Block copolymers, synthesis and application as dehydrating and desalting of heavy crudes

Abstract

The present invention is related to formulations consisting of block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium and block copolymers ,-di-amine of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w, that are effective in the dewatering and desalting crude whose specific gravities are within the range of 14 to 23API.

Claims

1. Block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium characterized by having following structural general formulas (1) to (5): ##STR00004## where R is ##STR00005## and R represents triblock copolymers with molecular weights in the range from 1000 to 4000 Daltons, of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w type, obtained by the use of ethylene glycol as an initiator, w and y are whole numbers consistent with the molecular weight, R.sub.1, R.sub.2 and R.sub.3 radicals are independently selected from the group consisting of CH.sub.2(CH.sub.2).sub.AB; -CEGJ; CH.sub.2CHLM; CH.sub.2(CH.sub.2).sub.QM; ##STR00006## where A is a number between 1 and 9, B is H, E, G and J are a radical independently selected from the group consisting of: H, methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, n-butyl, phenyl, cyclohexyl, and cyclopentyl, L is a radical represented by methyl or ethyl, and M is a hydroxyl group, Q is a number between 1 and 5, T is represented by groups E, G and J, NO.sub.2, Cl, F and Br, R.sub.4 is a radical independently selected from the group consisting of (CH.sub.2).sub.AB; OU; CH(C.sub.6H.sub.5).sub.2; and C(C.sub.6H.sub.5).sub.3, where A is a number between 1 and 9; B is H, U is a radical independently selected from the group consisting of methyl, ethyl and benzyl, R.sub.5 is a radical independently selected from the group consisting of -(2-methyl-phenyl), -(4-methyl-phenyl), and -(4-phenyl-phenyl); R.sub.6 is a radical independently selected from the group consisting of -(4-methoxy-phenyl), -(4-piperazinyl), and NO.sub.2; R.sub.7 is a radical independently selected from the group consisting of Br, (phenyl-sulfanyl), and (methyl-sulfanyl); R.sub.8 is a radical independently selected from the group consisting of NO.sub.2 and Br; R.sub.9 is Br; R.sub.10 is (octyloxy); R.sub.11 is Br; R.sub.12 is a radical selected from the group consisting of -methyl, -(4-methyl-phenyl), and -(2-methoxy-phenyl); R.sub.13 is a radical selected from the group consisting of NO.sub.2, -(4-methyl-phenyl), -(3-methyl-phenyl), -(2-methoxy-phenyl), and -(3-methoxy-phenyl); R.sub.14 radical represented by -methyl, -(2-phenoxy-ethoxy), -(4-nitro-phenoxy), -(4-phenoxy-butoxy), and Z is a radical independently selected from the group consisting of methanesulfonate, benzenesulfonate and para-toluenesulfonate.

2. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium according to claim 1, wherein R represents triblock copolymers with molecular weights in range from 1000 to 4000 Daltons.

3. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium according to claim 1, where aliphatic amines can be linear or branched, functionalized or unfunctionalized aliphatic group.

4. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium according to claim 1, having the structural formula 2, where aromatic amines are derivatives derived of 1H-alkyl-imidazole, 1H-aryl-imidazole, 1H-alkyl-functionalized-imidazole and 1H-aryl-functionalized-imidazole.

5. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-isoquinolinium according to claim 1, having the structural formula 3, where aromatic amines are derivatives derived of isoquinoline functionalized and unfunctionalized.

6. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-quinolinium according to claim 1, having the structural formula 4, where aromatic amines are derivatives derived of quinoline functionalized and unfunctionalized.

7. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-pyridinium according to claim 1, having the structural formula 5, where aromatic amines are derivatives derived of pyridine functionalized and unfunctionalized.

8. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium having the structural formulas 1-5 according to claim 1, for dewatering and desalting crude oils having specific gravities are between 14 and 23API.

9. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium for dewatering and desalting crude oils having specific gravities between 14 and 23API according to claim 8, where the copolymer is admixed with the crude oil at a concentration of 0.01% to 5% by weight in an organic inert solvent formulation having boiling point of 35 C. to 200 C.

