)

ADDITIVE COMPOSITION FOR DEMULSIFICATION OF WATER-IN-OIL EMULSION, AND METHOD OF USE THEREOF, AND METHOD OF DEMULSIFICATION

ADDITIVZUSAMMENSETZUNG ZUR EMULSIONSSPALTUNG VON WASSER-IN-ÖL-EMULSION UND VERFAHREN ZUR VERWENDUNG DAVON UND VERFAHREN ZUR EMULSIONSSPALTUNG

COMPOSITION D'ADDITIF POUR LA DÉSÉMULSIFICATION D'UNE ÉMULSION D'EAU DANS L'HUILE, PROCÉDÉ D'UTILISATION DE CETTE COMPOSITION, ET PROCÉDÉ DE DÉSÉMULSIFICATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 01.07.2015 IN 2515MU2015

(43)Date of publication of application:
09.05.2018 Bulletin 2018/19

(73)Proprietor: Dorf Ketal Chemicals (India) Private Limited
Mumbai 400 064, Maharashtra (IN)

(72)Inventor:
  • SUBRAMANIYAM, Mahesh
    Mumbai Maharashtra 400064 (IN)

(74)Representative: Herrero & Asociados, S.L. 
Cedaceros, 1
28014 Madrid
28014 Madrid (ES)


(56)References cited: : 
US-A- 2 499 370
US-A1- 2004 014 824
US-A- 3 259 587
US-A1- 2013 233 770
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Field of the invention:



    [0001] The present invention relates to additive composition for demulsification of water-in-oil emulsion.

    [0002] In particular, the present invention relates to additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil.

    [0003] More particularly, the present invention relates to additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil in the desalter unit of the refinery.

    [0004] Even more particularly, the present invention relates to additive composition for demulsification of water-in-oil emulsion caused by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the additive composition comprises:
    1. a. a compound selected from the group comprising glyoxal, neutralized glyoxal and mixture thereof; and
    2. b. one or more demulsifiers.


    [0005] In one embodiment, the present invention relates to a method of demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.

    [0006] In another embodiment, the present invention relates to a method of using the additive composition of the present invention for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.

    Background of the invention:



    [0007] The water-in-oil emulsions are formed in various industrial operations, and are responsible for substantial loss of various industrial ingredients including difficulties in separation of oil. Therefore, breaking of water-in-oil emulsions during the processing of oil is the requirement of the industry, particularly of the crude oil refinery industry wherein the wash water gets mixed with crude oil in the desalter unit of the refinery and forms water-in-oil emulsion.

    [0008] Presently, the water-in-oil emulsion caused by mixing of wash water and crude oil is broken by addition of demulsifier to the wash water.

    [0009] The main problem of using the demulsifiers is that these are to be used in higher amounts and required continuously through the processing of crude oil, which results in substantial increase in cost of processing of crude oil.

    [0010] Another problem of using the demulsifiers is that these are expensive, which also results in substantial increase in cost of processing of crude oil.

    [0011] More importantly, the presently used demulsifiers are condensation product of nonyl phenols, and presently, there is a need to reduce consumption of nonyl phenols in view of their cost and environmental adverse effects. US 2004/014824, US 3 259 587, US 2 499 370 and US 2013/233770 all disclose compositions for demulsification of water-in-oil emulsions.

    Need of the invention:



    [0012] Therefore, there is a need to reduce, if total elimination is not possible, the requirement of demulsifiers so that above-discussed problems of use of demulsifiers may, at least, be minimized without loss of or sacrificing the industrial output of the crude oil processing units.

    Problem to be solved by the Invention:



    [0013] Therefore, the present invention aims at providing a solution to above-described existing industrial problems by providing:
    1. i) effective additive composition for demulsification of water-in-oil emulsions, and
    2. ii) method of using the additive composition for demulsification of water-in-oil emulsions, and
    3. iii) method for demulsification of water-in-oil emulsions by employing the additive composition.

    Objects of the invention:



    [0014] The composition and the methods of the invention are defined in the appended claims. Accordingly, the main object of the present invention is to provide:
    1. i) an additive composition for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.


    [0015] Accordingly, the other object of the present invention is to provide:
    ii) a method of demulsification of water-in-oil emulsions by employing an additive composition of the present invention, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.

    [0016] Accordingly, another object of the present invention is to provide:
    iii) a method of using the additive composition of the present invention for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions caused by mixing of wash water and crude oil, more particularly of water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery.

    [0017] Accordingly, an object of the present invention is to provide an additive composition for demulsification of water-in-oil emulsions, which is preferably caused by mixing of wash water and crude oil, more preferably for demulsification of the water-in-oil emulsions caused by mixing of wash water and crude oil in the desalter unit of the refinery so as to reduce the amount of the presently used demulsifiers, which are condensation product of nonyl phenols, and hence, to reduce consumption of nonyl phenols, and thereby to reduce cost of processing and associated environmental adverse effects.