10. The block copolymers ,-di-aryl or alkyl sulfonates of poly(ethylene oxide).sub.w-poly(propylene oxide)-poly(ethylene oxide).sub.w of bis-ammonium for dewatering and desalting crude oils having specific gravities between 14 and 23API according to claim 8, at concentrations of 100 to 600 ppm, or mixtures thereof.

11. A method of dewatering and desalting crude oil, comprising: mixing a dewatering and desalting agent and a crude, wherein said dewatering an desalting agent comprises at least one compound selected from the group consisting of a compound of Formula 2, Formula 3, and Formula 4; ##STR00007## and R represents a copolymer with a molecular weight in the range from 1000 to 4000 Daltons, w and y are independently a whole number consistent with the molecular weight, R.sub.4 is a radical independently selected from the group consisting of (CH.sub.2).sub.AB; OU, CH(C.sub.6H.sub.5).sub.2; and C(C.sub.6H.sub.5).sub.3, where A is a number between 1 and 9; B is H, U is a radical independently selected from the group consisting of methyl, ethyl and benzyl; R.sub.5 is a radical independently selected from the group consisting of -(2-methyl-phenyl), -(4-methyl-phenyl), and -(4-phenyl-phenyl); R.sub.6 is a radical independently selected from the group consisting of -(4-methoxy-phenyl), -(4-piperazinyl), and NO.sub.2; R.sub.7 is a radical independently selected from the group consisting of Br, (phenyl-sulfanyl), and (methyl-sulfanyl); R.sub.8 is a radical independently selected from the group consisting of NO.sub.2 and Br; R.sub.9 is Br; R.sub.10 is (octyloxy); R.sub.11 is Br; R.sub.12 is a radical selected from the group consisting of -methyl, -(4-methyl-phenyl), and -(2-methoxy-phenyl); R.sub.13 is a radical selected from the group consisting of NO.sub.2, -(4-methyl-phenyl), -(3-methyl-phenyl), -(2-methoxy-phenyl), and -(3-methoxy-phenyl); R.sub.14 radical represented by -methyl, -(2-phenoxy-ethoxy), -(4-nitro-phenoxy), -(4-phenoxy-butoxy), and Z is a radical independently selected from the group consisting of methanesulfonate, benzenesulfonate and para-toluenesulfonate.

12. The method of claim 11, wherein said copolymer is a mixture in a solvent having a boiling point of about 35 C. to about 200 C., said method comprising adding said mixture to the crude oil.

13. The method of claim 12, wherein said solvent is selected from the group consisting of dichloromethane, chloroform, benzene, toluene, xylene, turbosine, naphtha and mixtures thereof, and where said mixture is added in an amount of 0.01% to 5% by weight.

14. The method of claim 11, wherein said dewatering and desalting agent comprises a mixture of two of said copolymers in a ratio of about 1:1 to said crude oil.

15. The method of claim 11, wherein said dewatering and desalting agent comprises a mixture including at least one copolymer of Formula 3 or Formula 4.

16. The method of claim 11, wherein said dewatering and desalting agent comprises a mixture including at least one copolymer of Formula 2.

17. The method of claim 11, wherein said dewatering and desalting agent comprises a mixture of a copolymer of Formula 2 and at least one copolymer of Formula 3 or Formula 4.

18. The method of claim 11, wherein said dewatering and desalting agent comprises a mixture of a copolymer of Formula 2 and a compound of Formula 4.

19. The method of claim 11, wherein said dewatering and desalting agent comprises a mixture of a copolymer of Formula 2 and a copolymer of Formula 3.

20. The method of claim 11, wherein said crude oil has a specific gravity of about 14 to 23API, and said dewatering and desalting agent is added at a concentration of at least 100 ppm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The figures of this application are graphic showing the results of the assessment of the dewatering and desalting activity of crude oil by the addition of the block copolymers ,-bifunctionalized with tertiary amines (aliphatic and aromatics), individually and in a formulation containing the copolymers. In these examples, the crude oil has gravities in the range of 14-23API. In addition, the results of a commercial formulation so-called IMP-RHS-5 are included.

(2) FIG. 1 is a graph showing the demulsifying activity of (23H-26H) triblock copolymers ,-bifunctionalized with tertiary amines, on CM1 crude oil at 80 C. and 600 ppm.

(3) FIG. 2 is a graph showing the demulsifying activity of (27H-29H) triblock copolymers ,-bifunfunctionalized with tertiary amines, on CM1 crude oil at 80 C. and 600 ppm.

(4) FIG. 3 is a graph showing the demulsifying activity of (26H to 27H-29H) (300 ppm/300 ppm) formulation of triblock copolymers of ,-bifunctionalized with tertiary amines on CM1 crude oil at 80 C.

(5) FIG. 4 is a graph showing the demulsifying activity of compositions of (24H to 25H-29H) (300 ppm/300 ppm) triblock copolymers of ,-bifunctionalized with tertiary amines on CM1 crude oil at 80 C.

(6) FIG. 5 is a graph showing the demulsifying activity of compositions of (23H to 24H-29H) (300 ppm/300 ppm) triblock copolymers of ,-bifunctionalized with tertiary amines on CM1 crude oil at 80 C.

(7) FIG. 6 is a graph showing the demulsifying activity of compositions of (26H/28H) triblock copolymers of ,-bifunctionalized with tertiary amines on crude oil CM1 at 80 C.

(8) FIG. 7 is a graph showing the demulsifying activity of compositions of (26H27H) triblock copolymers of ,-bifunctionalized with tertiary amines on CM1 crude oil at 80 C.

(9) FIG. 8 is a graph showing the demulsifying activity of compositions of (25H to 26H-29H) (300 ppm/300 ppm) triblock copolymers in -bifunctionalized with tertiary amines and IMP-RHS5 formulation at 600 ppm on CM2 crude oil at 80 C.

(10) FIG. 9 is a graph showing the demulsifying activity of compositions of (26H to 27H-29H) (300 ppm/300 ppm) triblock copolymers in ,-bifunctionalized with tertiary amines and IMP-RHS5 formulation at 600 ppm on CM2 crude oil at 80 C.

(11) FIG. 10 is a graph showing the demulsifying activity of compositions of (26H/27H) triblock copolymers based on ,-bifunctionalized with tertiary amines and the IMP-RHS5 commercial formulation on CM3 crude oil at 80 C.

DETAILED DESCRIPTION OF THE INVENTION

(12) The present invention relates to the synthesis of novel block copolymers with low polydispersity like poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), using ethylene glycol as initiator, and where the copolymers are ,-bifunctionalized with tertiary amines (aliphatic and aromatic). The efficiency of the above copolymers is attributed to having a polydispersity of about 1.02 to 1.20, the bifunctionalization with tertiary amines (aliphatic and aromatic) and molecular weights in the range of 1000 to 4000 Daltons, and preferably 1200 to 2700 Daltons.

(13) The experimental process development for synthesizing the above-described compounds, consisted in the following three steps:

(14) 1. Synthesis of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-polyoxyethylene).sub.w block copolymers. In one embodiment, the alkylene oxide has the formula R discussed below.

(15) 2. Alkyl and aryl sulfonation of the terminal ,-hydroxyl groups of the poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w block copolymers.

(16) 3. Nucleophilic substitution of ,-alkyl and arylsulfonates of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w block copolymers with tertiary amines (aliphatics and aromatics).

(17) One method of producing block copolymers of poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) and derivatives thereof is disclosed in commonly owned U.S. 2010/0140141, which is hereby incorporated by references in its entirety.

(18) The novel ,-bifunctionalized block copolymers with tertiary amines (aliphatics and aromatics), is shown in the equations (1) to (5):

(19) ##STR00001##
where R

(20) ##STR00002##
and where:

(21) R represents triblock copolymers with a molecular weight ranging between 1000 and 4000 Daltons, of poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene).sub.w.

(22) The poly(oxyethylene).sub.w-poly(oxypropylene).sub.y-poly(oxyethylene), as the starting material is preferably obtained using ethylene glycol as an initiator.

(23) w and y are numbers ranging between of 10 to 60, preferably between 15 to 55, even more preferably between 15 and 50.