    [0018] Other objects and advantages of present invention will become more apparent from the following description when read in conjunction with examples, which are not intended to limit scope of present invention.

    Description and Preferred Embodiments of the Invention:



    [0019] With aim to overcome above-described industrial problems of the prior art and to achieve above-described objects of the present invention, the inventor has found that when a compound selected from the group comprising glyoxal, neutralized glyoxal, and a mixture thereof is added to one or more demulsifiers, the said compound, surprisingly and unexpectedly, results in substantial improvement of demulsification efficiency of the demulsifier, and thereby, results in substantial reduction of requirement of amount of the demulsifier, which results in substantial decrease in cost of processing of crude oil, and associated environmental adverse effects.

    [0020] Further, as the glyoxal and neutralized glyoxal are less expensive than the demulsifiers, it further results in substantial decrease in cost of processing of the crude oil.

    [0021] The present invention relates to a demulsification composition for demulsification of water-in-oil emulsion caused due to wash water in the crude oil, wherein the composition comprises:
    1. a. a compound selected from the group comprising:
      1. (i) glyoxal,
      2. (ii) neutralized glyoxal, and
      3. (iii) a mixture thereof; and
    2. b. at least one demulsifier,
      wherein the demulsifier is selected from the group comprising:
      1. (i) condensation product of:
        1. i) nonyl phenol and amyl phenol, and formaldehyde;
        2. ii) nonyl phenol and butyl phenol, and formaldehyde;
        3. iii) nonyl phenol and formaldehyde;
        4. iv) amyl phenol and formaldehyde;
        5. v) butyl phenol and formaldehyde;
        6. vi) alkyl phenol and formaldehyde; or
        7. vii) a mixture thereof;
      2. (ii) condensation product of:
        1. i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;
        2. ii) cardanol, nonyl phenol and butyl phenol, and formaldehyde;
        3. iii) cardanol, nonyl phenol and formaldehyde;
        4. iv) cardanol, amyl phenol and formaldehyde;
        5. v) cardanol, butyl phenol and formaldehyde;
        6. vi) cardanol, alkyl phenol and formaldehyde; or
        7. vii) a mixture thereof;
      3. (iii) oxyalkylated condensation product thereof;
      4. (iv) oxyalkylated condensation product thereof obtained by oxyalkylation with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof;
      5. (v) oxyalkylated copolymer or oxyalkylated polymer of the condensation product.


    [0022] The present invention relates to a method of demulsification of water-in-oil emulsions, wherein the water-in-oil emulsion is treated with the demulsification composition of the present invention.

    [0023] The present invention relates to a method of using the demulsification composition of the present invention for demulsification of water-in-oil emulsion, wherein the demulsification composition of the present invention is added to the water-in-oil emulsion formed due to mixing of wash water in the crude oil.

    [0024] In accordance with the present invention, the neutralized glyoxal is glyoxal having pH neutral to basic. The inventor has observed that the glyoxal is very acidic, and therefore, it may cause corrosion. Accordingly, neutralizing the glyoxal till its pH is neutral to basic avoids corrosion of crude oil processing unit, and still improves demulsification efficiency of the demulsifier.

    [0025] In accordance with the present invention, the neutralized glyoxal is obtained by neutralizing the glyoxal with an amine or alkaline medium.

    [0026] As per the present invention, the amine may include (or comprises) triethanol amine (TEA).

    [0027] As per the present invention, the alkaline medium may include (or comprises) sodium hydroxide aqueous solution.

    [0028] In accordance with the present invention, the neutralized glyoxal may also include (or comprise) neutralized derivative of glyoxal. Therefore, in the present invention, the term "neutralized glyoxal" or the term "neutralized derivative of glyoxal" have one and same meaning unless otherwise explicitly described.

    [0029] In accordance with the present invention, the pH neutral to basic includes a pH varying from about 7 to about 12.

    [0030] In accordance with one of the embodiments of the present invention, the demulsifier is selected from the group comprising condensation product of:
    1. i) nonyl phenol and amyl phenol, and formaldehyde;
    2. ii) nonyl phenol and butyl phenol, and formaldehyde;
    3. iii) nonyl phenol and formaldehyde;
    4. iv) amyl phenol and formaldehyde;
    5. v) butyl phenol and formaldehyde;
    6. vi) alkyl phenol and formaldehyde; and
    7. vii) a mixture thereof.


    [0031] In accordance with one of the embodiments of the present invention, the demulsifier is selected from the group comprising condensation product of:
    1. i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;
    2. ii) cardanol, nonyl phenol and butyl phenol, and formaldehyde;
    3. iii) cardanol, nonyl phenol and formaldehyde;
    4. iv) cardanol, amyl phenol and formaldehyde;
    5. v) cardanol, butyl phenol and formaldehyde;
    6. vi) cardanol, alkyl phenol and formaldehyde; and
    7. vii) a mixture thereof.


    [0032] In accordance with one of the preferred embodiments of the present invention, the above-described condensation product is oxyalkylated.

    [0033] Therefore, in accordance with one of the embodiments of the present invention, the demulsifier is selected from the group comprising oxyalkylated condensation product of:
    1. i) nonyl phenol and amyl phenol, and formaldehyde;
    2. ii) nonyl phenol and butyl phenol, and formaldehyde;
    3. iii) nonyl phenol and formaldehyde;
    4. iv) amyl phenol and formaldehyde;
    5. v) butyl phenol and formaldehyde;
    6. vi) alkyl phenol and formaldehyde; and
    7. vii) a mixture thereof.


    [0034] Therefore, in accordance with one of the embodiments of the present invention, the demulsifier is selected from the group comprising oxyalkylated condensation product of:
    1. i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;
    2. ii) cardanol, nonyl phenol and butyl phenol, and formaldehyde;
    3. iii) cardanol, nonyl phenol and formaldehyde;
    4. iv) cardanol, amyl phenol and formaldehyde;
    5. v) cardanol, butyl phenol and formaldehyde;
    6. vi) cardanol, alkyl phenol and formaldehyde; and
    7. vii) a mixture thereof.


    [0035] In accordance with one of the preferred embodiments of the present invention, the above-described condensation products is oxyalkylated with ethylene oxide, propylene oxide, butylene oxide or their mixtures to result in oxyalkylated copolymers or oxyalkylated polymers thereof.

    [0036] Therefore, in accordance with one of the embodiments of the present invention, the demulsifier is selected from the group comprising:
    1. i) oxyalkylated nonyl phenol and amyl phenol formladehyde copolymers;
    2. ii) oxyalkylated nonyl phenol and butyl phenol formladehyde copolymers;
    3. iii) oxyalkylated nonyl phenol formaldehyde polymers;
    4. iv) oxyalkylated amyl phenol formaldehyde polymers;
    5. v) oxyalkylated butyl phenol formaldehyde polymers;
    6. vi) oxyalkylated alkyl phenol formaldehyde polymers; and
    7. vii) a mixture thereof.


    [0037] Therefore, in accordance with one of the embodiments of the present invention, the demulsifier may be selected from a group comprising:
    1. i) oxyalkylated cardanol, nonyl phenol and amyl phenol, and formaldehyde copolymers;
    2. ii) oxyalkylated cardanol, nonyl phenol and butyl phenol, and formaldehyde copolymers;
    3. iii) oxyalkylated cardanol, nonyl phenol and formaldehyde polymers;
    4. iv) oxyalkylated cardanol, amyl phenol and formaldehyde polymers;
    5. v) oxyalkylated cardanol, butyl phenol and formaldehyde polymers;
    6. vi) oxyalkylated cardanol, alkyl phenol and formaldehyde polymers; and
    7. vii) a mixture thereof.


    [0038] It may be noted that term "copolymer" means a polymer made from two different phenols and the term "polymer" means a polymer made from one phenol.

    [0039] In accordance with the present invention, the molecular weight of the demulsifier of the present invention may vary from about 2000 to about 20000 daltons as measured by Gel Permeation Chromatography using the tetrahydro furan (THF) as solvent.

    [0040] In accordance with the present invention, the composition comprises:
    1. a) about 0.1 to about 99.1 % by weight of the compound selected from the group comprising glyoxal, neutralized glyoxal, and a mixture thereof; and
    2. b) about 99.1 to about 0.1 % by weight of the one or more demulsifiers.


    [0041] In accordance with one of the preferred embodiments of the present invention, the composition may comprise:
    1. a) about 0.1 ppm to about 1000 ppm of the compound selected from the group comprising glyoxal, neutralized glyoxal, and a mixture thereof; and
    2. b) about 0.5 ppm to about 200 ppm of the one or more demulsifiers, depending upon the nature of the crude oil.


    [0042] It may be noted that as per present invention, the additive composition may be added to the crude oil phase or to the desalter wherein wash water is mixed with crude oil and forms a water-in-oil emulsion.

    [0043] Accordingly, in one embodiment, the present invention relates to
    a method of demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions formed by mixing of wash water and crude oil, more particularly of water-in-oil emulsions formed by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the water-in-oil emulsion formed due to mixing of wash water in the crude oil is treated with
    the present demulsification composition comprising:
    1. a. a compound selected from the group comprising glyoxal, neutralized glyoxal, and a mixture thereof; and
    2. b. at least one demulsifier.