(24) R.sub.1, R.sub.2 and R.sub.3 are independently radicals selected from the group consisting of

(25) CH.sub.2(CH.sub.2).sub.AB; -CEGJ; CH.sub.2CHLM; CH.sub.2(CH.sub.2).sub.QM;

(26) ##STR00003##
where A is a number between 1 and 19, B is H.
EGJ are independently radicals represented by: H, methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, n-butyl, phenyl, cyclohexyl, cyclopentyl.
L is a radical represented by methyl and ethyl and M is a hydroxyl group, Q is a number between 1 and 5; T is represented by the EGJ groups and NO.sub.2, Cl, F, Br.
R.sub.4 is independently a radical represented by (CH.sub.2).sub.AB; OU; CH(C.sub.6H.sub.5).sub.2; C(C.sub.6H.sub.5).sub.3, where A is a number between 1 and 19, B is H; U is independently a radical represented by methyl, ethyl, and benzyl.

(27) R.sub.5 is independently a radical represented by -2(methyl-phenyl), -(4-methyl-phenyl), -(4-phenyl-phenyl); R.sub.6 is independently a radical represented by -(4-methoxy-phenyl), -(4-piperazinyl), NO.sub.2; R.sub.7 is independently a radical represented by Br, (phenyl-sulfanyl), (methyl-sulfanyl); R.sub.6 is independently a radical represented by NO.sub.2 and bromide: R is independently a radical represented by Br; R.sub.10 is independently a radical represented by (-octyloxy-); R.sub.11 is independently a radical represented by Br; R.sub.12 is independently a radical represented by -methyl, -(4-methyl-phenyl), -(2-methoxy-phenyl); R.sub.13 is a radical represented by NO.sub.2, -(4-methyl-phenyl), -(3-methyl-phenyl), -(2-methyl-phenyl), -(2-methoxy-phenyl), -(3-methoxy-phenyl); R.sub.14 is a radical represented by -methyl, -(2-phenoxy-ethoxy), -(4-nitro-phenoxy), -(4-phenoxy-butoxy).

(28) Z is independently a radical represented by methansulfonate, benzensulfonate and para-toluenesulfonate.

(29) The preferred amines of the present invention for producing the block copolymers are: dibutylhexadecylamine, triisooctylamine, trioctylamine, 2-ethyl-N,N-bis(2-ethylhexyl)-hexylamine, dimethyl-docosyl-amine, N,N-dimethyl-hexadecylamine, trihexylamine, 1-benzyl-1H-imidazole, 1-methyl-1H-imidazole, 1-pentyl-1H-imidazole, 1-butyl-1H-imidazole, 1-vinyl-1H-imidazole, 1-ethyl-1H-imidazole, 1-lauryl-1H-imidazol, 1-cyano-1H-imidazol, 1-hexyl-1H-imidazole, 1-propyl-1H-imidazole, 1-benzyloxy-1H-imidazole, 1-ethoxy-1H-imidazole, 1-methoxy-1H-imidazole, 1-methoxymethyl-1H-imidazole, 1-benzhydryl-1H-imidazole, 1-(diethoxymethyl)-1H-imidazole, 1-(triphenylmethylmethyl)-1-imidazole, 1-(2-methyl-phenyl)-isoquinoline, 1-(4-methyl-phenyl)-isoquinoline, 1-(4-phenyl-phenyl)-isoquinoline, 3-(4-methoxy-phenyl)-isoquinoline, 3-(4-piperazinyl)-isoquinoline, 3-nitro-isoquinoline, 4-bromo-isoguinoline, 4-phenyl-sulfanyl-isoquinoline, 4-methyl-sulfanyl-isoguinoline, 5-nitro-isoquinoline, 5-bromo-isoguinoline, 6-bromo-isoquinoline, 7-octyloxy-isoguinoline, 5,8-dibromo-isoquinoline, quinoline, 8-(2-phenoxy-ethoxy)-quinoline, 2,8-dimethyl-quinoline, 3-nitroquinoline, 3-(3-methyl-phenyl)-quinoline, 3-(2-methyl-phenyl)-quinoline, 3-(4methoxy-phenyl)-quinoline, 3-(3-methoxy-phenylyquinoline, 3-(2-methoxy-phenyl)-quinoline, 2-(benzyloxy)-quinoline, 2-(4-methyl-phenyl)-quinoline, 2-(2-methoxy-phenyl)-quinoline, 8-(4-nitro-phenoxy)-quinoline, 8-(4-phenoxy-butoxy)-quinoline, 2,8-dimethyl-quinoline, 3,4-dimethyl-pyridine, 4-(4-nitro-phenyl)-pyridine, pyridine, 3-(4-bromo-phenyl)-pyridine, 3-(4--nitro-phenyl)-pyridine, and 4-(cyclohexyl-methyl)-pyridine.