    [0044] Accordingly, in one embodiment, the present invention relates to
    a method of using the present additive composition for demulsification of water-in-oil emulsions, particularly of water-in-oil emulsions formed by mixing of wash water and crude oil, more particularly of water-in-oil emulsions formed by mixing of wash water and crude oil in the desalter unit of the refinery, wherein the present demulsification composition comprising:
    1. a. a compound selected from the group comprising glyoxal, neutralized glyoxal, and a mixture thereof; and
    2. b. at least one demulsifier,
    is added to the water-in-oil emulsion formed due to mixing of wash water in the crude oil.

    [0045] The present invention is now described with the help of following examples, which are not intended to limit scope of the present invention, but have been incorporated for the sake of illustrating the advantages of the present invention over the prior art.

    Examples:



    [0046] The present compositions have been tested for their demulsification efficiency.

    [0047] In the following examples,
    1. 1. the 'blank' is without any additive;
    2. 2. compound 'A' is demulsifier, which is base catalysed nonylphenol formaldehyde resin and used for comparison;
    3. 3. the present compositions comprise
      1. i) compound 'A' and glyoxal; or
      2. ii) compound 'A' and neutralized glyoxal, wherein the glyoxal has been neutralized with triethanol amine (TEA); and
    4. 4. the comparative compositions comprise:
      1. a) compound 'A', and a compound selected from glycolic acid, glyoxylic acid, DL-malic acid, benzaldehyde, or glutaraldehyde.


    [0048] In the following examples, the compound 'A' (the demulsifier) is 50% active, the glyoxal is 40% active, the neutralized glyoxal comprises 40% active glyoxal neutralized with 100% active triethanol amine (TEA); the glycolic acid, the glyoxylic acid and the DL-malic acid are 40% active.

    [0049] In the following examples, the present additive composition and the prior art or comparative additive composition was added to the water-in-oil emulsion of water and crude oil formed after mixing of water and crude oil.

    [0050] The results confirm that the addition of a compound selected from a group comprising glyoxal, neutralized glyoxal, and mixture thereof in one or more of the demulsifiers results in substantial increase of demulsification efficiency of the demulsifier. Accordingly, the present compositions overcome problems of the prior art.

    [0051] In the following examples, the tests were carried out in portable electric desalter (PED) or electrostatic separator at 130°C, with water-in-oil emulsion comprising 5% by vol of wash water (pH of wash water was 6.6), and 95% by vol of crude oil from Western part of India.

    [0052] In the following examples, 100 ml of water-in-oil emulsion of above is taken.

    [0053] The values in the following Table 1 are of % by vol of water separated in PED tubes, i.e. 50% in below table means only 2.5 ml of initial 5 ml of wash water has been separated.
    Table-1
    AdditiveDosage of Additive (ppm)After 5 minAfter 10minAfter 15 minAfter 20 min
    Blank -- 0 0 0 0
    Compound 'A' (no additive) 10 52 60 60 64
    Compound 'A' + glyoxal (as per the present invention) 10 + 0.4 80 90 90 94
    Compound 'A' + glyoxal neutralized with TEA (as per the present invention) 10 + 0.4 80 90 94 94
    Compound 'A' + glycolic acid (comparative composition) 10 + 0.4 56 60 60 64
    Compound 'A' + glyoxylic acid (comparative composition) 10 + 0.4 56 60 60 60
    Compound 'A' + DL-malic acid (comparative composition) 10 + 0.4 60 70 70 74
    Compound 'A' + benzaldehyde (comparative composition) 10 + 0.4 52 60 60 60
    Compound 'A' + glutaraldehyde (comparative composition) 10 + 0.4 52 60 60 60


    [0054] In above Table - 1, the expression "10 + 0.4" means that the composition comprises:
    1. a) 10 ppm of Compound 'A' (the demulsifier); and
    2. b) 0.4 ppm of the second component, which is either the glyoxal or the neutralized glyoxal (as per the present invention); or the glycolic acid, the glyoxylic acid; the DL-malic acid; the benzaldehyde; or the glutaraldehyde (for the purpose of comparison).


    [0055] The above Table-1 confirms that the additives of the present invention, for example, glyoxal and the glyoxal neutralized with TEA till pH of glyoxal becomes neutral to basic. i.e. > or = to pH 7 have surprising and unexpected effects in improving the demulsification efficiency of the demulsifier to demulsify the water-in-oil emulsion formed by mixing of wash water in the crude oil.

    [0056] Therefore, above experimental findings confirm synergistic, surprising and unexpected effects, and technical advantages of the present compositions in demulsifying the water-in-oil emulsion formed by mixing of wash water in the crude oil.

    [0057] Furthermore, above experimental findings also confirm that the present compositions have better demulsification efficiency to demulsify the water-in-oil emulsion formed by mixing of wash water in the crude oil.

    [0058] Furthermore, as amount of demulsifier has been substantially reduced to achieve desired demulsification efficiency, the present compositions are more economical and environmental friendly.

    [0059] It may be noted that the term "about" as employed herein is not intended to enlarge scope of claimed invention, but has been incorporated only to include permissible experimental errors of the field of the present invention.


    Claims

    1. A demulsification composition for demulsification of water-in-oil emulsion caused due to wash water in the crude oil, wherein the composition comprises:

    a. a compound selected from the group comprising:

    (i) glyoxal,

    (ii) neutralized glyoxal, and

    (iii) a mixture thereof; and

    b. at least one demulsifier,
    wherein the demulsifier is selected from the group comprising:

    (i) condensation product of:

    i) nonyl phenol and amyl phenol, and formaldehyde;

    ii) nonyl phenol and butyl phenol, and formaldehyde;

    iii) nonyl phenol and formaldehyde;

    iv) amyl phenol and formaldehyde;

    v) butyl phenol and formaldehyde;

    vi) alkyl phenol and formaldehyde; or

    vii) a mixture thereof;

    (ii) condensation product of:

    i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;

    ii) cardanol, nonyl phenol and butyl phenol, and formaldehyde;

    iii) cardanol, nonyl phenol and formaldehyde;

    iv) cardanol, amyl phenol and formaldehyde;

    v) cardanol, butyl phenol and formaldehyde;

    vi) cardanol, alkyl phenol and formaldehyde; or

    vii) a mixture thereof;

    (iii) oxyalkylated condensation product thereof;

    (iv) oxyalkylated condensation product thereof obtained by oxyalkylation with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof;

    (v) oxyalkylated copolymer or oxyalkylated polymer of the condensation product.


     
    2. The demulsification composition as claimed in claim 1, wherein the neutralized glyoxal is glyoxal having pH neutral to basic.
     
    3. The demulsification composition as claimed in claim 1 or 2, wherein the pH neutral to basic comprises a pH varying from about 7 to about 12.
     
    4. The demulsification composition as claimed in any one of the preceding claims 1 to 3, wherein the neutralized glyoxal is obtained by neutralizing the glyoxal with an amine or alkaline medium.
     
    5. The demulsification composition as claimed in claim 4, wherein the amine comprises triethanol amine (TEA).
     
    6. The demulsification composition as claimed in claim 4, wherein the alkaline medium comprises sodium hydroxide aqueous solution.
     
    7. The demulsification composition as claimed in any one of the preceding claims 1 to 6, wherein the neutralized glyoxal comprises neutralized derivative of glyoxal.
     
    8. The demulsification composition as claimed in claim 1, wherein the oxyalkylated condensation product is selected from the group comprising:

    i) nonyl phenol and amyl phenol, and formaldehyde;

    ii) nonyl phenol and butyl phenol, and formaldehyde;

    iii) nonyl phenol and formaldehyde;

    iv) amyl phenol and formaldehyde;

    v) butyl phenol and formaldehyde;

    vi) alkyl phenol and formaldehyde; and

    vii) a mixture thereof.


     
    9. The demulsification composition as claimed in claim 1, wherein the oxyalkylated condensation product is selected from the group comprising:

    i) cardanol, nonyl phenol and amyl phenol, and formaldehyde;

    ii) cardanol, nonyl phenol and butyl phenol, and formaldehyde;

    iii) cardanol, nonyl phenol and formaldehyde;

    iv) cardanol, amyl phenol and formaldehyde;

    v) cardanol, butyl phenol and formaldehyde;

    vi) cardanol, alkyl phenol and formaldehyde; and

    vii) a mixture thereof.


     
    10. The demulsification composition as claimed in claim 1, wherein the demulsifier is selected from the group comprising:

    i) oxyalkylated nonyl phenol and amyl phenol formaldehyde copolymers;

    ii) oxyalkylated nonyl phenol and butyl phenol formaldehyde copolymers;

    iii) oxyalkylated nonyl phenol formaldehyde polymers;

    iv) oxyalkylated amyl phenol formaldehyde polymers;

    v) oxyalkylated butyl phenol formaldehyde polymers;

    vi) oxyalkylated alkyl phenol formaldehyde polymers; and

    vii) a mixture thereof.


     
    11. The demulsification composition as claimed in claim 1, wherein the demulsifier is selected from the group comprising:

    i) oxyalkylated cardanol, nonyl phenol and amyl phenol, and formaldehyde copolymers;

    ii) oxyalkylated cardanol, nonyl phenol and butyl phenol, and formaldehyde copolymers;

    iii) oxyalkylated cardanol, nonyl phenol and formaldehyde polymers;

    iv) oxyalkylated cardanol, amyl phenol and formaldehyde polymers;

    v) oxyalkylated cardanol, butyl phenol and formaldehyde polymers;

    vi) oxyalkylated cardanol, alkyl phenol and formaldehyde polymers; and

    vii) a mixture thereof.