(30) Examples of particularly preferred copolymers include:

(31) ,-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-ammonium, where the aliphatic amines can be linear or branched, functionalized or unfunctionalized aliphatic groups,

(32) -di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-ammonium, where the aromatic amines are derivatives of 1H-alkyl-imidazole, 1H-aryl-imidazole, 1H-alkyl-functionalized-imidazole and 1H-aryl-functionalized-imidazole,

(33) ,-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-isoquinolinium, where the aromatic amines are derivatives of isoquinoline that can be functionalized or unfunctionalized,

(34) ,-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-quinolinium, where the aromatic amines are derivatives of quinolone that can be functionalized or unfunctionalized,

(35) ,-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-pyridinium, where the aromatic amines are derivatives of pyridine can be functionalized or unfunctionalized.

Synthesis of Functionalized Block Copolymers

(36) The experimental procedure earlier mentioned was described widely in previous applications U.S. 2010/0140141 and MX/2008/015156; the present invention is distinguished from previous processes because the nucleophilic substitution is carried out with tertiary amines (aliphatic and aromatic) according to the present invention.

(37) The following is a detailed description of one embodiment of the present invention.

(38) Nucleophilic Substitution of the ,-Alkyl and Aryl Sulfonates of the Block Copolymers Poly(Ethylene Oxide)-Poly(Propylene Oxide)-Poly(Ethylene Oxide) with Tertiary Amines)

(39) 10 mmoles of the copolymer ,-dialkyl-sulfonate-ester or ,-diaryl-sulfonate-ester of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide).sub.w. (Mn=2200-2500 g/mole, I=1.12) and 50 mL of toluene were put in a bottom rounded flask with three necks, magnetic stirrer, condenser and addition funnel. Afterwards, 10.2 mmole of the aliphatic or aromatic tertiary amine dissolved in toluene were slowly added to the copolymer, keeping the temperature between 30 and 35 C. and submitted to a reflux heating for 17 hours. After this time, the solvent was eliminated at reduced pressure.

(40) Once the copolymers were obtained, they were submitted to characterization using the following instrumental methods:

(41) 1.Spectrometer of Fourier transform infrared Brucker tensor model 27, employing ATR method with OPUS software.

(42) 2.Spectrometer of nuclear magnetic resonance Varian model BB at 200 MHz to obtain .sup.1H and 50 MHz .sup.13C spectra, employing deuterated chloroform and deuterated dimethylsulfoxide as solvents. The signal shifts are given in parts per million () referred to the tetramethylsilane (TMS) as internal standard.

(43) 3.Size exclusion chromatograph (SEC) of Agilent model 1100, furnished with Plegl column and using tetrahydrofurane (THF) as eluent, used to determine the distribution of the copolymers molecular weights and polydispersity(I).

(44) TABLE-US-00001 TABLE NO. 1 Molecular mass number averages (Mn) and polydispersity index (/) of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide).sub.w, (POE-POP-POE) copolymers prepared using potassium ethylene glycolate as initiator. Copolymer Mn (g/mole) / Physical state A 4000 1.15 Solid B 4000 1.12 Viscous liquid C 2900 1.17 Viscous liquid D 2700 1.11 Viscous liquid E 2400 1.12 Viscous liquid F 1700 1.14 Viscous liquid G 1350 1.15 Viscous liquid Where: A, B, C, D, E, F, and G are poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y- poly(ethylene oxide).sub.w, (POE.sub.w-POP.sub.y-POE.sub.w) copolymers, which exhibit different molecular weight number averages and polydispersity index, so they were labeled with letters A to G.