     
    12. The demulsification composition as claimed in any one of the preceding claims 1 to 11, wherein the composition comprises:

    a) about 0.1 to about 99.1 % by weight of the compound selected from the group comprising glyoxal, neutralized glyoxal, and a mixture thereof; and

    b) about 99.1 to about 0.1 % by weight of the one or more demulsifiers.


     
    13. A method of demulsification of water-in-oil emulsions, wherein the water-in-oil emulsion is treated with the demulsification composition as claimed in any one of the preceding claims 1 to 12.
     
    14. A method of using the demulsification composition as claimed in any one of the preceding claims 1 to 12 for demulsification of water-in-oil emulsion, wherein the demulsification composition is added to the water-in-oil emulsion formed due to mixing of wash water in the crude oil.
     


    Ansprüche

    1. Demulgierungszusammensetzung zum Demulgieren einer Wasser-in-ÖI-Emulsion, die durch Waschwasser in Rohöl erhalten wird, wobei die Zusammensetzung aufweist:

    a. eine Verbindung, die ausgewählt ist aus der Gruppe bestehend aus:

    (i) Glyoxal;

    (ii) neutralisiertem Glyoxal; und

    (iii) einem Gemisch davon; und

    b. mindestens einem Demulgator,
    wobei der Demulgator ausgewählt ist aus der Gruppe bestehend aus:

    (i) einem Kondensationsprodukt von:

    i) Nonylphenol und Amylphenol und Formaldehyd;

    ii) Nonylphenol und Butylphenol und Formaldehyd;

    iii) Nonylphenol und Formaldehyd;

    iv) Amylphenol und Formaldehyd;

    v) Butylphenol und Formaldehyd;

    vi) Alkylphenol und Formaldehyd; oder

    vii) einem Gemisch davon;

    (ii) einem Kondensationsprodukt von:

    i) Cardanol, Nonylphenol und Amylphenol und Formaldehyd;

    ii) Cardanol, Nonylphenol und Butylphenol und Formaldehyd;

    iii) Cardanol, Nonylphenol und Formaldehyd;

    iv) Cardanol, Amylphenol und Formaldehyd;

    v) Cardanol, Butylphenol und Formaldehyd;

    vi) Cardanol, Alkylphenol und Formaldehyd; oder

    vii) einem Gemisch davon;

    (iii) einem oxyalkylierten Kondensationsprodukt davon;

    (iv) einem oxyalkylierten Kondensationsprodukt davon, das erhalten wird durch Oxyalkylierung mit Ethylenoxid, Propylenoxid, Butylenoxid oder Gemischen davon;

    (v) einem oxyalkylierten Copolymer oder einem oxyalkylierten Polymer des Kondensationsprodukts.


     
    2. Demulgierungszusammensetzung nach Anspruch 1, wobei das neutralisierte Glyoxal Glyoxal mit einem pH-Wert von neutral bis basisch ist.
     
    3. Demulgierungszusammensetzung nach Anspruch 1 oder 2, wobei der pH-Wert neutral bis basisch ein pH-Wert im Bereich von etwa 7 bis etwa 12 ist.
     
    4. Demulgierungszusammensetzung nach einem der vorhergehenden Ansprüche 1 bis 3, wobei das neutralisierte Glyoxal durch Neutralisieren des Glyoxals mit einem Amin oder einem alkalischen Mittel erhalten wird.
     
    5. Demulgierungszusammensetzung nach Anspruch 4, wobei das Amin Triethanolamin (TEA) aufweist.
     
    6. Demulgierungszusammensetzung nach Anspruch 4, wobei das alkalische Mittel eine wässrige Natriumhydroxidlösung aufweist.
     
    7. Demulgierungszusammensetzung nach einem der vorhergehenden Ansprüche 1 bis 6, wobei das neutralisierte Glyoxal ein neutralisiertes Derivat von Glyoxal aufweist.
     
    8. Demulgierungszusammensetzung nach Anspruch 1, wobei das oxyalkylierte Kondensationsprodukt ausgewählt ist aus der Gruppe bestehend aus:

    i) Nonylphenol und Amylphenol und Formaldehyd;

    ii) Nonylphenol und Butylphenol und Formaldehyd;

    iii) Nonylphenol und Formaldehyd;

    iv) Amylphenol und Formaldehyd;

    v) Butylphenol und Formaldehyd;

    vi) Alkylphenol und Formaldehyd; und

    vii) einem Gemisch davon.


     
    9. Demulgierungszusammensetzung nach Anspruch 1, wobei das oxyalkylierte Kondensationsprodukt ausgewählt ist aus der Gruppe bestehend aus:

    i) Cardanol, Nonylphenol und Amylphenol und Formaldehyd;

    ii) Cardanol, Nonylphenol und Butylphenol und Formaldehyd;

    iii) Cardanol, Nonylphenol und Formaldehyd;

    iv) Cardanol, Amylphenol und Formaldehyd;

    v) Cardanol, Butylphenol und Formaldehyd;

    vi) Cardanol, Alkylphenol und Formaldehyd; und

    vii) einem Gemisch davon.