(45) The spectroscopic characterization of some bifunctionalized copolymers is now depicted. These examples are illustrative but not limiting:

(46) (IMP-CF23H) ,-di-para-toluensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide), of bis-tri-octyl-ammonium: viscous liquid; I.R. cm.sup.1: 2978, 2953, 2870, 2790, 1595, 1459, 1383, 1354, 1174, 1100, 1069, 977, 825, 775, 752; .sup.13C NMR (DMSO-d.sub.6): 13.9, 17.1, 21.6, 21.2, 21.8, 25.7, 25.8, 42.7, 60.5, 60.7, 63.2, 70.2, 70.5, 72.9, 73.5, 75.1, 75.4, 75.7, 127.9, 130.0, 132.7, 145.1.

(47) (IMP-CF24H) ,-di-benzensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide), of bis-tri-hexyl-ammonium: viscous liquid; I.R. cm.sup.1: 2975, 2948, 2865, 2790, 1595, 1459, 1383, 1354, 1172, 1100, 1069, 975, 825, 775, 751; .sup.13C NMR (DMSO-d.sub.6): 14.0, 17.1, 22.5, 25.7, 27.0, 42.6, 60.6, 60.7, 63.2, 70.2, 70.5, 72.9, 73.5, 75.1, 75.4, 75.7, 127.9, 129.41, 134.6, 135.1.

(48) (IMP-CF25H) ,-di-benzensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide).sub.w of bis-1H-methyl-imidazolium: viscous liquid; I.R. cm.sup.1: 3049, 2930, 2858, 1571, 1468, 1385, 1170, 1102, 1018, 895, 767, 655 .sup.13C NMR (DMSO d.sub.6): 17.2, 36.2, 42.8, 60.6, 60.8, 63.1, 70.2, 70.4, 72.8, 75.1, 75.5, 75.7, 121.9, 123.7, 129.4, 134.5, 135.2, 137.6.

(49) (IMP-CF26H) ,-di-benzensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide) of bis-1H-butyl-imidazolium: viscous liquid; I.R. cm.sup.1: 3052, 2945, 2863, 1565, 1465, 1380, 1165, 1102, 1018, 896, 765, 655; .sup.13C NMR (DMSO-d.sub.6): 15.5, 17.2, 22.3, 31.0, 36.2, 45.1, 60.6, 60.8, 63.1, 70.2, 70.4, 72.8, 75.1, 75.5, 75.7, 122.1, 123.6, 127.4, 129.2, 133.5, 136.2, 137.6.

(50) (IMP-CF27H) -di-benzensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide).sub.w of bis-isoquinolinium: viscous liquid; I.R. cm.sup.1: 3023, 2971, 2965, 2856, 1641, 1607; 1583, 1526, 1482, 1470, 1390, 1177, 1173, 1165, 1112, 1105, 983, 946, 819, 759; .sup.13C NMR (DMSO-d.sub.6): 17.1, 46.1, 60.4, 60.7, 64.1, 70.3, 70.4, 72.9, 75.2, 75.3, 75.7, 126.4, 127.1, 127.8, 128.0, 129.4, 131.2, 134.0, 134.5, 135.2, 137.0, 137.3, 150.2.

(51) (IMP-CF28H) -di-benzensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide), of bis-quinolinium: viscous liquid; I.R. cm.sup.1: 3056, 3024, 2950, 2921, 2865, 2728, 1624, 1598, 1590, 1525, 1466, 1407, 1383, 1276, 1209, 1175, 1165, 1153, 1134, 1105, 989, 875, 801, 777, 771; .sup.13C NMR (DMSO-d.sub.6): 17.2, 45.8, 60.4, 60.7, 64.1, 70.3, 70.4, 72.9, 75.2, 75.3, 75.7, 118.9, 122.2, 127.8, 129.3, 129.7, 129.80, 130.7, 135.1, 135.2, 137.3, 147.2, 149.5.

(52) (IMP-CF29H) ,-di-benzensulfonate of poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide).sub.w of bis-pyridinium: viscous liquid; I.R. cm.sup.1: 3068, 3010, 2970, 2960, 2850, 1633, 1620, 1598, 1482, 1436, 1388, 1275, 1217, 1174, 1162, 1108, 980, 872, 750; .sup.13C NMR (DMSO-d.sub.6): 17.1, 45.9, 60.4, 60.9, 64.0, 70.3, 70.4, 72.9, 75.2, 75.2, 75.7, 127.4, 128.0, 129.6, 134.1, 135.2, 142.1, 146.0.

(53) A second feature of the present invention is directed to the preparation of dewatering and desalting agents and formulations based on poly(ethylene oxide).sub.w-poly(propylene oxide).sub.y-poly(ethylene oxide).sub.w block copolymers --bifunctionalized with tertiary amines (aliphatics and aromatics), using solvents with boiling point between 35 to 200 C., preferably dichloromethane, chloroform, benzene, toluene, xylenes, turbosine, naphtha, individually or mixtures thereof. Prepared solutions include amounts ranging from 100 ppm (0.01 wt. %) to 50000 ppm (5 wt %) of the copolymers.

(54) A third feature of the present invention is relates to the application of the prepared solutions in methods for dehydrating end desalting agents of crude oils with gravities ranging between 14-23API, by adding small volumes of dissolution or formulation and avoiding the solvent effect influenced on the emulsion breaking.

(55) Individual and Prepared Composition Evaluation from the Block Copolymer ,-Bifunctionalized with Tertiary Amines Aliphatic and Aromatics, as Dehydrating End Desalting Agents on Crude Oils with API Gravities Ranging Between 14-23API.

(56) Different concentrated dissolutions and formulations were prepared for each of the bifunctionalized copolymers from 5 to 40% by weight, employing disolvents with boiling point is ranging from 35 to 200 C., preferably dichloromethane, chloroform, benzene, toluene, xylenes, turbosine, naphtha, individually or in mixtures thereof, and adding small volumes of the dissolution to avoid the solvent effect influenced on the emulsion breaking. Block copolymers bifunctionalized were prepared in concentrations of 100 to 50000 ppm.

(57) Three crude oils identified as CM1, CM2 and CM3 used in this evaluation were characterized as is shown following:

(58) TABLE-US-00002 TABLE NO. 2 Physicochemistry characterization of crude oils Test CM1 CM2 CM3 API gravity 14.9 19.3 22.2 Sal content (lbs/1000 ls) 10870 248 7050 Paraffin (wt. %) 4.4 3.6 3.7 Distilled water (vol. %) 26.0 20 13.0 Water/sediment (vol. %) 24.7 19 12.6 Runoff Temperature ( C.) 18 30 24 Kinematic viscosity (mm.sup.2/s) 2302 343 1161.4 Heptane Insoluble (wt. %) 10.2 10.8 7.7 Saturated (wt. %) 11.8 20.7 13.9 Aromatics (wt. %) 31.7 26.8 39.7 Resins (wt. %) 45.7 43.4 39.1 Asphaltenes (wt. %) 10.8 9.1 7.3 MW Cryoscopy (g/mole) 511 370 374 CII 0.296 0.424 0.274

(59) Evaluation procedure was described in detail in U.S. 2010/0140141 and U.S. 2012/026312, which are hereby incorporated by reference in their entirety. Then and by way of demonstration that involves no limitation, it shows the graphic results, in the concentration intervals applied ranging from 100 ppm to 1200 ppm.

(60) From FIGS. 1 and 2 (application concentration 600 ppm on CM1 crude oil), it observes that IMP-CF26H, IMP-CF27H, and IMP-CF28H bifunctionalized copolymers are able to break up the emulsion with high yields giving 84% (390 minutes), 81% (210 minutes), and 77% (390 minutes), respectively; whereas the formulation IMP-RHS5 (25 minutes) breaks up very quickly then stays stable in efficiency 58%.