     
    10. Demulgierungszusammensetzung nach Anspruch 1, wobei der Demulgator ausgewählt ist aus der Gruppe bestehend aus:

    i) oxyalkylierten Nonylphenol- und Amylphenol-Formaldehyd-Copolymeren;

    ii) oxyalkylierten Nonylphenol- und Butylphenol-Formaldehyd-Copolymeren;

    iii) oxyalkylierten Nonylphenol-Formaldehyd-Polymeren;

    iv) oxyalkylierten Amylphenol-Formaldehyd-Polymeren;

    v) oxyalkylierten Butylphenol-Formaldehyd-Polymeren;

    vi) oxyalkylierten Alkylphenol-Formaldehyd-Polymeren; und

    vii) einem Gemisch davon.


     
    11. Demulgierungszusammensetzung nach einem der Ansprüche 1 bis 10, wobei der Demulgator ausgewählt ist aus der Gruppe bestehend aus:

    i) oxyalkylierten Cardanol-, Nonylphenol-, Amylphenol- und Formaldehyd-Copolymeren;

    ii) oxyalkylierten Cardanol-, Nonylphenol-, Butylphenol- und Formaldehyd-Copolymeren;

    iii) oxyalkylierten Cardanol-, Nonylphenol- und Formaldehyd-Polymeren;

    iv) oxyalkylierten Cardanol-, Amylphenol- und Formaldehyd-Polymeren;

    v) oxyalkylierten Cardanol-, Butylphenol- und Formaldehyd-Polymeren;

    vi) oxyalkylierten Cardanol-, Alkylphenol- und Formaldehyd-Polymeren; und

    vii) einem Gemisch davon.


     
    12. Demulgierungszusammensetzung nach einem der vorhergehenden Ansprüche 1 bis 11, wobei die Zusammensetzung aufweist:

    a) etwa 0,1 bis etwa 99,1 Gew.-% der Verbindung, die ausgewählt ist aus der Gruppe bestehend aus Glyoxal, neutralisiertem Glyoxal und einem Gemisch davon; und

    b) etwa 99,1 bis etwa 0,1 Gew.-% des einen oder der mehreren Demulgatoren.


     
    13. Verfahren zum Demulgieren von Wasser-in-ÖI-Emulsionen, wobei die Wasser-in-ÖI-Emulsion mit der Demulgierungszusammensetzung nach einem der vorhergehenden Ansprüche 1 bis 12 behandelt wird.
     
    14. Verfahren zum Verwenden der Demulgierungszusammensetzung nach einem der vorhergehenden Ansprüche 1 bis 12 zum Demulgieren einer Wasser-in-ÖI-Emulsion, wobei die Demulgierungszusammensetzung der Wasser-in-ÖI-Emulsion zugegeben wird, die durch Mischen von Waschwasser mit Rohöl erhalten wird.
     


    Revendications

    1. Composition de désémulsification pour la désémulsification d'une émulsion eau dans due à de l'eau de lavage dans de l'huile brute, dans laquelle la composition comprend :

    a. un composé sélectionné parmi le groupe comprenant :

    (i) de l'éthanedial,

    (ii) de l'éthanedial neutralisé, et

    (iii) un mélange de ceux-ci ; et

    b. au moins un agent désémulsionneur,
    dans laquelle l'agent désémulsionneur est sélectionné parmi le groupe comprenant :

    (i) un produit de condensation de :

    i) nonylphénol et amylphénol, et formaldéhyde ;

    ii) nonylphénol et butylphénol, et formaldéhyde ;

    iii) nonylphénol et formaldéhyde ;

    iv) amylphénol et formaldéhyde ;

    v) butylphénol et formaldéhyde ;

    vi) alkylphénol et formaldéhyde ; ou

    vii) un mélange de ceux-ci ;

    (ii) un produit de condensation de :

    i) cardanol, nonylphénol et amylphénol, et formaldéhyde ;

    ii) cardanol, nonylphénol et butylphénol, et formaldéhyde ;

    iii) cardanol, nonylphénol et formaldéhyde ;

    iv) cardanol, amylphénol et formaldéhyde ;

    v) cardanol, butylphénol et formaldéhyde ;

    vi) cardanol, alkylphénol et formaldéhyde ; ou

    vii) un mélange de ceux-ci ;

    (iii) un produit de condensation oxyalkylé de ceux-ci ;

    (iv) un produit de condensation oxyalkylé de ceux-ci obtenu par oxyalkylation avec de l'oxyde d'éthylène, de l'oxyde de propylène, de l'oxyde de butylène ou des mélanges de ceux-ci ;

    (v) un copolymère oxyalkylé ou un polymère oxyalkylé du produit de condensation.