(61) Continuing with CM1 crude oil, shown in FIG. 3 that IMP-CF 26H/IMP-CF 27H (300 ppm/300 ppm) composition reached 100% of yield on the emulsion breaking at 360 minutes of treatment, therefore, there is a synergy between these two copolymers, because individually (600 ppm) only reached 84% and 81% of yield on the emulsion breaking.

(62) In FIG. 4, it is observed that the best composition is IMP-CF 24H/IMP-CF 28H (89%, 300 minutes) and IMP-CF24H/IMP-CF27H with 85% of efficiency at 300 minutes of treatment; whereas in FIG. 5 is observed that IMP-CF23H/IMP-CF28H and IMP-CF23H/IMP-CF26H compositions are able to break up the emulsion with 85% of yield at 300 minutes, all these formulations were applied on CM1 crude oil in concentration of 300 ppm/300 ppm, and to overcome the efficiency of the novel evaluated copolymers individually, again it observes that there exists a synergy with this novel kind of copolymers.

(63) In FIG. 6 (CM1 crude oil), in the left side, it is represented the emulsion breaking efficiency using the IMP-CF26H/IMP-CF28H composition in different concentrations, the best of all is 250 ppm/250 ppm, giving 96% at 5 hours, showing that exists major synergism at low concentration, thus the formulation of 300 ppm/300 ppm breaks up the emulsion at 390 minutes with an efficiency of 78%.

(64) On the right side of the same FIG. 7, the efficiency of the IMP-CF26H/IMP-CF27H composition, at 300 ppm/300 ppm, shows 100% of rupture, whereas the concentrations of 250/250 and 200/200 ppm/ppm reached 96% of the emulsion breaking in the same time. The range of concentrations applied in both compositions ranging from 100 ppm/100 ppm to 300 ppm/300 ppm.

(65) TABLE-US-00003 TABLE NO. 3 Efficiency in the crude desalting CM1 with different compositions. Dehydrated Salt Desalted Composition ppm/ppm % Time.sup.1 Remains.sup.2 % IMP-CF26H/ 300/300 100 360 2600 76.0 IMP-CF 27H IMP-CF26H/ 250/250 96 300 2850 73.8 IMP-CF27H IMP-CF26H/ 200/200 96 300 2475 77.2 IMP-CF27H IMP-CF26H/ 250/250 96 300 1010 90.7 IMP-CF28H .sup.1(minutes), .sup.2(lbs/1000 barrels)

(66) Desalted data shown in Table No. 3 indicate that the highest percentage (901%) was achieved with the IMP-CF26H/IMP-CF28H (250 ppm/250 ppm) composition, other compositions have similar values.

(67) FIG. 8 shows the results of the formulations prepared from the IMP-CF25H/IMP-CF29H and IMP-CF25H/IMP28H copolymers which breaks the 100% of the water-in-oil emulsion, in 150 minutes and 320 minutes, respectively when they are applied over CM2 crude oil, whereas FIG. 9 clearly shows that the best compositions were IMP-CF26H/IMP-CF29H and IMP-CF26H/IMP-CF28H, both formulations achieved 100% of rupture at 150 minutes and 280 minutes respectively.

(68) FIG. 10 (Crude oil CM3) shows that the best composition is composed by IMP-CF26H/IMP-CF27H 300 ppm/300 ppm compared to IMP-CF26H/IMP-CF27H, which reach the emulsion breaking at 120 minutes with an efficiency of 92%.

(69) TABLE-US-00004 TABLE NO. 4 Efficiency of desalting process in the CM3crude oil with different compositions Dehydrated Salt Desalted Composition ppm/ppm % Time.sup.1 Remains.sup.2 % IMP-CF26H/ 300/300 92 120 2475 65.0 IMP-CF27H IMP-CF26H/ 250/250 86 100 2600 63.1 IMP-CF27H .sup.1(minutes), .sup.2(lbs/1000 barrels)

(70) The results of Table No. 4 indicate that the higher dehydration percentage the greater desalting percentage.

(71) Thus, the compositions prepared from the block copolymers bifunctionalized with tertiary amines of this invention together with the block copolymers bifunctionalized with secondary amines are more effective in the dehydrated and desalted of Mexican crude oils than the IMP-RHS-5 commercial formulation.