     
    2. Composition de désémulsification selon la revendication 1, dans laquelle l'éthanedial neutralisé est de l'éthanedial ayant un pH neutre à basique.
     
    3. Composition de désémulsification selon la revendication 1 ou 2, dans laquelle le pH neutre à basique comprend un pH variant d'environ 7 à environ 12.
     
    4. Composition de désémulsification selon l'une quelconque des revendications 1 à 3 précédentes, dans laquelle l'éthanedial neutralisé est obtenu par neutralisation de l'éthanedial avec une amine ou un milieu alcalin.
     
    5. Composition de désémulsification selon la revendication 4, dans laquelle l'amine comprend de la triéthanolamine (TEA).
     
    6. Composition de désémulsification selon la revendication 4, dans laquelle le milieu alcalin comprend une solution aqueuse d'hydroxyde de sodium.
     
    7. Composition de désémulsification selon l'une quelconque des revendications 1 à 6 précédentes, dans laquelle l'éthanedial neutralisé comprend un dérivé neutralisé de l'éthanedial.
     
    8. Composition de désémulsification selon la revendication 1, dans laquelle le produit de condensation oxyalkylé est sélectionné parmi le groupe comprenant :

    i) du nonylphénol et de l'amylphénol, et du formaldéhyde ;

    ii) du nonylphénol et du butylphénol, et du formaldéhyde ;

    iii) du nonylphénol et du formaldéhyde ;

    iv) de l'amylphénol et du formaldéhyde ;

    v) du butylphénol et du formaldéhyde ;

    vi) de l'alkylphénol et du formaldéhyde ; et

    vii) un mélange de ceux-ci.


     
    9. Composition de désémulsification selon la revendication 1, dans laquelle le produit de condensation oxyalkylé est sélectionné parmi le groupe comprenant :

    i) du cardanol, du nonylphénol et de l'amylphénol, et du formaldéhyde ;

    ii) du cardanol, du nonylphénol et du butylphénol, et du formaldéhyde ;

    iii) du cardanol, du nonylphénol et du formaldéhyde ;

    iv) du cardanol, de l'amylphénol et du formaldéhyde ;

    v) du cardanol, du butylphénol et du formaldéhyde ;

    vi) du cardanol, de l'alkylphénol et du formaldéhyde ; et

    vii) un mélange de ceux-ci.


     
    10. Composition de désémulsification selon la revendication 1, dans laquelle l'agent désémulsionneur est sélectionné parmi le groupe comprenant :

    i) des copolymères de nonylphénol et d'amylphénol-formaldéhyde oxyalkylés ;

    ii) des copolymère de nonylphénol et de butylphénol-formaldéhyde oxyalkylés ;

    iii) des polymères de nonylphénol-formaldéhyde oxyalkylés ;

    iv) des polymères d'amylphénol-formaldéhyde oxyalkylés ;

    v) des polymères de butylphénol-formaldéhyde oxyalkylés ;

    vi) des polymères d'alkylphénol-formaldéhyde oxyalkylés ; et

    vii) un mélange de ceux-ci.


     
    11. Composition de désémulsification selon la revendication 1, dans laquelle l'agent désémulsionneur est sélectionné parmi le groupe comprenant :

    i) des copolymères de cardanol, de nonylphénol et d'amylphénol, et de formaldéhyde oxyalkylés ;

    ii) des copolymère de cardanol, de nonylphénol et de butylphénol, et de formaldéhyde oxyalkylés ;

    iii) des polymères de cardanol, de nonylphénol et de formaldéhyde oxyalkylés ;

    iv) des polymères de cardanol, d'amylphénol et de formaldéhyde oxyalkylés ;

    v) des polymères de cardanol, de butylphénol et de formaldéhyde oxyalkylés ;

    vi) des polymères de cardanol, d'alkylphénol et de formaldéhyde oxyalkylés ; et

    vii) un mélange de ceux-ci.


     
    12. Composition de désémulsification selon l'une quelconque des revendications 1 à 11 précédentes, dans laquelle la composition comprend :

    a) d'environ 0,1 à environ 99,1 % en poids du composé sélectionné parmi le groupe comprenant de l'éthanedial, de l'éthanedial neutralisé, et un mélange de ceux-ci ; et

    b) d'environ 99,1 à environ 0,1 % en poids des un ou plusieurs agents désémulsionneurs.


     
    13. Procédé de désémulsification d'émulsions eau dans huile, dans lequel l'émulsion eau dans huile est traitée avec la composition de désémulsification selon l'une quelconque des revendications 1 à 12 précédentes.
     
    14. Procédé d'utilisation de la composition de désémulsification selon l'une quelconque des revendications 1 à 12 pour la désémulsification d'une émulsion eau dans huile, dans lequel la composition de désémulsification est ajoutée à l'émulsion eau dans huile formée par mélange d'eau de lavage dans de l'huile brute.
     




    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description